US2013159A - Process of chemically transforming photographic images - Google Patents
Process of chemically transforming photographic images Download PDFInfo
- Publication number
- US2013159A US2013159A US444359A US44435930A US2013159A US 2013159 A US2013159 A US 2013159A US 444359 A US444359 A US 444359A US 44435930 A US44435930 A US 44435930A US 2013159 A US2013159 A US 2013159A
- Authority
- US
- United States
- Prior art keywords
- silver
- image
- complex
- images
- photographic images
- 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
- 238000000034 method Methods 0.000 title description 23
- 230000001131 transforming effect Effects 0.000 title description 11
- 229910052709 silver Inorganic materials 0.000 description 42
- 239000004332 silver Substances 0.000 description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 28
- -1 silver halide Chemical class 0.000 description 17
- 239000000126 substance Substances 0.000 description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 3
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 239000001828 Gelatine Substances 0.000 description 2
- 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 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical compound [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001579016 Nanoa Species 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DPPGFDBIEYDQOT-UHFFFAOYSA-N [Ag].NC(=N)N Chemical compound [Ag].NC(=N)N DPPGFDBIEYDQOT-UHFFFAOYSA-N 0.000 description 1
- LDWQDNOXUOTDFO-UHFFFAOYSA-L [Mn](=O)(=O)(SC#N)SC#N Chemical compound [Mn](=O)(=O)(SC#N)SC#N LDWQDNOXUOTDFO-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 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 1
- 238000005213 imbibition Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical class [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical class [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000000844 transformation Methods 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
Definitions
- This invention relates to a process of chemically transforming photographic images.
- the present process now, opens up new possibilities of obtaining chemical compounds by way of the photographic silver image, or of the silver halide residual image, in a very simple manner, the said images hitherto being incapable of being converted at all into these compounds, or
- the essential feature of the process according to the invention consists in subjecting the image forming substance for instance AgBr, AgCl to the action of complex forming solvents, chemical agentsbeing added to the latter which together with the complex combination result in soluble reaction product.
- the process of the chemical reaction or transformation according to the present invention is mainly a physical process, that is to say a double or mutual reaction or transformation is attained by employing a dissolving process in combination with a simultaneous precipitating process.
- the image formingsub'stance, for which AgBr or AgCl is preferably selected is subjected to the action of a solvent which possesses a strong solvent action for the said substance while the solution and the agent added to the solvent, must be insoluble or only slightly soluble therein.
- the function of the process may be best understood by an example with a simple solvent alan inthough this permits only a limited selection of transforming possibilities.
- the silver chloride will be dissolved in the ammonium hydroxide and transformed with the ammonium molybdate into silver molybclate which is slightly soluble in diluted ammonium hydroxide and 'pre- I cipitated in place of the former silver chloride image.
- the solvent is used according to the present process not unnecessarily concentrated but 'in a dilution which effects a good but not too quick solution of the image substance, in the above case a solu-, tion of about 10% ammonium hydroxide.
- the transforming agent for instance, ammonium molybdate is added thereto usually concentrated.
- a formation of the kind of a double salt solution and its further use forchemical transformation according to the present process takes place in the following manner by way of example:
- the silver halide image is bathed in a diluted solution of about 2-5%, manganic thiocyanate whereupon the silver halide becomes transparent to the extent of the formation of its complex combination.
- a compound is obtained whichis capable of reaction and can be used for further transformation.
- the thiocyanate group cyanate reducing reactions may be carried out, as hereinafter described, or the manganese may be used for oxidation processes by transforming the same in the known manner by an alkaline of the. added manganic thiobath into a manganese dioxide image from which oxidation dye images can be produced.
- a silver image is bleached in the known manner to form a silver chloride or bromide image and the latter' is bathed in a thiosiamine solution of to 1% to which is added sodium phosphotungstate in a concentration according to the above-mentioned indications 2.
- silver phosphotungstate complex will be precipitated as the silver halide passes into solution in the thiosiamine. This precipitated matter is a means for fixing basic dyes in a waterproof and light fast manner. Therefore it is possible to obtain dye images by bathing the phosphotung'state image in a solution of a basic dye and subsequently removing the phosphotungstate image by treatment in a solution of thiosulphate.
- azo dyes possess as components organic sulphonic acids and therefore azo dye images of an unlimited variety can be produced by the transformation of the silver image into the same and by a subsequent coupling bath with diazo components.
