US2319344A - Process for stabilizing prints obtained by photographic bleaching - Google Patents
Process for stabilizing prints obtained by photographic bleaching Download PDFInfo
- Publication number
- US2319344A US2319344A US309482A US30948239A US2319344A US 2319344 A US2319344 A US 2319344A US 309482 A US309482 A US 309482A US 30948239 A US30948239 A US 30948239A US 2319344 A US2319344 A US 2319344A
- Authority
- US
- United States
- Prior art keywords
- grams
- sensitizer
- bleaching
- stabilizing
- layer
- 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
- 238000004061 bleaching Methods 0.000 title description 12
- 238000000034 method Methods 0.000 title description 9
- 230000000087 stabilizing effect Effects 0.000 title description 2
- 239000000243 solution Substances 0.000 description 11
- 230000001376 precipitating effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229960002523 mercuric chloride Drugs 0.000 description 5
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 5
- 150000003585 thioureas Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000009877 rendering Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- SHXOKQKTZJXHHR-UHFFFAOYSA-N n,n-diethyl-5-iminobenzo[a]phenoxazin-9-amine;hydrochloride Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=[NH2+])C2=C1 SHXOKQKTZJXHHR-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- LUTSRLYCMSCGCS-BWOMAWGNSA-N [(3s,8r,9s,10r,13s)-10,13-dimethyl-17-oxo-1,2,3,4,7,8,9,11,12,16-decahydrocyclopenta[a]phenanthren-3-yl] acetate Chemical compound C([C@@H]12)C[C@]3(C)C(=O)CC=C3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 LUTSRLYCMSCGCS-BWOMAWGNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CEQDTIAWONPGPC-UHFFFAOYSA-N carbamoylsulfamic acid Chemical compound NC(=O)NS(O)(=O)=O CEQDTIAWONPGPC-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- -1 compound salts Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten 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
- G03C7/02—Direct bleach-out processes; Materials therefor; Preparing or processing such materials
Definitions
- the present invention is based on the idea that an intimate contact is necessary between the dyestuffs and the sensitiz'ers, for imparting to these dye-stufis a good sensitiveness to light, and that 4 the dissociation of the sensitizer and of the dyestufi, considerably diminish the sensitivenessto light of the dye-stuffs.
- thg layers are treated, after exposure to light, by one or more solutions having the property of precipitating the sensitizer.
- precipitating the sensitizer a dissociation of the dyestuffs and sensitizers is obtained.
- the most simple method of carrying into practice this process consists in the fact that the layer,,,after exposure tolight is introduced in an aqueous solution capable- 0f completely precipitating the sensitizer.
- Use is made for instance of a, solution of mercuric chloride as solution for precipitating the thiourea derivative.
- a highly soluble thiourea derivative the elimination of the sensitizer from the layer takes place extremely rapidly, since, among other reascns, the concentration of the sensitizer in the bath is constantly practically null, .owing to the precipitation.
- Another advantage in this case is that by choosing a suitable concentration of the mercury salt, the precipitate is only formed in the precipitating bath and not-on the layer itself, as it is soluble in an excess of the thiourea derivative.
- the sensitizer is soluble inwater, it will be generally, first of all, eliminated. for the mailer part by washing in water, and alone the last traces of sensitizer, practically extraordinarily diflicult to eliminate, will be precipitated in a suitable manner; The layer will be perfectly desensitized thereby, as an adsorption of the remaining portions of sensitizer on the dyestufi v particles will no longer be possible.
- this action can be obtained by the use of a suitable bath, if need be, even before eliminating the sensitizer by washing; the sensitizer can also be eliminated by washing in a bath having the faculty of precipitating dyestuffs; the dyestufis can alsobe rendered insoluble beforehand, when manufacturing the sensitized layer;
- the dyestulI can be rendered insoluble in the very bath intended for precipitating thesensitizer.
- This latter result is obtained in case it is a question of basic dyestuffs, for instance, by the above mentioned bath, consisting in a solution of mercuric chloride.
- the Nile blue dyestufl Schotz, VII, edition No. 1029 is;
- oi organic quaternary ammonium bases also called cationactive substances, or use can be made for rendering the dyestufl. insoluble, oi soluble derivatives of tin, silicon, tungsten, and
- molybdenum As mentioned use can be made for precipitating the sensitizer and rendering the dyestufis insoluble, of a single solution, if need be, a solution of a plurality of products,
- Results are also obtained for instance with certain compound salts of tin and silicon.
- Example 1.-'1'he following solution is prepared: 200 grams of water, 30 grams of ammonium chlorostannate, 18 grams of silicotungstic acid.
- a paper bleaching print prepared with basic dyestufls is treated in a bath of this solution, it is washed with water for 5 minutes,.then it is dried.
- the stability to light of the print will thus' correspond to the initial stability of the basic dyestuffs incorporated, and the tints to the initial colours.
- Example Z.A layer of. the solution according to Example 1 is applied on an exposed bleaching out layer. It is dried. The layer is nearly completely desensitized, without changing the tints.
