US2529981A - Bleaching silver images - Google Patents
Bleaching silver images Download PDFInfo
- Publication number
- US2529981A US2529981A US631500A US63150045A US2529981A US 2529981 A US2529981 A US 2529981A US 631500 A US631500 A US 631500A US 63150045 A US63150045 A US 63150045A US 2529981 A US2529981 A US 2529981A
- Authority
- US
- United States
- Prior art keywords
- silver
- images
- quinone
- bath
- layer containing
- 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
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052709 silver Inorganic materials 0.000 title claims description 27
- 239000004332 silver Substances 0.000 title claims description 27
- 238000004061 bleaching Methods 0.000 title description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 28
- 239000000975 dye Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000001013 indophenol dye Substances 0.000 description 4
- 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 4
- -1 potassium ferricyanide Chemical compound 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 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 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Inorganic materials [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin 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
Description
Patented Nov. 14, 1950 BLEACHING SILVER IMAGES Paul W. Vittum, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 28, 1945, Serial No. 631,500
.4 Claims. 1
This application relates to color photograph and particularly to the removal of silver images in color photography.
In photographic color processes, such as those in which a colored image is formed by development with a primary aromatic amino developing agent in the presence of a coupler compound, the silver images formed in the development are generally present in the emulsion layer after the dye images are formed. 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. A similar bath containing 50 grams of potassium ferricyanide and 20 grams of sodium chloride per liter of water, to which has been added 1 to 5 grams of potassium chromate or potassium dichromate to retard the corrosive action of the bath on iron and iron alloys, has also been used.
The ferricyanide and halide bleach baths are not entirely satisfactory in that certain optical sensitizing dyes in the emulsion layer are not destroyed by them and these may cause stain in the emulsion layer. A further disadvantage is that any ferricyanide remaining in the element may be converted to iron oxide and produce a brown stain and there is also the objectionable corrosive action on stainless steel or iron alloys unless a chromate or dichromate is used in the bath.
A bleach bath containing quinone, acid, and an organic solvent has also been used to convert silver images to silver salt in the presence of a developed dye image. A bath of this type is disclosed in Mannes and Godowsky U. S. Patent 2,113,329, page 2, column 2, lines 16 to 21. This bath cannot be used in the final stages of a color process because it destroys the dyes as well as converts the silver to a silver salt.
It is therefore an object of the present invention to provide a method of bleaching silver images which overcomes the aforementioned difiiculties. A further object is to provide a method for converting the silver images to a silver salt without destroying dye images present in the emulsion layer. A still further object is to provide a bleach bath not containing iron salts.
These objects are accomplished by bleaching the silver with a strong acid solution of a quinone containing an alkali metal chloride or bromide, and substantially free of organic 501-- vent. By strong acid solution I mean a solution having a pH of about 1.5 to'about 3.5.
The bleach bath employed according to my invention may be used in any process in which silver images are present in a photographic layer together with dye images. The dye'images may be those formed by color development as described in Mannes, Godowsky, and Wilder U. S. Patent 2,252,718; Mannes and GodoWskyUjS. Patents 2,113,329 a'nd 2,304,940; orJelley and Vittum U. S. Patent 2,322,027. The dyes may also be azo dyes such as those used in the silver dye bleach process of color photography. After all of the steps of color processing the photographic layer or element is treated with the bleach bath of my invention followed by. hypo to remove the silver salts formed'by the bleach bath.
The emulsion layers containing the silver-and dye images treated according to my invention may be coated on glass-support-s or on supports of cellulose ester, synthetic resin, or paper.
The following examples illustrate baths which may be used according to my invention:
. -Ezrampl l Quinone "grams; 5 Glacial acetic acid cc 10 Potassium bromide gram-s 10 Hydrochloric acid (35%) cc 5 Water to liter 1 Example 2 Quinone grams 2.5 Glacial acetic acid do 5 Potassium bromide do 10 Hydrochloric acid (35%) cc 5 Water to liter 1 The bath was adjusted to a pH of 1.8.
Example 3 Quinone grams 2.5 Glacial acetic acid do 5 Potassium bromide do 10 Concentrated sulfuric acid cc 3 Water to liter 1 The bath was adjusted to a pH of 1.8.
Example 4 Quinone grams 2.5 Glacial acetic acid do 5 Potassium bromide do 10 'sulfamic acid do 3 Water to liter 1 The bath Was adjusted to a pH of 1.8.
3 Example 5 Quinone grams 2.5 Glacial acetic acid do 5 Potassium bromide do Ortho phosphoric acid (85%) cc 9 Water to liter 1 The bath was adjusted to a pH of 1.8.
In these formulas a chloride, such as potassium chloride, may be substituted for the potassium bromide.
In place of quinone, chloroquinone or toluquinone may be used. In place of potassium chloride or bromide, ammonium or sodium chloride or bromide ma be used. No organic solvent for the dyes in the emulsion should be present. The bath is followed by a dilute solution of sodium bisulfite, for example, a 1% solution to react with the retained quinone, and the element is then fixed for about four minutes in hypo, washed and dried.
