US3293036A - Bleach-fix compositions and process for producing colored photographic images - Google Patents
Bleach-fix compositions and process for producing colored photographic images Download PDFInfo
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- US3293036A US3293036A US263391A US26339163A US3293036A US 3293036 A US3293036 A US 3293036A US 263391 A US263391 A US 263391A US 26339163 A US26339163 A US 26339163A US 3293036 A US3293036 A US 3293036A
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- fixing
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- bleach
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- 238000000034 method Methods 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 title description 8
- 239000002253 acid Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 7
- -1 SILVER HALIDE Chemical class 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004061 bleaching Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 3
- 150000002443 hydroxylamines Chemical class 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 230000003019 stabilising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 2
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- ZIUZDRMIXJKUNY-UHFFFAOYSA-N 3-[2-carboxyethyl(ethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC)CCC(O)=O ZIUZDRMIXJKUNY-UHFFFAOYSA-N 0.000 description 1
- NUVIBPSQTHIMKV-UHFFFAOYSA-N 5-(3-heptadecyl-5-oxo-4h-pyrazol-1-yl)-2-phenoxybenzenesulfonic acid Chemical compound O=C1CC(CCCCCCCCCCCCCCCCC)=NN1C(C=C1S(O)(=O)=O)=CC=C1OC1=CC=CC=C1 NUVIBPSQTHIMKV-UHFFFAOYSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FRTNIYVUDIHXPG-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN FRTNIYVUDIHXPG-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 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
- G03C7/421—Additives other than bleaching or fixing agents
Definitions
- the material after development generally is rinsed or treated in a stop fixing bath. Thereafter, the metallic silver formed in the development is oxidised in .a bleach-fixing Ibath. Generally, complexes of trivalent iron or cobalt are used as oxidising agents in this case. The silver compound formed is fixed together with the residual silver halide.
- the rinsing and treatment with the stop-fixing bath between the developing bath and the bleach-fixing bath serves primarily for the removal of the excess developer substance and the alkali from the photographic layer. However, this is generally not achieved completely, so that certain proportions of developer substance pass into the oxidising bleach-fixing bath. In this bath, the developer is oxidised to form products which react with the color couplers incorporated into the photographic layers, so that more especially color fogging occurs in the uppermost layer.
- a bleach-fixing bath in which on the one hand no color fogging occurs and, on the other hand, the density of the cyan dyestuff is not reduced.
- a bleachfixing bat-h having a pH value below 7.0 has the disadvantage that it destroys more cyan dyestuff when fresh than when used.
- the invention has for its object the solution of the last-mentioned problem.
- water-soluble derivatives of these two compounds can also be used for the present purpose.
- Example 1 A multi-layer color photographic material, containing 3-(p-stearylamino lbenzoylacetamino)-isophth-alic acid as a yellow color coupler, 1-(4'-phenoxy-3'sulphophenyl)- 3-heptadecyl-5-pyrazolone as a magenta color coupler and 1-hydroxy-4sulpho-2-naphtho ic acid octadecylamide as a cyan color coupler is developer in a developer having the following composition:
- a color image is obtained without the slightest indication of a color fogging.
- Example 2 The development takes place as indicated in Example 1 and the further processing is effected in a stop-fixing bath with the following composition:
- the immediately following bleach-fixing bath has the following composition:
- the color image obtained is completely free from color fogging.
- the baths according to the invention can have a pH value between 7 and 9 and advantageously between 7.5 and 8.0.
- the bleachfixing bath is advantageously followed by a rinsing and a stabilising bath which has a pH value of approximately 7.
- a rinsing or a stop-fixing bath Interposed between the developing bath and the bleach-fixing bath is a rinsing or a stop-fixing bath, which has a pH value between 7.0 and 9.0, advantageously 7.0 and 8.0, or both.
- suitable bleaching agents comprises complex salts of trivalent iron (German No. 866,605) or cobalt, as de'scnibed, for example, in German No. 9'5 4,475,
- Diethylene triaminepentaacetic acid (HOOCCH NCH CH N- (CH COOH -CH CH N- (CH COOH) 2 Nitrilo-triacetie aoid N-(CH COOH) Ethylaminediprop-ionic acid (bis-(2-carboxyethyl)ethylamine);
- Any water-soluble thiosulphate may be used as fixing agent such as alkali thiosulphates or ammonium thiosulphate.
