US3702247A - Color photographic process using a bleach-fix solution containing a selenosulfate - Google Patents
Color photographic process using a bleach-fix solution containing a selenosulfate Download PDFInfo
- Publication number
- US3702247A US3702247A US105955A US3702247DA US3702247A US 3702247 A US3702247 A US 3702247A US 105955 A US105955 A US 105955A US 3702247D A US3702247D A US 3702247DA US 3702247 A US3702247 A US 3702247A
- Authority
- US
- United States
- Prior art keywords
- bleach
- fix
- silver
- bath
- colour
- 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 abstract description 10
- 229910052709 silver Inorganic materials 0.000 abstract description 44
- 239000004332 silver Substances 0.000 abstract description 44
- 239000000463 material Substances 0.000 abstract description 39
- -1 COLOUR SILVER HALIDE Chemical class 0.000 abstract description 24
- 239000007800 oxidant agent Substances 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 13
- ORWQBKPSGDRPPA-UHFFFAOYSA-N 3-[2-[ethyl(methyl)amino]ethyl]-1h-indol-4-ol Chemical compound C1=CC(O)=C2C(CCN(C)CC)=CNC2=C1 ORWQBKPSGDRPPA-UHFFFAOYSA-N 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 22
- 239000007844 bleaching agent Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- 239000000975 dye Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000004697 chelate complex Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 6
- UOMQUZPKALKDCA-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UOMQUZPKALKDCA-UHFFFAOYSA-K 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- CJCPHQCRIACCIF-UHFFFAOYSA-L disodium;dioxido-oxo-selanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=[Se] CJCPHQCRIACCIF-UHFFFAOYSA-L 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 4
- PBKADZMAZVCJMR-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;dihydrate Chemical compound O.O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O PBKADZMAZVCJMR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YNPKJCSIKJCODK-UHFFFAOYSA-N disodium boric acid hydrogen borate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OB(O)O.OB(O)O.OB(O)O.OB([O-])[O-] YNPKJCSIKJCODK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- URAJEEIDMHNVKE-UHFFFAOYSA-N (2-amino-4-methylphenyl) hydrogen sulfate Chemical compound CC1=CC=C(OS(O)(=O)=O)C(N)=C1 URAJEEIDMHNVKE-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- QBZGAULXCVZXFL-UHFFFAOYSA-N 2,3-dimethylquinoxalin-6-amine Chemical compound C1=C(N)C=C2N=C(C)C(C)=NC2=C1 QBZGAULXCVZXFL-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000001429 visible spectrum 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
- 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
- This invention relates to the processing of photographic material comprising silver halide emulsion layers to yield material having colour dye images therein.
- a developable silver salt image is developed with an aromatic primary amino developing agent of the paraphenylene diamine type (a so-called colour developer) in the presence of a compound (a so-called colour coupler) which will combine with the oxidation products of the color developer to form an azomethine or quinone-imine dye.
- the dye is thus formed in situ with the developed silver image.
- the product must be treated with a bleach bath and a fixing bath or a combined bleach-fix bath thereby to remove silver and any residual silver halide or other silver salt, leaving in the product only the dye image.
- the photographic material comprises at least one silver halide emulsion layer which includes as a dispersion therein an organic dyestulf of the type which can be destroyed (or bleached) by finely divided silver in a suitable treatment bath.
- the organic dyestulf is usually an azo dye.
- Most commonly three such silver halide emulsion layers are present each of which is sensitive to a different region of the visible spectrum and each of which contains a different azo dye.
- the usual processing sequence for the production of a dye image in the material is after an imagewise exposure to develop the material in a black and white developer. The development is then stopped and the unexposed silver halide is fixed out.
- the material is treated in a dye-bleach bath which oxidises the silver image and simultaneously reduces (bleaches) the dye in the region of the silver image.
- the silver salts and any residual silver must then be removed. This is usually accomplished by washing the material after its treatment in the dye-bleach bath and then treating it in a bleach bath followed by a fixing bath or treating it in a combined bleach-fix bath.
