US3772020A - Persulfate bleach-fix solution - Google Patents

Persulfate bleach-fix solution Download PDF

Info

Publication number
US3772020A
US3772020A US00200614A US3772020DA US3772020A US 3772020 A US3772020 A US 3772020A US 00200614 A US00200614 A US 00200614A US 3772020D A US3772020D A US 3772020DA US 3772020 A US3772020 A US 3772020A
Authority
US
United States
Prior art keywords
agent
fixing
persulfate
concentration
per liter
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
US00200614A
Inventor
E Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Application granted granted Critical
Publication of US3772020A publication Critical patent/US3772020A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • Typical bleaching compositions for color photographic elements include ferricyanides, ferric chloride and iron ammonium ethylenediamine tetraacetic acid complexes.
  • a fixing agent for example, thiosulphate or thiocyanate
  • numerous problems occur.
  • ferricyanide bleaching agents their combination with a thiosulphate fixing agent results in decomposition of the fixing agent when sufficient bleach is used to achieve satisfactory bleachmg.
  • R, and R are selected from the group consistingof H, CH C ll and C ll, and n is an integer from 1 to 4.
  • Specifically preferred among this class of accelerators are those compounds wherein R, and R are selected from the group consisting of CH and C H, and n is either 2 or 3.
  • potassium persulfate (X 8 0 is used as the bleaching agent, and the above-described preferred accelerators also serve as the fixing agent.
  • the present invention also provides an improved method of color processing color photographic light sensitive elements comprising, at least, the steps of color development, stop-fixing and bleach-fixing comprising processing the light sensitive element in a bath containing a water-soluble persulfate, preferably potassium persulfate, and a compound represented by the general formula:
  • R, and R are selected from the group consisting of H, CH C H and C l-I and n is an integer from I to 4.
  • the bleaching solutions of the present invention generally comprise aqueous solutions of a water-soluble persulfate salt as the bleaching agent, i.e., an alkali metal or ammonium persulfate, and at least one bleach accelerator which also serves as fixing agent selected from the group of compounds having the generic formula:
  • R and R are selected from the group consisting of H, CH C I-I and C ll, and n is an integer from 1 to 4.
  • Specifically preferred among these accelerators are those wherein R, and R are selected from the group consisting of CH and C H and n is either 2 or 3. Potassium persulfate has proven particularly effective as the bleaching agent.
  • the concentration of the persulfate oxidizing agent in the bleach-fix solutions of this invention ranges from about 0.05 to about 0.5 moles per liter of solution and preferably between about 0.1 and 0.4 moles per liter.
  • the concentration of the alkyl thiol fixing agent ranges from about 0.1 to about 2.0 moles per liter of solution and preferably from about 0.13 to about 1.5 moles per liter of solution.
  • Part A relates to the evaluation of thiol derivatives other than alkylaminoalkylthiols in a bleach-fix composition wherein the bleaching agent is potassium persulfate.
  • Part B relates to the evaluation of oxidizing agents other than persulfate in a bleach-fix composition wherein the fixing agent is diethy-laminoethane thiol.
  • Part C relates to the evaluation of homologs of diethylaminoethane thiol in a bleach-fix composition wherein the bleaching agent is potassium persulfate.
  • Part A Five samples of Eastman Color Print Film (Type 5385) were sensitornetrically exposed to a graduateddensity test object (step tablet), color developed, acidstopped, washed and dried in conventional fashion.
  • Part B A sample of a conventional supported light-sensitive gelatinous silver halide coating was flash-exposed and developed.
  • the infra-red (IR) density of the developed The infra-red (IR) density of the developed, silver in 5 silver was measured to be 2.96.
  • the quantity of silvereach step is recorded in column 1 of Table I.
  • the quanplus-silver halide was found to be 182 mg per square tity of silver-plus-silver halide (in mg/ft of coating) foot of coating. These two values are recorded in the present in each step, as determined by quantitivative first line of Table II.
  • Solution Z 1120 to 1 liter 2O K,Fe(CN), (potassium ferricyanide) 80 g (0.25 mole) g i 50 g (25 mole) 2,2-Diethylaminoethane thiol 50 g 0.33 mole)
  • aqueous bleach-fix solutions comprising a watersoluble persulfate and alkylaminoalkylthiols exhibit unique properties which are not duplicated in similar solutions containing either different oxidizing agents or fixing agents.
  • EXAMPLE 1 A sample of Kodak Ektachrome MS Reversal Color Film, Type 2027, was sensitometrically exposed to a multicolor test object, MQ-developed, washed, reversal color developed, washed and bleach-fixed in a l-liter aqueous solution containing 40 g potassium persulfate and 50 g diethylaminoethanethiol. The sample was completely bleach-fixed in 1.5 minutes at a temperature of 71F.
  • EXAMPLE 2 The procedure described in Example 1 was successfully repeated with two similar bleach-fix solutions, wherein the potassium persulfate was replaced with equal molar quantities of sodium persulfate and ammonium persulfate, respectively.
  • bleach-fix compositions can, of course, be utilized to treat any conventional silver or silver halide emulsion wherein it is sought to remove unwanted silver and/or silver halide and in conjunction with all of the conventional development, washing, stabilizing, etc., steps described in the discussion of the prior art set forth above.
  • the use of these compositions in such processes is considered an integral part of this invention.
  • Concentrates of the bleach-fixing solutions described above may of course be prepared to reduce shipping costs incident to the shipping of the solvent (water) or even in dry powder form to increase the storage life only increasing the stability of such concentrates over long periods of time.
  • the ultimate user When prepared as dry powder mixture or as concentrates the ultimate user simply dissolves the powder or concentrate in a suitable amount of water to provide the above-prescribed concentrations in the working bleach-fix solution.
  • Such dry powder mixtures and/or concentrates which are brought to working solution concentration levels at the time of use are therefore to be included within the scope of this disclosure as well as the appended claims.
  • alkylaminoalkylthiols of the solution of the present invention may be supplied in the form of acid salts of these materials, for example 2,2- diethylaminoethane thiol l-lCl, to permit greater ease of dissolution of these materials and increase their availability.
  • acid salts for example 2,2- diethylaminoethane thiol l-lCl
  • dissociation products thereof ie., HCl
  • a bleach-fix composition for use in processing of photographic elements comprising a water-soluble persulfate bleaching agent and a fixing agent of the formula:
  • R and R are selected from the group consisting of H, CH C l-l and C l-l and n is an integer of from 1 to 4.
  • concentration of said bleaching agent is from about 0.05 to about 05 moles per liter and the concentration of said fixing agent is from about 0.1 to about 2.0 moles per liter.
  • N-(CHa) n S H wherein R and R are selected from the group consisting of H, CH C l-l and C l-L, and n is an integer of from 1 to 4.
  • bleaching agent is selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.
  • R and R are CH or C,H and n is 2 or 3.
  • bleaching agent is potassium persulfate and said fixing agent is 2,2-diethylaminoethanethiol.