- the bleach-fixing bath may contain as stabilizing agents any water-soluble sulfite, bisulfiite or metasulfite. Furthermore the bleach-fixing bath may have an additional content of water-soluble iodides according to our copending application Ser. No. 95,735, now abandoned.
- the photographic material which shall the treated according to the invention may be developed by means of any developer composition known per se.
- the pH value of the bleach-fixing bath can be adjusted by the addition of phosphates, carbonates or borates of alkali or alkalineearth metals.
- the reducing agent according to the invention should be added in an amount of between 0.2-5 g. per litre, preferably in an amount of 0.5-3 g. per litre.
- the anion of the hydrazine respectively hydroxylamine salts to be used are not critical. Preferred are salts of the said compounds with acids such as sulphuric acid or hydrochloric acid.
- a process for the production of a photographic image which comprises (a) imagewise exposure of a photographic multilayer color material comprising at least one light-sensitive silver halide emulsion layer which contains a color coupler capable of reacting with an oxidation product of a color-forming developer to form a dye.
- a bleach-fixing bath containing (1) a bleaching agent selected from the group consisting of ferric and cob altic complex salts of a member selected from the group consisting of hydroxypolycarboxylic and aminopolycarboxylic acids, (2) a fixing agent consisting of a water-soluble salt of thiosulfuric acid, said fixing bath having a pH value of between 7 and 9,
- the improvement according to which the simultaneously bleaching and fixing is accomplished in efiective contact with a reducing agent selected from the class consisting of a hydrazine salt, a water-soluble ihydroxylamine salt and formamidine-sulphinic acid.
- a reducing agent selected from the class consisting of a hydrazine salt, a water-soluble ihydroxylamine salt and formamidine-sulphinic acid.
- a composition for the simultaneous bleaching and fixing of an exposed and developed photographic color material comprising at least one light-sensitive silver halide emulsion layer which contains a color coupler capable of reacting with an oxidation product of a colorforming developer-to form a dye, which contains (1) a bleaching agent of the group consisting of ferric and co'baltic complex salts of a member selected from the group consisting of hydroxynolvcar-boxylic and aminopolycarboxylic acids,
- a fixing agent consisting of a water-soluble salt of thiosulfuric acid
- a reducing agent selected from the class consisting of a hydrazine salt, a water-soluble hydroxylamine salt and a formamidine-sulphinic acid in an amount of between 0.2 and 5 g. per liter of the composition.
- composition as'defined in claim 3 containing the ferric complex salt of ethylenediaminetetraacetic acid as 6 bleaching agent (I) and sodium thiosulfate as the fixing 768,401 2/1957 Great Britain. agent (II). 774,194 5/ 1957 Great Britain.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
United States Patent M 4 Claims. (or. 96-60) This invention relates to an improved processing for exposed color photographic materials, in which bleachfixing baths and also stop-fixing baths are used, which baths contain reducing agents.
In the conventional processing of exposed color photographic materials, the material, after development generally is rinsed or treated in a stop fixing bath. Thereafter, the metallic silver formed in the development is oxidised in .a bleach-fixing Ibath. Generally, complexes of trivalent iron or cobalt are used as oxidising agents in this case. The silver compound formed is fixed together with the residual silver halide.
The rinsing and treatment with the stop-fixing =bath between the developing bath and the bleach-fixing bath serves primarily for the removal of the excess developer substance and the alkali from the photographic layer. However, this is generally not achieved completely, so that certain proportions of developer substance pass into the oxidising bleach-fixing bath. In this bath, the developer is oxidised to form products which react with the color couplers incorporated into the photographic layers, so that more especially color fogging occurs in the uppermost layer.