- the photographic material then contains a dye image only; this dye image being usually a direct positive reproduction of the original.
- the amount of residual silver left after the dyebleach step is not negligible because this material requires to be processed so that the dye-bleach step is terminated before all the image silver has been used in reducing the dye.
- an effective silver bleach step succeeds the dye-bleach step in order to ensure that the residual silver is removed as completely as possible from the material.
- a bleach-fix bath comprises a mild oxidising agent for example a ferric chelate complex, a cup'ric complex a salt or a cobalt (III) complex together with a silver halide solvent or fixing agent for example a water-soluble thiosulphate or a water-soluble thiocyanate.
- a mild oxidising agent for example a ferric chelate complex, a cup'ric complex a salt or a cobalt (III) complex
- a silver halide solvent or fixing agent for example a water-soluble thiosulphate or a water-soluble thiocyanate.
- Strong oxidising agents cannot be used because they tend to oxidise the silver halide solvent.
- Sta'ble bleach-fix solutions comprising ferric chelate complexes and sodium thiosulphate may be obtained but because of the weak oxidising power of the ferric chelate complex such bleach-fix baths can only be used commercially for the processing of photographic materials with a fairly low silver content.
- a bleach-fix step which comprises treating the photographic material with a stable bleach-fix bath which comprises an aqueous solution of a mild oxidising agent and a silver halide solvent which is either a water-soluble thiosulphate or a water-soluble thiocyanate in the presence of a bleach-fix accelerator which is a water-soluble selenosulphate of the general formula MSeSO where M is a divalent metal ion, or two monovalent meta ions, or two quarternary ammonium groups or two substituted quaternary ammonium groups.
- stable bleach-fix bath which comprises an aqueous solution of a mild oxidising agent and a silver halide solvent is meant a bleach-fix bath wherein the oxidising agent is strong enough to bleach the silver but is not strong enough to oxidise the silver halide solvent, i.e. the thiocyanate or the thiosulphate, to an appreciable degree.
- the preferred mild oxidising agents for use in the present invention are ferric chelate complexes or diaquotetrammine-cobalt (III) complexes.
- ferric chelate complex is meant a co-ordination compound of the ferric ion and a compound which comprises nitrogen and/or oxygen-containing co-ordinating groups.
- the most important co-ordinating groups are amino, heterocyclic nitrogen, carboxyl and carbonyl groups.
- the preferred ferric chelate complex for use in the bleach-fix step of the present invention is a ferric ethylenediaminetetraacetic acid complex. Itis to be understood that this compound may be used as such in the preparation of a bleach-fix bath or it may he formed in situ in a bleach-fix bath by ethylenediaminetetraacetic acid reacting with a ferric salt e.g. ferric chloride. In the examples which follow the ferric ethylenediaminetetraacetic acid complex has been formed in situ.
- ferric chelate complexes which may be used in the present invention are for example pyridine-2:6-dicarboxylatoferrate (III) complex, iminodiacetatoferrate (III) complex and nitrilo-triacetateferrate (III) complex.
- the alkali metal selenosulfates may be prepared by dissolving elemental selenium in alkaline sulphite solution. Crystalline alkali metal selenosulphate may be obtained from this solution or this solution may be used as such, i.e. a quantity of this solution may be added to the bath which is to contain the selenosulphate.
- the bleach-fix accelerators of use in the present invention are preferably added to the bleach-fix bath but they may be present during the bleach-fixing treatment adsorbed to or absorbed in the colour photographic material.
- the bleach-fix accelerators of use in the present invention may be present in any treatment bath or wash bath which is used in the colour development process between the development step and the bleach-fix step. Exemplary of such baths are stop baths and stop-fix baths.
- the bleach-fix accelerators should not be present, however, in the developing solution as they interfere with the development of the colour material. For the same reason the bleach-fix accelerators of use in the present invention should not be present initially in the photographic material.
