US2507183A - Silver bleach for color materials - Google Patents
Silver bleach for color materials Download PDFInfo
- Publication number
- US2507183A US2507183A US584494A US58449445A US2507183A US 2507183 A US2507183 A US 2507183A US 584494 A US584494 A US 584494A US 58449445 A US58449445 A US 58449445A US 2507183 A US2507183 A US 2507183A
- Authority
- US
- United States
- Prior art keywords
- acid
- quinone
- bleach
- silver
- hydroquinone
- 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
Links
- 239000007844 bleaching agent Substances 0.000 title description 16
- 229910052709 silver Inorganic materials 0.000 title description 11
- 239000004332 silver Substances 0.000 title description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 10
- 239000000463 material Substances 0.000 title description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 28
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 24
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 14
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- -1 potassium ferricyanide Chemical compound 0.000 description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- WOGWYSWDBYCVDY-UHFFFAOYSA-N 2-chlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=CC(=O)C=CC1=O WOGWYSWDBYCVDY-UHFFFAOYSA-N 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- This application relates to color photography and particularly to the removal of silver images from emulsion layers in color photography.
- Quinone bleach baths are inconvenient to prepare because the quinone dissolves very slowly in aqueous solutions.
- the common organic solvents are inconvenient or adversely influence the solution.
- Quinone is quickly soluble in hot glacial acetic acid, but this requires handling hot liquid and is an inconvenience in the preparation of the bleach bath. Any liquid is undesirable where the ingredients of the bath must be packaged for sale and kept for a period of time before being purchased by the ultimate user.
- Suitable oxidizing agents for this purpose are alkali metal salts of oxygen acids capable of oxidizing hydroquinone to quinone.
- Suitable alkali metal salts are the sodium, potassium, and ammonium salts, such as ammonium persulfate, potassium permanganate and potassium dichromate.
- the hydroquinone is mixed with solution may contain glacial acetic acid as in the case of the prior art quinone bleach baths, although this is unnecessary. Acids which may be used include hydrochloric and sulfuric acid, or the acid may be obtained in solution from sodium acid sulfate or sulfamic acid.
- the bleach bath also may contain a soluble bromide or chloride to cause the formation of silver halide from the oxidized silver.
- the bleach baths of our invention When packaged in dry form, the bleach baths of our invention preferably contain the hydroquinone in one compartment and the oxidizing agent and potassium bromide in another compartment. If a dry acid former, such as sodium acid sulfate, is used, it may be placed in the container with the hydroquinone.
- acid former we mean a substance which forms an acid when dissolved in water, such as sodium acid sulfate, sulfamic acid, etc.
- quinone derivatives of quinone, such as chloroquinone or toluquinone.
- the bleach bath in use isfollowed by a dilute solution of sodium bisulfite, for example, a 1% solution of bisulfite to react with the retained quinone, and the photographic element is then fixed for about 4 minutes in hypo, washed and dried.
- a dry powder composition for preparation of an acid quinone bleach bath by mixing with water comprising hydroquinone, sodium hydrogen sulfate, and potassium dichromate.
Description
Patented May 9, 1950 SILVER BLEACH FOR COLOR MATERIALS Lot S. Wilder, Rochester, N. Y., and Kent 0.
Brannock, Oak Ridge, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application March 23, 1945, Serial No. 584,494
1 Claim.
This application relates to color photography and particularly to the removal of silver images from emulsion layers in color photography.
In photographic color processes in which a colored image is formed by development with a primaryaromatic amino developing agent in the presence of a coupler compound, the silver images formed during development are present in the. emulsion layer together with dye images. These silver images are generally removed by converting them to a silver salt which is soluble or which is removed by hypo. A bath of this type containing potassium ferricyanide and potassium bromide is disclosed in Mannes, Godowsky and Wilder U. S. Patent 2,252,718, granted August 19, 1941.
Silver bleach baths containing quinone and an acid have also been used for removal of silver. A bath of this type is disclosed in Mannes and Godowsky U. S. Patent 2,113,329, granted April 5, 1938. These quinone bleach baths cannot be used in the final stages because they destroy the image dyes as well as convert the silver to a silver salt. A quinone bleach bath suitable for removal of silver in the presence of a dye image is described in Vittum U. S. patent application Serial No. 541,843, filed June 23, 1944, now abandoned.