This fogging can be prevented if the pH value of the processing baths following the developer bath are adjusted to a value of 7, so that no coupling can occur. This applies more especially in respect of the bleach-fixing bath, of which the pH values can be between 6.3 and 7. In these bleach-fixing baths, however, a serious disadvantage arises, namely that the cyan dyestuffs, which are formed by coupling of a naphthol derivative with the oxidation product of a p-iphenylene diamine derivative, are partially destroyed, the amount destroyed depending on the Redox potential value of the respective bath and the destruction being stronger as the pH value of the bath is lower.
Accordingly, only a very narrow pH range exists for a bleach-fixing bath, in which on the one hand no color fogging occurs and, on the other hand, the density of the cyan dyestuff is not reduced. In addition, a bleachfixing bat-h having a pH value below 7.0 has the disadvantage that it destroys more cyan dyestuff when fresh than when used.
The aforementioned disadvantages could therefore be avoided either by working at pH values below 7 and preventing the retrogression of the cyan image with suitable additives or other measures, or by working at pH values above 7 and suppressing the formation of a color fogging by introducing additives.
The invention has for its object the solution of the last-mentioned problem.
It has now been found that it is possible to work without disadvantageous consequences with bleach-fixing baths 3,293,036 Patented Dec. 20, 1966 and/or stop-fixing baths, etc., which have a pH value above 7, if certain reducing agents are added to these alkali baths. After numerous known reducing agents have proved to be inoperative, it was surprisingly found that hydrazine salts, hydroxyl ammonium salts and formarnidine-sulphinic acid completely prevent the formation of color fogging. The substances used according to the invention are used in quantities of advantageously 0.2 to 5 g. per litre of aqueous processing bath. The compounds can either be added to the bleach-fixing bath or to other baths which are used in the processing step between the developer and the bleach-fixing bath, for example, stop-baths or stop-fixing baths.
In addition to simple hydrazine or hydroxyl ammonium salts, the water-soluble derivatives of these two compounds can also be used for the present purpose.
With this method of processing, the cyan dyestuif is maintained fully and, in addition, the thiosulphate of the alkaline bleach-fixing bath is washed out during the subsequent rinsing in a shorter time than when using acid bleach-fixing baths. Moreover, by using an alkaline stop-fixing bath, any damage to the layer due to carbon dioxide being liberated, which damage can occur in acid stop-bath or stop-fixing baths, is avoided.
Example 1 A multi-layer color photographic material, containing 3-(p-stearylamino lbenzoylacetamino)-isophth-alic acid as a yellow color coupler, 1-(4'-phenoxy-3'sulphophenyl)- 3-heptadecyl-5-pyrazolone as a magenta color coupler and 1-hydroxy-4sulpho-2-naphtho ic acid octadecylamide as a cyan color coupler is developer in a developer having the following composition:
G. Sodium hexametaphosphate 2 Hydroxylamine sulphate 4 Anhydrous sodium sulphite 4 Potassium bromide 1 Anhydrous potassium carbonate N-butyl-w-sulphobutyl-p araphenylene diamine 5 Made up with water to 1000 cc The material is then treated in the following stop-fixing bath:
G. Sodium hexametaphosphate 2 Potassium d-ihydrogen phosphate 30 Anhydrous sodium sulphite 4 Anhydrous sodium thiosulphate 100 Thiosemicarbazide 3 Hydrazine sulphate 2 adjusted with potassium carbonate to pH=8.0 and made up with water to 1000 cc.; then immediately in the following bleach-fixing bath:
G. Tr-isodium ethylendiamine tetraacetic acid 30 Disodium hydrogen phosphate 15 Iron salt of ethylene diamine tetraacetic acid 30 Anhydrous sodium sulphite 2 Thiosemicarbazide 3 Anhydrous sodium thiosulphate Hydrazine sulphate 2 adjusted with potassium carbonate to pH=8.0 and made up with water to 1000 cc.
The material is then rinsed, and after treatment with a formalin-containing stabilising bath of pH=7.0 it is dried.
A color image is obtained without the slightest indication of a color fogging.
Example 2 The development takes place as indicated in Example 1 and the further processing is effected in a stop-fixing bath with the following composition:
G. Sodium hexametap'hosphate 2 Potassium dihydrogen phosphate 30 Anhydrous sodium sulphite 4 Anhydrous sodium th iosulphate 100 Thiosemicanbazide 3 Hydroxyl ammonium sulphate 5 adjusted with potassium carbonate to pH=8.0 and made up with Water to 1000 cc.