Landscapes

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

Abstract

Bleach-fix solutions utilizing a water-soluble persulfate as the silver oxidizing agent and an alkyl amino alkyl thiol as the fixing agent are described.

Description

United States Patent [191 Smith Nov. 13, 1973 PERSULFATE BLEACH-FIX SOLUTION FOREIGN PATENTS OR APPLICATIONS [75] Inventor: Edward A. Smith, Rochester, NY. 1,131,103 10/1968 Great Britain [73] Assignee: Eastman Kodak Company,
Rochester NY Primary Examiner--John D. Welsh Filed; 1971 AztorneyWilliam T. French et a1. [21] Appl. No.: 200,614
[52] U.S.- Cl 96/60 BF, 96/61, 252/186 [57] ABSTRACT [51] Int. Cl G03c 5/32 [58] Field Of Search 2 2/186; 96/60 F, Bleach-fix solutions utilizing a water-soluble persulfate 61 as the silver oxidizing agent and an alkyl amino alkyl thiol as the fixing agent are described. [56] References Cited UNITED STATES PATENTS 18 Claims, N0 Drawings 3,434,796 3/1969 Columbo 8/l37 PERSULFATE BLEACH-FIX SOLUTION This invention relates to bleach-fixing compositions for processing color photographic materials and to a method for the utilization of same.
BACKGROUND OF THE INVENTION As a general rule the processing of color photographic light sensitive elements is carried out by a process including at least color development, bleaching (silver removal) and fixing followed by washing, post hardening, stabilizing, etc. Various processing compositions dependent upon the types of color photographic light sensitive elements are required in these various processing steps which may, depending upon the nature of the element being processed, be preceded by other steps including prehardenin g, black and white developing, image reversal, etc.
Typical bleaching compositions for color photographic elements include ferricyanides, ferric chloride and iron ammonium ethylenediamine tetraacetic acid complexes. When an attempt is made to incorporate such bleaching compositions with a fixing agent, for example, thiosulphate or thiocyanate to provide a combined bleach-fixing bath, numerous problems occur. For example, in the case of ferricyanide bleaching agents their combination with a thiosulphate fixing agent results in decomposition of the fixing agent when sufficient bleach is used to achieve satisfactory bleachmg.
In the case of iron-EDTA complexes such materials are compatible with the fixing agents, however, the bleaching power of such combined solutions is generally insufficient so that accelerators, which in turn may cause fogging, staining, etc., have to be used.
The successful consolidation of the bleaching and fixing operations utilized in the processing of exposed color photographic elements into a single, simple step has therefor been the goal of skilled artisans in the photographic processing arts for a number of years. Although numerous attempts to achieve this goal have met with varying degrees of success nearly all such systems have met with problems not the least of which are the time involved in such a bleach-fixing operation, the expense involved for chemicals including bleach accelerators, etc., to make such solutions operate effectively, and detrimental affects on image dyes of color photographic materials.
It is therefore an object of the present invention to provide a bleachfix bath which is rapid, utilizes relatively inexpensive chemicals and does not adversely affect the image dyes of color photographic materials.
These and other objects which will be made clear from a reading of the following specifications are achieved through the use of bleach-fix baths containing a water soluble persulfate as the bleaching agent and bleach accelerators having the following generic formula:
wherein R, and R, are selected from the group consistingof H, CH C ll and C ll, and n is an integer from 1 to 4. Specifically preferred among this class of accelerators are those compounds wherein R, and R are selected from the group consisting of CH and C H, and n is either 2 or 3. Especially advantageous results have been achieved when potassium persulfate (X 8 0 is used as the bleaching agent, and the above-described preferred accelerators also serve as the fixing agent.