- the bleach-fix accelerators may be present in the wash bath which succeeds the dye-bleach treatment bath and precedes the bleach-fix bath but the bleach-fix accelerators should not be present during the dye-bleach treatment as they can interfere with this treatment step. Thus the bleach fix accelerators should not be present initially in the silver-dye-bleach photographic material.
- a stable bleach-fix bath which comprises a mild oxidising agent, as hereinbefore defined, a silver halide solvent which is either a water-soluble thiosulphate or a water-soluble thiocyanate and a water-sob uble selenosulphate as a bleach-fix accelerator.
- the mild oxidizing agent is a ferric chelate complex or a diaquotetramine-cobalt (III) complex.
- the concentration of selenosulphate present in the bleach-fix bath is greater than 1 g. per litre of bleach-fix bath. The most preferred amount being g. of bleach-fix accelerator per litre of bleach-fix bath.
- the blue sensitive layer contained a yellow colour coupler of the formula:
- the processing sequence was:
- EXAMPLE 2 A positive tripack colour material intended for the silver dye-bleach system comprising silver halide emulsions containing bleachable azo-dyes Cibachrome manufactured by Ciba-Geigy A.G. of Switzerland was given a neutral wedge exposure and processed, the processing sequence being as follows:
- Dye-bleach 20 minutes Sulphuric acid, 96% ml 27.5 Potassium iodide g 10 Solution of 0.3 g. 2,3-dimethyl-6-aminoquinoxaline in 50 ml ethnol ml Water to 1 litre.
- a stable bleach-fix bath which comprises an aqueous solution of a mild oxidising agent and a silver halide solvent which is either a water-soluble thiosulphatc or a water-soluble thiocyanate in the presence of a bleach-fix accelerator which is water-soluble selenosulphate of the formula MSeSO where M is two sodium ions, said oxidising agent being one which is strong enough to bleach the silver but is not strong enough to oxidise the silver halide solvent.
- ferric chelate complex is ferric ethylenediaminetetraacetic acid complex.
- a stable bleach-fix bath which comprises an aqueous solution of a mild oxidising agent, a silver halide solvent which is either a water-soluble thiosulphate or a water-soluble thiocyanate and a water-soluble bleach-fix accelerator which is a selenosulphate of the general formula MSeSO where M is two sodium ions, said oxidising agent being one which is strong enough to bleach the silver but is not strong enough to oxidise the silver halide solvent.
- a stable bleach-fix bath according to claim 6 wherein the ferric chelate complex is ferric ethylenediaminetetraacetic acid complex.
- a stop-fix bath which comprises an aqueous acid solution of a silver halide solvent selected from a watersoluble thiosulphate or a water-soluble thiocyanate and a water-soluble bleach-fix accelerator which is a selenosulphate of the general formula MSeSO where M is two sodium ions.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
THIS APPLICATION DESCRIBES A COLOUR DEVELOPMENT PROCESS FOR COLOUR SILVER HALIDE PHOTOGRAPHIC MATERIAL, WHEREIN THE MATERIAL AFTER DEVELOPMENT IS TREATED WITH A BLEACHFIX SOLUTION WHICH CONTAINS A MILD OXIDISING AGENT, A SILVER HALIDE SOLVENT AND AS A BLEACH-FIX ACCELERATOR A WATERSOLUBLE SPECIFIED SELENOSULFATE.
Description
United States Patent Oflice 3,702,247 Patented Nov. 7, 1972 3,702,247 COLOR PHOTOGRAPHIC PROCESS USING A BLEACH-FIX SOLUTION CONTAINING A SELENOSULFATE Alun Trefor Rhys Williams and David Gerald Alcock, Ilford, England, assignors to Ilford Limited, Ilford, Essex, England No Drawing. Filed Jan. 12, 1971, Ser. No. 105,955 Claims priority, application Great Britain, Jan. 13, 1970, 1,616/70 Int. Cl. G03c 7/00 US. Cl. 96-55 9 Claims ABSTRACT OF THE DISCLOSURE This application describes a colour development process for colour silver halide photographic material, wherein the material after development is treated with a bleachfix solution which contains a mild oxidising agent, a silver halide solvent and as a bleach-fix accelerator a watersoluble specified selenosulfate.