Quinone bleach baths are inconvenient to prepare because the quinone dissolves very slowly in aqueous solutions. The common organic solvents are inconvenient or adversely influence the solution. Quinone is quickly soluble in hot glacial acetic acid, but this requires handling hot liquid and is an inconvenience in the preparation of the bleach bath. Any liquid is undesirable where the ingredients of the bath must be packaged for sale and kept for a period of time before being purchased by the ultimate user.
It is, therefore, the principal object of the present invention to provide a simple and convenient method for the preparation of quinone bleach baths for use in color photography. A further object is to provide a bleach bath which may be packaged and kept in dry form. Other objects will appear from the following description of our invention.
These objects are accomplished by using as the source of the quinone a mixture of hydroquinone and an oxidizing agent for the hydroquinone which converts it to quinone in acid solution. Suitable oxidizing agents for this purpose are alkali metal salts of oxygen acids capable of oxidizing hydroquinone to quinone. Suitable alkali metal salts are the sodium, potassium, and ammonium salts, such as ammonium persulfate, potassium permanganate and potassium dichromate.
In the preparation of bleach baths according to our invention, the hydroquinone is mixed with solution may contain glacial acetic acid as in the case of the prior art quinone bleach baths, although this is unnecessary. Acids which may be used include hydrochloric and sulfuric acid, or the acid may be obtained in solution from sodium acid sulfate or sulfamic acid. The bleach bath also may contain a soluble bromide or chloride to cause the formation of silver halide from the oxidized silver.
When packaged in dry form, the bleach baths of our invention preferably contain the hydroquinone in one compartment and the oxidizing agent and potassium bromide in another compartment. If a dry acid former, such as sodium acid sulfate, is used, it may be placed in the container with the hydroquinone. By acid former we mean a substance which forms an acid when dissolved in water, such as sodium acid sulfate, sulfamic acid, etc.
The following formulas illustrate bleach baths prepared according to our invention.
Formula 1 Hydroquinone g 2.5 Ammonium persulfate g 5.14 Potassium bromide g 10 Glacial acetic acid cc 5 Hydrochloric acid (conc.) cc 5 Water to 1 liter.
Formula 2 Hydroquinone g 2.5 Potassium permanganate g 1.4 Potassium bromide g 10 Sulfuric acid (conc.) cc 1 Glacial acetic acid cc 5 Hydrochloric acid (conc.) cc 5 Water to 1 liter.
Formula 3 Hydroquinone g 2.5 Potassium dichromate g 2.2 Potassium bromide g 10 Sulfuric acid (conc.) cc 1 Hydrochloric acid (conc.) cc 5 Water to 1 liter.
The following formula illustrates a dry powder mixture for preparing one liter of solution according to our invention:
Formula 4 A NaHSO g 28 Hydroquinone g 1.25
B Potassium dichromate g 1.5 Potassium bromide g 10 3 Formula 5 Sulfamic acid g 12 Hydroquinone g 1.25 Potassium dichromate g 1.5 Potassium bromide g 10 Water to 1 liter.
In place of quinone, derivatives of quinone, such as chloroquinone or toluquinone. may be used. The bleach bath in use isfollowed by a dilute solution of sodium bisulfite, for example, a 1% solution of bisulfite to react with the retained quinone, and the photographic element is then fixed for about 4 minutes in hypo, washed and dried.
It will be understood that the examples and formulas included herein are illustrative only and that our invention is to be taken as limited only by the scope of the appended claim.
We claim:
A dry powder composition for preparation of an acid quinone bleach bath by mixing with water, comprising hydroquinone, sodium hydrogen sulfate, and potassium dichromate.
LOT S. WILDER. KENT C. BRANNOCK.