The immediately following bleach-fixing bath has the following composition:
adjusted with potassium carbonate to pH=8.0 and made up with water to 1000 cc.
The material is then rinsed and, after treatment with a formalin-containing stabilising bath of pH==7 .0, the material is dried.
The color image obtained is completely free from color fogging.
The same result is obtained if the hydrazine or hydroxyl ammonium sulphate in the aforementioned example is replaced by formamidine sulphinic acid.
The baths according to the invention can have a pH value between 7 and 9 and advantageously between 7.5 and 8.0.
In the process according to the invention, the bleachfixing bath is advantageously followed by a rinsing and a stabilising bath which has a pH value of approximately 7. Interposed between the developing bath and the bleach-fixing bath is a rinsing or a stop-fixing bath, which has a pH value between 7.0 and 9.0, advantageously 7.0 and 8.0, or both.
Having thus described our invention we now state that we believe our invention to be capable of numerous variations. For example suitable bleaching agents comprises complex salts of trivalent iron (German No. 866,605) or cobalt, as de'scnibed, for example, in German No. 9'5 4,475,
preferably with hydr-oxypolycarboxylic and aminopolycarboxylic acids, are eifect-ive as bleaching agents. Complex salts of trivalent iron with aminopolycarboxylic acids such as with the following acids are particularly preferred.
Ethylenediaminetetraacetic acid;
Diethylene triaminepentaacetic acid; (HOOCCH NCH CH N- (CH COOH -CH CH N- (CH COOH) 2 Nitrilo-triacetie aoid N-(CH COOH) Ethylaminediprop-ionic acid (bis-(2-carboxyethyl)ethylamine);
H C N CH CH CO0H) 2 Any water-soluble thiosulphate may be used as fixing agent such as alkali thiosulphates or ammonium thiosulphate. The bleach-fixing bath may contain as stabilizing agents any water-soluble sulfite, bisulfiite or metasulfite. Furthermore the bleach-fixing bath may have an additional content of water-soluble iodides according to our copending application Ser. No. 95,735, now abandoned.
Moreover it is clear to those skilled in the art that the photographic material which shall the treated according to the invention may be developed by means of any developer composition known per se. The pH value of the bleach-fixing bath can be adjusted by the addition of phosphates, carbonates or borates of alkali or alkalineearth metals. The reducing agent according to the invention should be added in an amount of between 0.2-5 g. per litre, preferably in an amount of 0.5-3 g. per litre. The anion of the hydrazine respectively hydroxylamine salts to be used are not critical. Preferred are salts of the said compounds with acids such as sulphuric acid or hydrochloric acid.
We claim:
1. In a process for the production of a photographic image which comprises (a) imagewise exposure of a photographic multilayer color material comprising at least one light-sensitive silver halide emulsion layer which contains a color coupler capable of reacting with an oxidation product of a color-forming developer to form a dye.
(b) developing the said material to form a silver and a color image, and (c) simultaneously bleaching and fixing the said developed material to remove the silver image from the light-struck areas and the silver halide from the areas not struck by light by a bleach-fixing bath containing (1) a bleaching agent selected from the group consisting of ferric and cob altic complex salts of a member selected from the group consisting of hydroxypolycarboxylic and aminopolycarboxylic acids, (2) a fixing agent consisting of a water-soluble salt of thiosulfuric acid, said fixing bath having a pH value of between 7 and 9,
the improvement according to which the simultaneously bleaching and fixing is accomplished in efiective contact with a reducing agent selected from the class consisting of a hydrazine salt, a water-soluble ihydroxylamine salt and formamidine-sulphinic acid.
2. A process as defined in claim 1 in which the bleachfixing bath contains the said reducing agent in an amount of 0.2-5 g. per liter.