This invention relates to the processing of photographic material comprising silver halide emulsion layers to yield material having colour dye images therein.
In the processing of conventional colour photographic material a developable silver salt image is developed with an aromatic primary amino developing agent of the paraphenylene diamine type (a so-called colour developer) in the presence of a compound (a so-called colour coupler) which will combine with the oxidation products of the color developer to form an azomethine or quinone-imine dye. The dye is thus formed in situ with the developed silver image. Subsequently the product must be treated with a bleach bath and a fixing bath or a combined bleach-fix bath thereby to remove silver and any residual silver halide or other silver salt, leaving in the product only the dye image.
In the silver-dye-bleach process of colour photography the photographic material comprises at least one silver halide emulsion layer which includes as a dispersion therein an organic dyestulf of the type which can be destroyed (or bleached) by finely divided silver in a suitable treatment bath. The organic dyestulf is usually an azo dye. Most commonly three such silver halide emulsion layers are present each of which is sensitive to a different region of the visible spectrum and each of which contains a different azo dye. The usual processing sequence for the production of a dye image in the material is after an imagewise exposure to develop the material in a black and white developer. The development is then stopped and the unexposed silver halide is fixed out. Then after washing the material is treated in a dye-bleach bath which oxidises the silver image and simultaneously reduces (bleaches) the dye in the region of the silver image. The silver salts and any residual silver must then be removed. This is usually accomplished by washing the material after its treatment in the dye-bleach bath and then treating it in a bleach bath followed by a fixing bath or treating it in a combined bleach-fix bath. The photographic material then contains a dye image only; this dye image being usually a direct positive reproduction of the original.
In one commercially available silver-dye-bleach material the amount of residual silver left after the dyebleach step is not negligible because this material requires to be processed so that the dye-bleach step is terminated before all the image silver has been used in reducing the dye. Thus in the processing of this silver-dyebleach material in particular it is essential that an effective silver bleach step succeeds the dye-bleach step in order to ensure that the residual silver is removed as completely as possible from the material.
In both the processing of conventional colour photographic material and in the processing of silver-dyebleach material the use of a combined bleach-fix bath is preferable because it results in a reduction of the processing time and of the cost of processing equipment required. Normally a bleach-fix bath comprises a mild oxidising agent for example a ferric chelate complex, a cup'ric complex a salt or a cobalt (III) complex together with a silver halide solvent or fixing agent for example a water-soluble thiosulphate or a water-soluble thiocyanate. Strong oxidising agents cannot be used because they tend to oxidise the silver halide solvent.
Sta'ble bleach-fix solutions comprising ferric chelate complexes and sodium thiosulphate may be obtained but because of the weak oxidising power of the ferric chelate complex such bleach-fix baths can only be used commercially for the processing of photographic materials with a fairly low silver content.
According to the present invention in the processing of colour photographic material comprising silver halide emulsion layers to yield material having colour dye images therein there is provided a bleach-fix step which comprises treating the photographic material with a stable bleach-fix bath which comprises an aqueous solution of a mild oxidising agent and a silver halide solvent which is either a water-soluble thiosulphate or a water-soluble thiocyanate in the presence of a bleach-fix accelerator which is a water-soluble selenosulphate of the general formula MSeSO where M is a divalent metal ion, or two monovalent meta ions, or two quarternary ammonium groups or two substituted quaternary ammonium groups.
By stable bleach-fix bath which comprises an aqueous solution of a mild oxidising agent and a silver halide solvent is meant a bleach-fix bath wherein the oxidising agent is strong enough to bleach the silver but is not strong enough to oxidise the silver halide solvent, i.e. the thiocyanate or the thiosulphate, to an appreciable degree.
The preferred mild oxidising agents for use in the present invention are ferric chelate complexes or diaquotetrammine-cobalt (III) complexes.