The present invention also provides an improved method of color processing color photographic light sensitive elements comprising, at least, the steps of color development, stop-fixing and bleach-fixing comprising processing the light sensitive element in a bath containing a water-soluble persulfate, preferably potassium persulfate, and a compound represented by the general formula:
wherein R, and R are selected from the group consisting of H, CH C H and C l-I and n is an integer from I to 4.
DETAILED DESCRIPTION OF THE INVENTION The bleaching solutions of the present invention generally comprise aqueous solutions of a water-soluble persulfate salt as the bleaching agent, i.e., an alkali metal or ammonium persulfate, and at least one bleach accelerator which also serves as fixing agent selected from the group of compounds having the generic formula:
wherein R and R are selected from the group consisting of H, CH C I-I and C ll, and n is an integer from 1 to 4. Specifically preferred among these accelerators are those wherein R, and R are selected from the group consisting of CH and C H and n is either 2 or 3. Potassium persulfate has proven particularly effective as the bleaching agent.
The concentration of the persulfate oxidizing agent in the bleach-fix solutions of this invention ranges from about 0.05 to about 0.5 moles per liter of solution and preferably between about 0.1 and 0.4 moles per liter. The concentration of the alkyl thiol fixing agent ranges from about 0.1 to about 2.0 moles per liter of solution and preferably from about 0.13 to about 1.5 moles per liter of solution.
The following discussion is divided into three parts each of which has a specific goal as described immediately hereinafter:
Part A relates to the evaluation of thiol derivatives other than alkylaminoalkylthiols in a bleach-fix composition wherein the bleaching agent is potassium persulfate.
Part B relates to the evaluation of oxidizing agents other than persulfate in a bleach-fix composition wherein the fixing agent is diethy-laminoethane thiol.
Part C relates to the evaluation of homologs of diethylaminoethane thiol in a bleach-fix composition wherein the bleaching agent is potassium persulfate. Part A Five samples of Eastman Color Print Film (Type 5385) were sensitornetrically exposed to a graduateddensity test object (step tablet), color developed, acidstopped, washed and dried in conventional fashion.
Part B A sample of a conventional supported light-sensitive gelatinous silver halide coating was flash-exposed and developed. The infra-red (IR) density of the developed The infra-red (IR) density of the developed, silver in 5 silver was measured to be 2.96. The quantity of silvereach step is recorded in column 1 of Table I. The quanplus-silver halide was found to be 182 mg per square tity of silver-plus-silver halide (in mg/ft of coating) foot of coating. These two values are recorded in the present in each step, as determined by quantitivative first line of Table II.
analytical silver analysis, is recorded in column 1a of Three other samples were exposed and developed Table I. similarly, and then treated for 90 seconds in Solutions Five additional samples of the same film were simi- X, Y and Z respectively. larly exposed, color developed, acid-stopped, washed and then bleach-fixed for 90 seconds respectively in $010051? :0 2 I 2 50g(0.5rnoe) Solutions A, B, C, D and E, whose compositions are Lzmemlaminoethanethiol given below. The samples were finally washed and ,c, c ,c ,sH 8 HCl] 50 g (0.33 mole) dried l-I,O to 1 liter Solution Y solution A, K,Cr,0 (Potassium dichromate) 75 g (0.25 mole) 50 (25 mole) 2,2-Diethylaminoethane thiol 50 g (0.33 mole) 2,2-diethylaminoethanethiol- 8 to 1 llter HCl(H5C2)2NCH2CH2SH-HC1 (Cpd. A). 50 g. (.338 mole). Solution Z 1120 to 1 liter 2O K,Fe(CN), (potassium ferricyanide) 80 g (0.25 mole) g i 50 g (25 mole) 2,2-Diethylaminoethane thiol 50 g 0.33 mole) B Mercaptoacetic acid, sodium salt "*0 to 1 met NaOOCCH2SH (Cpd. B). 38.5 g. (.33 mole). H to 1 liter solutiosn O: 0 1 The three samples were then washed, dried and evalfi,,f1i.;,;,;,y ;,;;,yg 5 m0 25 uated by determining the IR Density of the remaining (Cpdsilver and the quantity of silver-plus-silver halide. The H2O to 1 liter Solution D: results are listed in Table II.