3. A composition for the simultaneous bleaching and fixing of an exposed and developed photographic color material comprising at least one light-sensitive silver halide emulsion layer which contains a color coupler capable of reacting with an oxidation product of a colorforming developer-to form a dye, which contains (1) a bleaching agent of the group consisting of ferric and co'baltic complex salts of a member selected from the group consisting of hydroxynolvcar-boxylic and aminopolycarboxylic acids,
(2) a fixing agent consisting of a water-soluble salt of thiosulfuric acid, and
(3) a reducing agent selected from the class consisting of a hydrazine salt, a water-soluble hydroxylamine salt and a formamidine-sulphinic acid in an amount of between 0.2 and 5 g. per liter of the composition.
4. A composition as'defined in claim 3 containing the ferric complex salt of ethylenediaminetetraacetic acid as 6 bleaching agent (I) and sodium thiosulfate as the fixing 768,401 2/1957 Great Britain. agent (II). 774,194 5/ 1957 Great Britain.
777,635 6/1957 Great Britain. References Cited by the Examiner 6 G. Primary Examiner.
14 3 2 10 195 G A. D. RICCI, Assistant Examiner.
Claims (1)
1. IN A PROCESS FOR THE PRODUCTION OF A PHOTOGRAPHIC IMAGE WHICH COMPRISES (A) IMAGEWISE EXPOSURE OF A PHOTOGRAPHIC MULTILAYER COLOR MATERIAL COMPRISING AT LEAST ONE LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER WHICH CONTAINS A COLOR COUPLER CAPABLE OF REACTING WITH AN OXIDATION PRODUCT OF A COLOR-FORMING DEVELOPER TO FROM A DYE, (B) DEVELOPING THE SAID MATERIAL TO FORM A SILVER AND A COLOR IMAGE, AND (C) SIMULTANEOUSLY BLEACHING AND FIXING THE SAID DEVELOPED MATERIAL TO REMOVE THE SILVER IMAGE FROM THE LIGHT-STRUCT AREAS AND THE SILVER HALIDE FROM THE AREAS NOT STRUCK BY LIGHT BY A BLEACH-FIXING BATH CONTRAINING (1) A BLEACHING AGENT SELECTED FROM THE GROUP CONSISTING OF FERRIC AND COBALTIC COMPLEX SALTS OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROXYPOLYCARBOXYLIC AND AMINOPOLYCARBOXYLIC ACIDS, (2) A FIXING AGENT CONSISTING OF A WATER-SOLUBLE SALT OF THIOSULFURIC ACID, SAID FIXING BATH HAVING A PH VALUE OF BETWEEN 7 TO 9, THE IMPROVEMENT ACCORDING TO WHICH THE SIMULTANEOUSLY BLEACHING THE FIXING IS ACCOMPLISHED IN EFFECTIVE CONTACT WITH A REDUCING AGENT SELECTED FROM THE CLASS CONSISTING OF A HYDRAZINE SALT, A WATER-SOLUBLE HYDROXYLAMINE SALT AND FORMAMIDINE-SULPHINIC ACID.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA39881A DE1155980B (en) | 1962-04-05 | 1962-04-05 | Process for producing color photographic images by the color development process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3293036A true US3293036A (en) | 1966-12-20 |
Family
ID=6931630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US263391A Expired - Lifetime US3293036A (en) | 1962-04-05 | 1963-03-07 | Bleach-fix compositions and process for producing colored photographic images |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3293036A (en) |
| BE (1) | BE630320A (en) |
| CH (1) | CH433982A (en) |
| DE (1) | DE1155980B (en) |
| GB (1) | GB988967A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3607277A (en) * | 1967-10-14 | 1971-09-21 | Agfa Gevaert Ag | Photographic viscous processing |
| JPS4852233A (en) * | 1971-11-01 | 1973-07-23 | ||
| US3931004A (en) * | 1972-04-21 | 1976-01-06 | Fuji Photo Film Co., Ltd. | Method of treating waste liquids from photographic processings |
| US4518680A (en) * | 1983-02-17 | 1985-05-21 | Konishiroku Photo Industry Co., Ltd. | Bleach-fixing solution and processing of light-sensitive color photographic material by use thereof |
| US4828970A (en) * | 1986-04-18 | 1989-05-09 | Konishiroku Photo Industry Co., Ltd. | Method for processing a light-sensitive silver halide color photographic material by controlling the pH value of the bleach fixing solution |