- Example 3 On an exposed bleaching out layer containing naphtionic red, oxalic acid and diethanolallylsulpho-urea, is spread a solution of. m diacetylamino phenyl trimethylammonium chloride. it is then washed for a few minutes. Perfect fastness to light is obtained.
- Example 4 After exposure a trichroiiie bleaching out layer is treated. containing as dyestuffs only basic dyestuffs and sulphocarbamic derivatives, as sensitizers, first of all in the following bath: 200 grams of water, 10 grams of mercuric chloride, 1 gram of concentrated hydrochloric acid. Then it is washed in the following bath: 1000 grams of water, 50 grams of sulphourea.
- Example 5 A bleaching out layer is prepared as. follows: in 1000 grams of water are dissolved grams of gelatlne, 5 grams of hydrochloric acid, 4 grams of Nile blue sulphate, 6.5 grams of Flavindulin O, 3.5 grams of sulphopyronine G. 100 grams of acetamide and grams of oxalic acid. Then, the mixture of grams of diethylallylsulpho-urea and 25 grams of mercuric chloride which was previously heated with 50 grams of water, is added. It is spread on paper, exposed to light under a negative and the proof is washed for 15 minutes.
Description
by washing,
2. Rendering thedyestufi, or respectively the Patented May18, 1943 PROCESS FOR STABILIZING- PRINTS. 013-" TAIN ED BY PHOTOGRAPHIC BLEACHING Andi- Polgar and Charles Halmos, Paris, France; vested in the Alien Property Custodian No Drawing. Application December 15, 1939, Serial No. 309,482. In France December 15, 1938 1 Claim. (01. 95-7 The present invention has for object various treatments of bleaching layers sensitized by thiocarbamic derivatives, in order to ensure or improve the stability of the prints obtained by photographic bleaching.
It is known that the methods proposed up to now for fixing the bleaching layers against the action of light nearly exclusively belong to the dyeing art, as mordanting by tanin, treatment with copper solutions, etc. The inconveniences of these-methods consisted in the coloration of thelight parts of the proofs printed, in the changing, sometimes fundamental, of the tints obtained and in the necessityof eiiecting. long washings for eliminating the agent in excess.
It has also been proposed, especially for completing the treatments mentioned, to use baths of organic solvents, such as alcohol for elimihating the sensitizers. It has been, proposed, for instance for basic dye-stuffs, to convert them into borofluoric derivatives and to eliminate the sensiti'zer by dissolution in a suitable solvent. It has been proposed to use powerful oxidising agents (nitrous acid) or powerful reducing agents (sulphurous acid) for destroying them. These processes allow of only incompletely attaining the result sought for and are sometimes prejudicial to the organic materials'with which they are placed in contact, and particularly the substratum, the dye-stufis andthe support.
The present invention is based on the idea that an intimate contact is necessary between the dyestuffs and the sensitiz'ers, for imparting to these dye-stufis a good sensitiveness to light, and that 4 the dissociation of the sensitizer and of the dyestufi, considerably diminish the sensitivenessto light of the dye-stuffs.
. According to the invention, thg layers are treated, after exposure to light, by one or more solutions having the property of precipitating the sensitizer. By precipitating the sensitizer a dissociation of the dyestuffs and sensitizers is obtained.
' It need be, respectively 80001111128 to the composition of the layer and according to the dyestuiis it contains, the precipitation of the semi-- tizer will be completed by one or both of the following accessory means:
1. Elimination of the sensitizer from the layer dyestuffs insoluble.
The most simple method of carrying into practice this process consists in the fact that the layer,,,after exposure tolight is introduced in an aqueous solution capable- 0f completely precipitating the sensitizer. Use is made for instance of a, solution of mercuric chloride as solution for precipitating the thiourea derivative. case of a highly soluble thiourea derivative, the elimination of the sensitizer from the layer takes place extremely rapidly, since, among other reascns, the concentration of the sensitizer in the bath is constantly practically null, .owing to the precipitation. Another advantage in this case is that by choosing a suitable concentration of the mercury salt, the precipitate is only formed in the precipitating bath and not-on the layer itself, as it is soluble in an excess of the thiourea derivative.
If the sensitizer is soluble inwater, it will be generally, first of all, eliminated. for the mailer part by washing in water, and alone the last traces of sensitizer, practically extraordinarily diflicult to eliminate, will be precipitated in a suitable manner; The layer will be perfectly desensitized thereby, as an adsorption of the remaining portions of sensitizer on the dyestufi v particles will no longer be possible.