g s p u n 50 g. (.25 mole).
ys 5 EglgSSIECHNHQCO0H-HC1-HO 59' 3 (33 mole) TABLE II H2O to 1 liter Solution E:. Ag Ag/AgX X23208- 50 g. 5 mo e). (IR Dens.) Analysis 0 Untreated Check 2.96 132 N N Sample treated in Solution X 0.20 58 Sample treated in Solution Y 0.07 107 It LSH pm E) 10 (1 mole) Sample treated in Solution Z 0.07 172 f H From the above data it is clear that solution X efiec- 1120 to Inter tively bleached and fixed the developed sample. Solutions Y and Z effectively bleached the silver, but did The IR-densities and analytically determined Ag not adequately fix the silver halide. AgX coverages in each of the image steps of the so pro- 40 The persulfate therefore appears to be unique as an cessed samples are recorded in columns 2/2a, 3/3a, oxidizing agent in a bleach-fix composition together 4/4a, 5 /5a and 6/6a in Table I. with an alkylamino alkane thiol fixing agent such as TABLE I Control Cpd. A Cpd. B Cptl. C Cpd. D Cpd. E
Ag/AgX Col. 2, Ag/AgX Col. 3, Ag/AgX Col. 4, Ag/AgX Col. 5, Ag/AgX C51. 6, Ag/AgX C01. 1, IR dens. analys IR dens. analys. IR dens. analys. IR dens. nnalys. IR dens. analys. IR dens. analys.
The data in Table I indicate that Solution A effec- V 2,2-diethylaminoetliaiie thiolf PartC The procedures described in Part B were repeated with bleach-fix solutions whose compositions are given below. The results are listed in Table III.
Solution R 3 l-Aminoethanethiol HCl [I-I,NCH,CH,SH HCl] H 0 to 1 liter Solution S 50 g/l (0.25 mole) 37 g/l (0.25 mole) 50 g/l (0.25 mole) Dimethylaminopropanethiol HCl [(CH ),NCH,Cl-l CH SH l-lCl] H O to 1 liter Solution T K 5 0 Diisopropylaminoethanethiol l-lCl [(l-l C N-CH CH SH HCl] H O to 1 liter Solution U K S O Cystamine ZHCl [(SCH,Ch NH 2l-1Cl] R 0 to 1 liter 41 g/l (0.25 mole) 50 g/l (0.25 mole) 64.5 g/l (0.25 mole) 50 g/l (0.25 mole) 75 g/l (0.25 mole) From this data it appears that solutions S and T effectively bleached and fixed the developed sample. Solutions R and U effectively bleached the silver, but did not adequately fix the silver halide.
Only alkylaminoalkyl thiol homologs of diethylaminoethane thiol appear to be operable fixing agents in a bleach-fix composition according to this invention.
From the above three evaluations it seems clear that aqueous bleach-fix solutions comprising a watersoluble persulfate and alkylaminoalkylthiols exhibit unique properties which are not duplicated in similar solutions containing either different oxidizing agents or fixing agents.
The following examples will serve to further demonstrate the effectiveness of the bleach-fixing solutions of the instant invention and the scope of the invention described herein.
EXAMPLE 1 A sample of Kodak Ektachrome MS Reversal Color Film, Type 2027, was sensitometrically exposed to a multicolor test object, MQ-developed, washed, reversal color developed, washed and bleach-fixed in a l-liter aqueous solution containing 40 g potassium persulfate and 50 g diethylaminoethanethiol. The sample was completely bleach-fixed in 1.5 minutes at a temperature of 71F.
EXAMPLE 2 The procedure described in Example 1 was successfully repeated with two similar bleach-fix solutions, wherein the potassium persulfate was replaced with equal molar quantities of sodium persulfate and ammonium persulfate, respectively.
EXAMPLE 3 When the fixing agent in the solution according to Example 1 was replaced with the two other known fixing agents sodium thiocyanate and thiourea, an inoperable bleach-fix was obtained because of the rapid oxidation of the thiocyanate and the thiourea by the persulfate.
The foregoing bleach-fix compositions can, of course, be utilized to treat any conventional silver or silver halide emulsion wherein it is sought to remove unwanted silver and/or silver halide and in conjunction with all of the conventional development, washing, stabilizing, etc., steps described in the discussion of the prior art set forth above. The use of these compositions in such processes is considered an integral part of this invention.