- the insolubility of the respective complex silver combinations depends on the choice of the respective complex formers, and therefore in many cases preferably dialkylated thio-ureas, thiosemicarbazide, guanidine or similar suited substances are used in place, of thiosinamine.
- image intensifications may be directly produced by subsequently treating the bluish toned or dyed silver image in an alkaline bath.
- Silver sulphide is formed by the alkaline bath, which former intensifies the blue image and at the same time renders it black, if a readily decomposable sulphur compound is employed as complex-former.
- the thiocarbamide possesses a characteristic which in a purely physical way can be used for producing photographic dye images. If in addition to the thiocarbamide a silver compound is used which is quite insoluble in the same and if concentrated thiocarbamide of about,5% is used, the image will be transformed into "a transparent caoutchouc-like substance. Thelatter closes the pores of the gelatine at the image-places in a watertight manner as if the same had been treated with resin. After the image has been dried, it is placed into an acidic dye-solvent and at the same time a silver-compound'is taken which does not show any causticity for dyes. In view thereof the dye is fully repelled at the places of the complex silver image and, by its imbibition into the remaining part of the gelatine, a negative dye image is produced compared with the initial image.
- Process for toning silver images consisting in transforming the silver into silver halide, and subjecting the transformed image to a bath containing a complex forming solvent for the silver halide of the group of thiosinamine, thiourea, thiosemicarbazide, guanidine and containing also a reagent which immediately forms an insoluble precipitate with the silver complex, but which does not react with the silver halide.
- Process for toning silver images consisting in transforming the silver into silver halide and subjecting the transformed image to a bath containing a complex forming solvent for the silver halide of the group of thiosinamine, thiourea, thiosemicarbazide, guanidineand containing also azo dye components having a sulfonic acid grouping.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEL0074850 | 1929-04-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2013159A true US2013159A (en) | 1935-09-03 |
Family
ID=7283568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US444359A Expired - Lifetime US2013159A (en) | 1929-04-17 | 1930-04-14 | Process of chemically transforming photographic images |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2013159A (enrdf_load_stackoverflow) |
| BE (1) | BE373576A (enrdf_load_stackoverflow) |
| FR (1) | FR702027A (enrdf_load_stackoverflow) |
| GB (1) | GB333361A (enrdf_load_stackoverflow) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2500421A (en) * | 1944-11-03 | 1950-03-14 | Polaroid Corp | Photographic silver halide transfer process |
| US2616804A (en) * | 1945-08-13 | 1952-11-04 | Polaroid Corp | Sheet material containing a liquid for processing a silver halide layer |
| US2647055A (en) * | 1946-11-06 | 1953-07-28 | Polaroid Corp | Photographic product and process for forming a white image viewable against a dark background |
| US2698238A (en) * | 1947-02-08 | 1954-12-28 | Polaroid Corp | Photographic product and process |
| US3660092A (en) * | 1966-12-20 | 1972-05-02 | Agfa Gevaert Ag | Colorphotographic material |
| CN111094975A (zh) * | 2017-09-25 | 2020-05-01 | 哈希公司 | 使用非苛刻试剂的氯化物测量 |
-
0
- BE BE373576D patent/BE373576A/xx unknown
-
1929
- 1929-07-08 GB GB20907/29A patent/GB333361A/en not_active Expired
-
1930
- 1930-04-14 US US444359A patent/US2013159A/en not_active Expired - Lifetime
- 1930-09-16 FR FR702027D patent/FR702027A/fr not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2500421A (en) * | 1944-11-03 | 1950-03-14 | Polaroid Corp | Photographic silver halide transfer process |
| US2616804A (en) * | 1945-08-13 | 1952-11-04 | Polaroid Corp | Sheet material containing a liquid for processing a silver halide layer |
| US2647055A (en) * | 1946-11-06 | 1953-07-28 | Polaroid Corp | Photographic product and process for forming a white image viewable against a dark background |
| US2698238A (en) * | 1947-02-08 | 1954-12-28 | Polaroid Corp | Photographic product and process |
| US3660092A (en) * | 1966-12-20 | 1972-05-02 | Agfa Gevaert Ag | Colorphotographic material |
| CN111094975A (zh) * | 2017-09-25 | 2020-05-01 | 哈希公司 | 使用非苛刻试剂的氯化物测量 |
| CN111094975B (zh) * | 2017-09-25 | 2022-11-29 | 哈希公司 | 使用非苛刻试剂的氯化物测量 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB333361A (en) | 1930-08-14 |
| FR702027A (fr) | 1931-04-27 |
| BE373576A (enrdf_load_stackoverflow) |
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