Concerning the rendering of the dyestui! insoluble, this action can be obtained by the use of a suitable bath, if need be, even before eliminating the sensitizer by washing; the sensitizer can also be eliminated by washing in a bath having the faculty of precipitating dyestuffs; the dyestufis can alsobe rendered insoluble beforehand, when manufacturing the sensitized layer;
finally the dyestulI can be rendered insoluble in the very bath intended for precipitating thesensitizer. This latter result is obtained in case it is a question of basic dyestuffs, for instance, by the above mentioned bath, consisting in a solution of mercuric chloride. For instance, the Nile blue dyestufl (Schultz, VII, edition No. 1029) is;
by means of this bath, instantaneously precipitated, fined and maintained in the layer. For increasing the fastness of dyestufis to washin in case basic dyestufls are under consideration,
if acid dyestufls and more especially azoic dyestufls are contemplated, use'can be made, for
7 that purpose, oi organic quaternary ammonium bases, also called cationactive substances, or use can be made for rendering the dyestufl. insoluble, oi soluble derivatives of tin, silicon, tungsten, and
molybdenum. As mentioned use can be made for precipitating the sensitizer and rendering the dyestufis insoluble, of a single solution, if need be, a solution of a plurality of products,
For eliminating the activity by precipitating the thiourea derivatives as sensitizers, the most In the 2' suitable products are actually, mercury salts.
Results are also obtained for instance with certain compound salts of tin and silicon.
These latter salts have the property of forming 4 with an excess of thiocarbamic derivative or by mixture of sulpho-carbamide and mercuric chloride, these substances can also be incorporated beforehand, when manufacturing the sensitive layer.-
A few examples of the process according to the invention will be given hereinafter, it being understood that said examples are not limiting.
Example 1.-'1'he following solution is prepared: 200 grams of water, 30 grams of ammonium chlorostannate, 18 grams of silicotungstic acid. A paper bleaching print prepared with basic dyestufls is treated in a bath of this solution, it is washed with water for 5 minutes,.then it is dried. The stability to light of the print will thus' correspond to the initial stability of the basic dyestuffs incorporated, and the tints to the initial colours.
Example Z.A layer of. the solution according to Example 1 is applied on an exposed bleaching out layer. It is dried. The layer is nearly completely desensitized, without changing the tints.
' Example 3.-On an exposed bleaching out layer containing naphtionic red, oxalic acid and diethanolallylsulpho-urea, is spread a solution of. m diacetylamino phenyl trimethylammonium chloride. it is then washed for a few minutes. Perfect fastness to light is obtained. a
Example 4.After exposure a trichroiiie bleaching out layer is treated. containing as dyestuffs only basic dyestuffs and sulphocarbamic derivatives, as sensitizers, first of all in the following bath: 200 grams of water, 10 grams of mercuric chloride, 1 gram of concentrated hydrochloric acid. Then it is washed in the following bath: 1000 grams of water, 50 grams of sulphourea.
. Example 5.A bleaching out layer is prepared as. follows: in 1000 grams of water are dissolved grams of gelatlne, 5 grams of hydrochloric acid, 4 grams of Nile blue sulphate, 6.5 grams of Flavindulin O, 3.5 grams of sulphopyronine G. 100 grams of acetamide and grams of oxalic acid. Then, the mixture of grams of diethylallylsulpho-urea and 25 grams of mercuric chloride which was previously heated with 50 grams of water, is added. It is spread on paper, exposed to light under a negative and the proof is washed for 15 minutes.
We claim Process for stabilizing prints obtained by photographic bleaching of layers containing bleaching dyestuffs and thiourea derivatives,
consisting in eliminating, after exposure of the ANDRE POLGAR. cmanss HALMOS.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR728252X | 1938-12-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
US2319344A true US2319344A (en) | 1943-05-18 |
Family
ID=9111735
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US309482A Expired - Lifetime US2319344A (en) | 1938-12-15 | 1939-12-15 | Process for stabilizing prints obtained by photographic bleaching |
Country Status (4)
Country | Link |
---|---|
US (1) | US2319344A (en) |
DE (1) | DE728252C (en) |
FR (1) | FR847597A (en) |
GB (1) | GB597147A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2855300A (en) * | 1956-08-10 | 1958-10-07 | Chalkley Lyman | Process for fixing images on dye cyanide photosensitized materials |
US3892569A (en) * | 1972-12-04 | 1975-07-01 | Gen Film Dev Corp | Photosensitive sheets comprising organic dyes and sensitizers |
-
1938
- 1938-12-15 FR FR847597D patent/FR847597A/en not_active Expired
-
1939
- 1939-12-09 DE DEP80123D patent/DE728252C/en not_active Expired
- 1939-12-12 GB GB32073/39A patent/GB597147A/en not_active Expired
- 1939-12-15 US US309482A patent/US2319344A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2855300A (en) * | 1956-08-10 | 1958-10-07 | Chalkley Lyman | Process for fixing images on dye cyanide photosensitized materials |
US3892569A (en) * | 1972-12-04 | 1975-07-01 | Gen Film Dev Corp | Photosensitive sheets comprising organic dyes and sensitizers |
Also Published As
Publication number | Publication date |
---|---|
GB597147A (en) | 1948-01-20 |
FR847597A (en) | 1939-10-12 |
DE728252C (en) | 1942-11-23 |
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