Concentrates of the bleach-fixing solutions described above may of course be prepared to reduce shipping costs incident to the shipping of the solvent (water) or even in dry powder form to increase the storage life only increasing the stability of such concentrates over long periods of time. When prepared as dry powder mixture or as concentrates the ultimate user simply dissolves the powder or concentrate in a suitable amount of water to provide the above-prescribed concentrations in the working bleach-fix solution. Such dry powder mixtures and/or concentrates which are brought to working solution concentration levels at the time of use are therefore to be included within the scope of this disclosure as well as the appended claims.
As should be clear from the foregoing discussion and examples, the alkylaminoalkylthiols of the solution of the present invention may be supplied in the form of acid salts of these materials, for example 2,2- diethylaminoethane thiol l-lCl, to permit greater ease of dissolution of these materials and increase their availability. When such salts are used, the dissociation products thereof (ie., HCl) will of course be present in the final working bleach-fix solution.
The invention has been described in detail with particular reference to preferred embodiments thereof; however, it should be understood that variations and modifications can be made within the spirit and scope of the invention and the same should not be limited except as set forth in the appended claims.
I claim:
11. A bleach-fix composition for use in processing of photographic elements, said composition comprising a water-soluble persulfate bleaching agent and a fixing agent of the formula:
N- cm). SH
wherein R and R are selected from the group consisting of H, CH C l-l and C l-l and n is an integer of from 1 to 4.
2. A composition as claimed in claim 1 wherein the concentration of said bleaching agent is from about 0.05 to about 0.5 moles per liter and the concentration of said fixing agent is from about 0.1 to about 2.0 moles per liter.
3. A composition as claimed in claim 11 wherein the v and R are Cll-I or C l l and n is 2 or 3.
6. A composition as claimed in claim ll wherein said bleaching agent is potassium persulfate and said fixing agent is 2,2-diethylaminoethanethiol.
7. In a method of photographic processing wherein an exposed photographic element is treated with a bleach-fixing solution containing both a bleaching agent and a fixing agent, the improvement wherein said wherein R and R are selected from the group consisting of H, CH C l-l and C ll, and n is an integer of from 1 to 4.
8. A method as claimed in claim 7 wherein the concentration of said bleaching agent is from about 0.05 to about 05 moles per liter and the concentration of said fixing agent is from about 0.1 to about 2.0 moles per liter.
9. A method as claimed in claim 7 wherein the concentration of said bleaching agent is from about 0.1 to about 0.4 moles per liter and the concentration of said fixing agent is from about 0.13 to about 1.5 moles per liter.
ment, stop-fixing, and bleach-fixing in solution containing a water-soluble persulfate bleaching agent and a fixing agent of the formula:
N-(CHa) n S H wherein R and R are selected from the group consisting of H, CH C l-l and C l-L, and n is an integer of from 1 to 4.
14. A method as claimed in claim 13 wherein the concentration of said bleaching agent is from about 0.05 to about 0.5 moles per liter and the concentration of said fixing agent is from about 0.1 to about 2.0 moles per liter.
15. A method as claimed in claim 13 wherein the concentration of said bleaching agent is from about 0.1 to about 0.4 moles per liter and the concentration of said fixing agent is from about 0.13 to about 1.5 moles per liter.
16. A method as claimed in claim 13 wherein said bleaching agent is selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.
17. A method as claimed in claim 13 wherein R and R are CH or C,H and n is 2 or 3.
18. A method as claimed in claim 13 wherein said bleaching agent is potassium persulfate and said fixing agent is 2,2-diethylaminoethanethiol.