4 REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,755,129 Pomeroy Apr. 15, 1930 1,755,130 Pomeroy Apr. 15, 1930 1,966,330 Burwell July 10, 1934 1,969,479 Seymour Aug. 7, 1934 2,019,718 Mannes et a1 Nov. 5, 1935 2,059,881 Mannes et a1 Nov. 3, 1936 2,113,329 Mannes et a1 Apr. 5, 1938 2,158,186 Hickman et a1 May 16, 1939 2,195,419 McQueen Apr. 2, 1940 2,313,523 Donovan et a1 Mar. 9, 1943 OTHER REFERENCES Conant, The Chemistry of Organic. Com.-
20 pounds, The Macmillan 00., New York, 1936;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US584494A US2507183A (en) | 1945-03-23 | 1945-03-23 | Silver bleach for color materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US584494A US2507183A (en) | 1945-03-23 | 1945-03-23 | Silver bleach for color materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2507183A true US2507183A (en) | 1950-05-09 |
Family
ID=24337545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US584494A Expired - Lifetime US2507183A (en) | 1945-03-23 | 1945-03-23 | Silver bleach for color materials |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2507183A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3061433A (en) * | 1958-08-04 | 1962-10-30 | Ilford Ltd | Process and solution for bleaching photographic images |
| US4546069A (en) * | 1983-07-20 | 1985-10-08 | Ciba-Geigy Ag | Method for processing photographic silver dye bleach materials |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1755129A (en) * | 1926-07-14 | 1930-04-15 | Famous Players Lasky Corp | Method of making composite photographs |
| US1755130A (en) * | 1926-07-14 | 1930-04-15 | Famous Players Lasky Corp | Method of making composite photographs |
| US1966330A (en) * | 1931-07-22 | 1934-07-10 | Eastman Kodak Co | Process for making two-color subtractive photographic prints on double-coated film |
| US1969479A (en) * | 1931-05-11 | 1934-08-07 | Eastman Kodak Co | Method of producing color photographic images by development |
| US2019718A (en) * | 1932-12-03 | 1935-11-05 | Leopold D Mannes | Differential treatment of color component images |
| US2059887A (en) * | 1935-02-27 | 1936-11-03 | Eastman Kodak Co | Differential treatment of multilayer films |
| US2113329A (en) * | 1934-06-15 | 1938-04-05 | Eastman Kodak Co | Color photography |
| US2158186A (en) * | 1938-03-09 | 1939-05-16 | Eastman Kodak Co | Toning and intensifying solutions |
| US2195419A (en) * | 1938-10-03 | 1940-04-02 | Du Pont Film Mfg Corp | Process for reducing the density of silver images and compositions therefor |
| US2313523A (en) * | 1940-06-18 | 1943-03-09 | Eastman Kodak Co | Photographic material |
-
1945
- 1945-03-23 US US584494A patent/US2507183A/en not_active Expired - Lifetime
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1755129A (en) * | 1926-07-14 | 1930-04-15 | Famous Players Lasky Corp | Method of making composite photographs |
| US1755130A (en) * | 1926-07-14 | 1930-04-15 | Famous Players Lasky Corp | Method of making composite photographs |
| US1969479A (en) * | 1931-05-11 | 1934-08-07 | Eastman Kodak Co | Method of producing color photographic images by development |
| US1966330A (en) * | 1931-07-22 | 1934-07-10 | Eastman Kodak Co | Process for making two-color subtractive photographic prints on double-coated film |
| US2019718A (en) * | 1932-12-03 | 1935-11-05 | Leopold D Mannes | Differential treatment of color component images |
| US2113329A (en) * | 1934-06-15 | 1938-04-05 | Eastman Kodak Co | Color photography |
| US2059887A (en) * | 1935-02-27 | 1936-11-03 | Eastman Kodak Co | Differential treatment of multilayer films |
| US2158186A (en) * | 1938-03-09 | 1939-05-16 | Eastman Kodak Co | Toning and intensifying solutions |
| US2195419A (en) * | 1938-10-03 | 1940-04-02 | Du Pont Film Mfg Corp | Process for reducing the density of silver images and compositions therefor |
| US2313523A (en) * | 1940-06-18 | 1943-03-09 | Eastman Kodak Co | Photographic material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3061433A (en) * | 1958-08-04 | 1962-10-30 | Ilford Ltd | Process and solution for bleaching photographic images |
| US4546069A (en) * | 1983-07-20 | 1985-10-08 | Ciba-Geigy Ag | Method for processing photographic silver dye bleach materials |
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