This application is a continuation-in-part of my application Serial No. 541,843, filed June 23, 1944, now abandoned.
It will be understood that the example included herein is illustrative only and that my invention is to be taken as limited only by the scope of the appending claims.
I claim: 1 l. The method of removing only the silver images from a photographic layer containing silver and color developed dye images of the class consisting of azomethine, indaniline and indophenol dyes, which comprises treating said layer containing said silver and dye images with a strong acid solution of a quinone having a pH of 1.5 to 3.5, said. solution containing an alkalimetal halide selected from the group consisting ofchlorides and bromides, but being free of organic solvent, followed by fixing.
'2. The method of removing only the silver images from a photographic layer containing silver and color developed dye images of the class consisting of azomethine, indaniline and indophenol dyes, which comprises treating said layer containing said silver and dye images with a hydrochloric acid solution of a quinone having a pH of 1.5 to 3.5, said solution containing an alkalimetal bromide, but being free of organic solvent, followed by fixing.
3. The method of removing only the silver images from a photographic layer containing silver and color developed dye images of the class consisting of azomethine, indaniline and indophenol dyes, which comprises treating said layer containing said silver and dye images with an aqueous solution of quinone having a pH of 1.5 to 3.5 and containing hydrochloric acid and potassium bromide, said solution being free of organic solvent, followed by fixing.
4. The method of removing only the silver images from a photographic layer containing silver and color developed dye images of the class consisting of azomethine, indaniline and indophenol dyes. which comprises treating said layer containing silver and dye images with a strong acid solution of a quinone having a, pH of 1.5 to 3.5, said solution containing bromide ions but being free of organic solvent, followed by fixing.
PAUL W. VITTUM.
REFERENCES crrsn 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 al Nov. 5, 1935 2,059,887 Mannes et a1. Nov. 3, 1936 2,113,329 Mannes Apr. 5, 1938 2,283,276 Middleton et al. May 19, 1942 OTHER REFERENCES Wall, Photographic Facts and Formulas, first edition, 1924, published by American Photographic Publishing 00., Boston, Mass, page 240 cited. (Copy in Div. 67.)
Claims (1)
1. THE METHOD OF REMOVING ONLY THE SILVER IMAGES FROM A PHOTOGRAPHIC LAYER CONTAINING SILVER AND COLOR DEVELOPED DYE IMAGES OF THE CLASS CONSISTING OF AZOMETHINE, INDANILINE AND INDOPHEONOL DYES, WHICH COMPRISES TREATING SAID LAYER CONTAINING SAID SILVER AND DYE IMAGES WITH A STRONG ACID SOLUTION OF A QUINONE HAVING A PH OF 1.5 TO 3.5, SAID SOLUTION CONTAINING AN ALKALIMETAL HALIDE SELECTED FROM THE GROUP CONSISTING OF CHLORIDES AND BROMIDES, BUT BEING FREE OF ORGANIC SOLVENT, FOLLOWED BY FIXING.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US631500A US2529981A (en) | 1945-11-28 | 1945-11-28 | Bleaching silver images |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US631500A US2529981A (en) | 1945-11-28 | 1945-11-28 | Bleaching silver images |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2529981A true US2529981A (en) | 1950-11-14 |
Family
ID=24531486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US631500A Expired - Lifetime US2529981A (en) | 1945-11-28 | 1945-11-28 | Bleaching silver images |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2529981A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3065074A (en) * | 1958-08-20 | 1962-11-20 | Polaroid Corp | 1,4-benzoquinone oxidizing agents for color transfer processes |
| US3716362A (en) * | 1969-07-30 | 1973-02-13 | Ciba Geigy Ag | Process for the removal of metallic silver from photographic material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1755130A (en) * | 1926-07-14 | 1930-04-15 | Famous Players Lasky Corp | Method of making composite photographs |
| US1755129A (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 |
| US2283276A (en) * | 1939-01-25 | 1942-05-19 | Du Pont | Photographic composition containing arylides of n-heterocyclic acylacetic acids and process of developing photographic images therewith |
-
1945
- 1945-11-28 US US631500A patent/US2529981A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1755130A (en) * | 1926-07-14 | 1930-04-15 | Famous Players Lasky Corp | Method of making composite photographs |
| US1755129A (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 |
| US2283276A (en) * | 1939-01-25 | 1942-05-19 | Du Pont | Photographic composition containing arylides of n-heterocyclic acylacetic acids and process of developing photographic images therewith |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3065074A (en) * | 1958-08-20 | 1962-11-20 | Polaroid Corp | 1,4-benzoquinone oxidizing agents for color transfer processes |
| US3716362A (en) * | 1969-07-30 | 1973-02-13 | Ciba Geigy Ag | Process for the removal of metallic silver from photographic material |
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