Claims (17)

  1. 2. A composition as claimed in claim 1 wherein the concentration of said bleaching agent is from about 0.05 to about 0.5 moles per liter and the concentration of said fixing agent is from about 0.1 to about 2.0 moles per liter.
  2. 3. A composition as claimed in claim 1 wherein the concentration of said bleaching agent is from about 0.1 to about 0.4 moles per liter and the concentration of said fixing agent is from about 0.13 to about 1.5 moles per liter.
  3. 4. A composition as claimed in claim 1 wherein said bleaching agent is selected from the group consisting of potassium persulfate, sodium persulfate and ammonim persulfate.
  4. 5. A composition as claimed in claim 1 wherein R1 and R2 are CH3 or C2H5 and n is 2 or 3.
  5. 6. A composition as claimed in claim 1 wherein said bleaching agent is potassium persulfate and said fixing agent is 2,2-diethylaminoethanethiol.
  6. 7. In a method of photographic processing wherein an exposed photographic element is treated with a bleach-fixing solution containing both a bleaching agent and a fixing agent, the improvement wherein said bleaching agent is a water-soluble persulfate and said fixing agent is a compound of the formula:
  7. 8. A method as claimed in claim 7 wherein the concentration of said bleaching agent is from about 0.05 to about 0.5 moles per liter and the concentration of said fixing agent is from about 0.1 to about 2.0 moles per liter.
  8. 9. A method as claimed in claim 7 wherein the concentration of said bleaching agent is from about 0.1 to about 0.4 moles per liter and the concentration of said fixing agent is from about 0.13 to about 1.5 moles per liter.
  9. 10. A method as claimed in claim 7 wherein said bleaching agent is selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.
  10. 11. A method as claimed in claim 7 wherein R1 and R2 are CH3 or C2H5 and n is 2 or 3.
  11. 12. A method as claimed in claim 7 wherein said bleaching agent is potassium persulfate and said fixing agent is 2,2-diethylaminoethanethiol.
  12. 13. A method of color processing an exposed photographic element comprising the steps of color development, stop-fixing, and bleach-fixinG in solution containing a water-soluble persulfate bleaching agent and a fixing agent of the formula:
  13. 14. A method as claimed in claim 13 wherein the concentration of said bleaching agent is from about 0.05 to about 0.5 moles per liter and the concentration of said fixing agent is from about 0.1 to about 2.0 moles per liter.
  14. 15. A method as claimed in claim 13 wherein the concentration of said bleaching agent is from about 0.1 to about 0.4 moles per liter and the concentration of said fixing agent is from about 0.13 to about 1.5 moles per liter.
  15. 16. A method as claimed in claim 13 wherein said bleaching agent is selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.
  16. 17. A method as claimed in claim 13 wherein R1 and R2 are CH3 or C2H5 and n is 2 or 3.
  17. 18. A method as claimed in claim 13 wherein said bleaching agent is potassium persulfate and said fixing agent is 2,2-diethylaminoethanethiol.
US00200614A 1971-11-19 1971-11-19 Persulfate bleach-fix solution Expired - Lifetime US3772020A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US20061471A 1971-11-19 1971-11-19

Publications (1)

Publication Number Publication Date
US3772020A true US3772020A (en) 1973-11-13

Family

ID=22742449

Family Applications (1)

Application Number Title Priority Date Filing Date
US00200614A Expired - Lifetime US3772020A (en) 1971-11-19 1971-11-19 Persulfate bleach-fix solution

Country Status (1)