| US5006456A (en) * | 1987-06-08 | 1991-04-09 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic light-sensitive materials using sulphinc acids and salts or their precursors |
| WO2001050196A1 (en) * | 2000-01-06 | 2001-07-12 | Trebla Chemical Company | One-part bleach-fix liquid concentrates |
| EP1160622A1 (en) * | 2000-05-27 | 2001-12-05 | Agfa-Gevaert N.V. | A bleach-fixing concentrate |
| US6455236B1 (en) * | 2000-01-06 | 2002-09-24 | Trebla Chemical Company | One-part bleach-fix liquid concentrates |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE14362C (en) * | C. MULLER in Fulda | Dobby for high and low shed | ||
| GB768401A (en) * | 1955-01-31 | 1957-02-13 | Leonar Werke Ag | Improvements in or relating to simultaneously developing and fixing or stabilizing photographic silver halide emulsions |
| GB774194A (en) * | 1954-06-19 | 1957-05-08 | Photo Chemical Company Ltd | Improvements in photographic bleach-fix baths |
| GB777635A (en) * | 1954-03-11 | 1957-06-26 | Gevaert Photo Prod Nv | Improvements in or relating to a process for simultaneously bleaching and fixing a photographic colour image |
-
0
- BE BE630320D patent/BE630320A/xx unknown
-
1962
- 1962-04-05 DE DEA39881A patent/DE1155980B/en active Pending
-
1963
- 1963-03-07 US US263391A patent/US3293036A/en not_active Expired - Lifetime
- 1963-03-12 CH CH312763A patent/CH433982A/en unknown
- 1963-03-27 GB GB12132/63A patent/GB988967A/en not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE14362C (en) * | C. MULLER in Fulda | Dobby for high and low shed | ||
| GB777635A (en) * | 1954-03-11 | 1957-06-26 | Gevaert Photo Prod Nv | Improvements in or relating to a process for simultaneously bleaching and fixing a photographic colour image |
| GB774194A (en) * | 1954-06-19 | 1957-05-08 | Photo Chemical Company Ltd | Improvements in photographic bleach-fix baths |
| GB768401A (en) * | 1955-01-31 | 1957-02-13 | Leonar Werke Ag | Improvements in or relating to simultaneously developing and fixing or stabilizing photographic silver halide emulsions |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3607277A (en) * | 1967-10-14 | 1971-09-21 | Agfa Gevaert Ag | Photographic viscous processing |
| JPS4852233A (en) * | 1971-11-01 | 1973-07-23 | ||
| US3931004A (en) * | 1972-04-21 | 1976-01-06 | Fuji Photo Film Co., Ltd. | Method of treating waste liquids from photographic processings |
| US4518680A (en) * | 1983-02-17 | 1985-05-21 | Konishiroku Photo Industry Co., Ltd. | Bleach-fixing solution and processing of light-sensitive color photographic material by use thereof |
| US4828970A (en) * | 1986-04-18 | 1989-05-09 | Konishiroku Photo Industry Co., Ltd. | Method for processing a light-sensitive silver halide color photographic material by controlling the pH value of the bleach fixing solution |
| US5006456A (en) * | 1987-06-08 | 1991-04-09 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic light-sensitive materials using sulphinc acids and salts or their precursors |
| WO2001050196A1 (en) * | 2000-01-06 | 2001-07-12 | Trebla Chemical Company | One-part bleach-fix liquid concentrates |
| US6455236B1 (en) * | 2000-01-06 | 2002-09-24 | Trebla Chemical Company | One-part bleach-fix liquid concentrates |
| EP1160622A1 (en) * | 2000-05-27 | 2001-12-05 | Agfa-Gevaert N.V. | A bleach-fixing concentrate |
| US20040058283A1 (en) * | 2000-05-27 | 2004-03-25 | Gustav Tappe | Bleach-fixing concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| BE630320A (en) | |
| CH433982A (en) | 1967-04-15 |
| GB988967A (en) | 1965-04-14 |
| DE1155980B (en) | 1963-10-17 |
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