By ferric chelate complex is meant a co-ordination compound of the ferric ion and a compound which comprises nitrogen and/or oxygen-containing co-ordinating groups. The most important co-ordinating groups are amino, heterocyclic nitrogen, carboxyl and carbonyl groups.
The preferred ferric chelate complex for use in the bleach-fix step of the present invention is a ferric ethylenediaminetetraacetic acid complex. Itis to be understood that this compound may be used as such in the preparation of a bleach-fix bath or it may he formed in situ in a bleach-fix bath by ethylenediaminetetraacetic acid reacting with a ferric salt e.g. ferric chloride. In the examples which follow the ferric ethylenediaminetetraacetic acid complex has been formed in situ.
Other ferric chelate complexes which may be used in the present invention are for example pyridine-2:6-dicarboxylatoferrate (III) complex, iminodiacetatoferrate (III) complex and nitrilo-triacetateferrate (III) complex.
The alkali metal selenosulfates may be prepared by dissolving elemental selenium in alkaline sulphite solution. Crystalline alkali metal selenosulphate may be obtained from this solution or this solution may be used as such, i.e. a quantity of this solution may be added to the bath which is to contain the selenosulphate.
The bleach-fix accelerators of use in the present invention are preferably added to the bleach-fix bath but they may be present during the bleach-fixing treatment adsorbed to or absorbed in the colour photographic material. In the processing of conventional colour photographic material i.e. colour negative or colour reversal material the bleach-fix accelerators of use in the present invention may be present in any treatment bath or wash bath which is used in the colour development process between the development step and the bleach-fix step. Exemplary of such baths are stop baths and stop-fix baths. The bleach-fix accelerators should not be present, however, in the developing solution as they interfere with the development of the colour material. For the same reason the bleach-fix accelerators of use in the present invention should not be present initially in the photographic material.
In the processing of silver-dye-bleach material the bleach-fix accelerators may be present in the wash bath which succeeds the dye-bleach treatment bath and precedes the bleach-fix bath but the bleach-fix accelerators should not be present during the dye-bleach treatment as they can interfere with this treatment step. Thus the bleach fix accelerators should not be present initially in the silver-dye-bleach photographic material.
According to another embodiment of the present invention there is provided a stable bleach-fix bath which comprises a mild oxidising agent, as hereinbefore defined, a silver halide solvent which is either a water-soluble thiosulphate or a water-soluble thiocyanate and a water-sob uble selenosulphate as a bleach-fix accelerator.
Preferably in this aspect of the invention the mild oxidizing agent is a ferric chelate complex or a diaquotetramine-cobalt (III) complex.
It is preferred that the concentration of selenosulphate present in the bleach-fix bath is greater than 1 g. per litre of bleach-fix bath. The most preferred amount being g. of bleach-fix accelerator per litre of bleach-fix bath.
The following examples will serve to illustrate the invention.
EXAMPLE 1 In this example a colour negative film was used, which was made up as follows:
Layer order and Silver coating weight in sensitivity: mg. of Ag/decimetre Non Blue sensitive 13.4 Colloidal silver filler layer Green sensitive topcoat 13.1 Intralayer Green sensitive subcoat 16.0 Interlayer Red sensitive topcoat 175 Red sensitive subcoat 13.6
Base of cellulose triacetate Total 73.6
In this film: the blue sensitive layer contained a yellow colour coupler of the formula:
N-C Ha the green sensitive layers each contained a magenta colour coupler of the formula:
@ Q (ii-Ca as 0 the red sensitive layers each contained a cyan colour coupler for the formula:
Cg: /C1sHa1 OH I? l C ONH COzH Samples from a batch of this colour negative tripack material (which is of the colour coupler substantive type) containing 73.6 mg. of silver per dm. as silver iodobromide emulsion were fogged and processed at 24 C.