Country Link
US (1) US3772020A (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841873A (en) * 1973-05-21 1974-10-15 Eastman Kodak Co Cobalt (iii) complex amplifier baths in color photographic processes
US3893858A (en) * 1973-03-26 1975-07-08 Eastman Kodak Co Photographic bleach accelerators
US3961957A (en) * 1973-05-18 1976-06-08 Ciba-Geigy Ag Dye bleach preparation for the photographic silver dye bleach process
DE2736886A1 (en) * 1976-08-18 1978-03-02 Konishiroku Photo Ind METHOD OF TREATING LIGHT SENSITIVE COLOR PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIALS
US4088486A (en) * 1975-08-06 1978-05-09 Eastman Kodak Company Process of bleaching silver images to form dye images using cobalt complexes and peroxides
US4097278A (en) * 1975-09-02 1978-06-27 Eastman Kodak Company Redox amplification process employing a combination of oxidizing agents
US4229522A (en) * 1977-10-26 1980-10-21 Fuji Photo Film Co., Ltd. Method for forming color images
US4268618A (en) * 1979-07-05 1981-05-19 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4292401A (en) * 1979-04-12 1981-09-29 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4293639A (en) * 1979-05-09 1981-10-06 Fuji Photo Film Co., Ltd. Bleaching compositions for photographic processing
DE3310956A1 (en) * 1982-03-25 1983-09-29 Fuji Photo Film Co., Ltd., Minami Ashigara, Kanagawa METHOD FOR TREATING A COLOR PHOTOGRAPHIC, LIGHT-SENSITIVE MATERIAL
US4458010A (en) * 1981-11-13 1984-07-03 Fuji Photo Film Co., Ltd. Process for bleaching color photographic sensitive materials
US4506007A (en) * 1983-04-08 1985-03-19 Fuji Photo Film Co., Ltd. Method for processing color photographic materials
US4508816A (en) * 1982-10-21 1985-04-02 Fuji Photo Film Co., Ltd. Method for bleaching color photosensitive material
DE3516417A1 (en) * 1984-05-21 1985-11-21 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa TREATMENT OR DEVELOPMENT METHOD FOR A COLOR PHOTOGRAPHIC MATERIAL
US4578345A (en) * 1983-10-31 1986-03-25 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4596764A (en) * 1984-07-03 1986-06-24 Fuji Photo Film Co., Ltd. Method of processing image-wise exposed silver halide color photographic material
EP0219841A2 (en) * 1985-10-18 1987-04-29 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials
US4914009A (en) * 1986-06-30 1990-04-03 Fuji Photo Film Co., Ltd. Process for forming direct positive color image comprising the use of bleach accelerators
EP0500045A1 (en) * 1991-02-19 1992-08-26 Fuji Photo Film Co., Ltd. Process of processing silver halide photographic material and photographic processing composition having a fixing ability
US5460924A (en) * 1992-12-14 1995-10-24 Eastman Kodak Company Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts
US6077650A (en) * 1999-06-28 2000-06-20 Eastman Kodak Company Stabilized bleaching compositions and method of processing color elements

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1131108A (en) * 1964-12-28 1968-10-23 Eastman Kodak Co Method and materials for photographic processes
US3434796A (en) * 1966-02-11 1969-03-25 United States Borax Chem Silver nitrate stain removal composition and method for using same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1131108A (en) * 1964-12-28 1968-10-23 Eastman Kodak Co Method and materials for photographic processes
US3434796A (en) * 1966-02-11 1969-03-25 United States Borax Chem Silver nitrate stain removal composition and method for using same

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3893858A (en) * 1973-03-26 1975-07-08 Eastman Kodak Co Photographic bleach accelerators
US3961957A (en) * 1973-05-18 1976-06-08 Ciba-Geigy Ag Dye bleach preparation for the photographic silver dye bleach process
US3841873A (en) * 1973-05-21 1974-10-15 Eastman Kodak Co Cobalt (iii) complex amplifier baths in color photographic processes
US4088486A (en) * 1975-08-06 1978-05-09 Eastman Kodak Company Process of bleaching silver images to form dye images using cobalt complexes and peroxides
US4097278A (en) * 1975-09-02 1978-06-27 Eastman Kodak Company Redox amplification process employing a combination of oxidizing agents
DE2736886A1 (en) * 1976-08-18 1978-03-02 Konishiroku Photo Ind METHOD OF TREATING LIGHT SENSITIVE COLOR PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIALS
US4229522A (en) * 1977-10-26 1980-10-21 Fuji Photo Film Co., Ltd. Method for forming color images
US4292401A (en) * 1979-04-12 1981-09-29 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4293639A (en) * 1979-05-09 1981-10-06 Fuji Photo Film Co., Ltd. Bleaching compositions for photographic processing
US4268618A (en) * 1979-07-05 1981-05-19 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4458010A (en) * 1981-11-13 1984-07-03 Fuji Photo Film Co., Ltd. Process for bleaching color photographic sensitive materials
DE3310956A1 (en) * 1982-03-25 1983-09-29 Fuji Photo Film Co., Ltd., Minami Ashigara, Kanagawa METHOD FOR TREATING A COLOR PHOTOGRAPHIC, LIGHT-SENSITIVE MATERIAL
US4446225A (en) * 1982-03-25 1984-05-01 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4508816A (en) * 1982-10-21 1985-04-02 Fuji Photo Film Co., Ltd. Method for bleaching color photosensitive material
US4506007A (en) * 1983-04-08 1985-03-19 Fuji Photo Film Co., Ltd. Method for processing color photographic materials
US4578345A (en) * 1983-10-31 1986-03-25 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4822725A (en) * 1984-05-21 1989-04-18 Fuji Photo Film Co., Ltd. Method for bleaching color photographic material
DE3516417A1 (en) * 1984-05-21 1985-11-21 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa TREATMENT OR DEVELOPMENT METHOD FOR A COLOR PHOTOGRAPHIC MATERIAL
DE3516417C2 (en) * 1984-05-21 1998-02-19 Fuji Photo Film Co Ltd Process for processing a silver halide color photographic material
US4596764A (en) * 1984-07-03 1986-06-24 Fuji Photo Film Co., Ltd. Method of processing image-wise exposed silver halide color photographic material
EP0219841A3 (en) * 1985-10-18 1989-03-22 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials
EP0219841A2 (en) * 1985-10-18 1987-04-29 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials
US4914009A (en) * 1986-06-30 1990-04-03 Fuji Photo Film Co., Ltd. Process for forming direct positive color image comprising the use of bleach accelerators
EP0500045A1 (en) * 1991-02-19 1992-08-26 Fuji Photo Film Co., Ltd. Process of processing silver halide photographic material and photographic processing composition having a fixing ability
US5460924A (en) * 1992-12-14 1995-10-24 Eastman Kodak Company Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts
US5536625A (en) * 1992-12-14 1996-07-16 Eastman Kodak Company Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts
US6077650A (en) * 1999-06-28 2000-06-20 Eastman Kodak Company Stabilized bleaching compositions and method of processing color elements

Similar Documents

Publication Publication Date Title
US3772020A (en) Persulfate bleach-fix solution
US2487569A (en) Antistain baths for color photographic materials
SU416970A3 (en) BLEACHING AND FIXING COMPOSITION
US4294914A (en) Photographic bleach compositions and methods of photographic processing
US4879413A (en) Process for the preparation of a solid adduct of sulfuric acid and urea
JPS6076745A (en) Method for processing color photographic sensitive material
US3772018A (en) Azodicarbonamides as photographic bleaching agents
US3960565A (en) Silver bleaching solutions
US3773510A (en) Additives to bleach/fix baths
JPS6119982B2 (en)
JPS61267761A (en) Treatment of silver halide color photographic sensitive material
US3809563A (en) Method for processing light-sensitive silver halide color photographic materials
US4040837A (en) Photographic bleach-fixer
US3645738A (en) Stabilizing silver image in presence of heterocyclic thioxo compound containing sulphogroup
US4125402A (en) Method of processing silver dye bleaching materials and preparations suitable for the dye and silver bleaching
US3591380A (en) Rapid stabilizing process for color photographic materials
US3615507A (en) Photographic bleach-fix solutions
US3619188A (en) Bleach-fix processing
US3642478A (en) Processes and compositions for converting zero valent metals photographic images to formazan dye images
US6221570B1 (en) One-part bleach-fix liquid concentrates
US3707374A (en) Photographic silver-bleaching composition
JPS5815784B2 (en) How to store bleach-fix solution separately
GB1275074A (en) Photographic silver halide processing methods
US3961958A (en) Process for fixing photographic material
US3761262A (en) Photographic color developing process