The processing sequence was:
Colour development: 6 minutes G. Sodium metaborate 53.3 Sodium hydroxide 2.0 Sodium sulphite anhydrous 3.9 Potassium bromide 0.70 Hydroxylamine sulphate 2.34 Sodium sulphate anhydrous 7.8 4 amino N ethyl N (4 hydroxybutyl) aniline sulphate Water to 1 litre. pH 10.5.
Stop-fix: 4 minutes Sodium thiosulphate pentahydrate g 171.0 Sodium acetate anhydrous g 31.4 Sodium sulphite anhydrous g 4.3 Acetic acid (glacial) ml Potassium alum g 17.0 Ammonium chloride g 43.0 Water to 1 litre. pH 4.3.
Wash: 4 minutes Bleach-fix: minutes Disodium tetraborate decahydrate g 12.5 Boric acid g 22.5 Sodium hydroxide g 10.0 Ethylene diaminetetraacetic acid g 16.2 Disodium salt of ethylenediaminetetraacetic acid dihydrate g 3.5 Ferric chloride w./v. soln.) ml 15 Sodium thiosulphate pentahydrate g 95.0 Sodium sulphite anhydrous g 4.0 Magnesium sulphate g 12.5 Water to 1 litre. pH 7.0. Wash: 4 minutes Conditioner: 4 minutes Disodium salt of ethylenediaminetetraacetic acid dihydrate g 0.50 Sodium carbonate anhydrous g 4.5 Formaldehyde (40% w./v. soln.) ml 10 Lissapol N (8% w./v. soln.) ml 1.7 Water to 1 litre. pH 10.7.
Wash: 4 minutes Dry CHzOCOCzH In this test a bleach-fix time of 45 minutes was required before all the residual silver had cleared from the film. This is referred to as the clearing time.
In another test samples of the same negative film were fogged and processed as above except for the bleach-fix stage where g. of crystalline sodium selenosulphate were added to the bleach-fix bath described above. In these tests an average clearing time of only 10 minutes was required before all the residual silver had cleared from the film. Thus the sodium selenosulphate has accelerated considerably the bleach-fix process.
EXAMPLE 2 A positive tripack colour material intended for the silver dye-bleach system comprising silver halide emulsions containing bleachable azo-dyes Cibachrome manufactured by Ciba-Geigy A.G. of Switzerland was given a neutral wedge exposure and processed, the processing sequence being as follows:
Development: 10 minutes p-Methyl-aminophenol-sulphate 1 Sodium sulphite anhydrous 20 Hydroquinone 4 Sodium carbonate anhydrous 10 Potassium bromide 2 Water to 1 litre.
Stopfix: 4 minutes G. Sodium thiosulphate pentahydrate 200 Sodium sulphite anhydrous 20 Water to 1 litre.
Wash: 8 minutes Dye-bleach: 20 minutes Sulphuric acid, 96% ml 27.5 Potassium iodide g 10 Solution of 0.3 g. 2,3-dimethyl-6-aminoquinoxaline in 50 ml ethnol ml Water to 1 litre.
Wash: 4 minutes Bleach-fix: 10 minutes Disodium tetraborate decahydrate -g 12.5 Boric acid g 22.5 Sodium hydroxide g 10.0 Ethylenediaminetetraacetic acid g 16.2 Disodium salt of ethylenediaminetetraacetic acid dihydrate -g 3.5 Ferric chloride (60% W./v. soln.) ml 15 Sodium thiosulphate pentahydrate g 95.0 Sodium sulphite anhydrous g 4.0 Sodium selenosulphate g 10 Water to 1 litre. Wash: 8 minutes Dry The processed material was satisfactory and substantially no residual silver was left in the material even in the areas of high exposure. Similar silver-dye-bleach material was exposed and processed using the same solutions as set forth above except that the bleach-fix solution contained no sodium selenosulphate. Even when the material had been treated in the bleach-fit bath for 25 minutes it was unsatisfactory because it had a high minimal density due to the incomplete removal of the residual silver in 116 areas of high exposure.
We claim as our invention:
1. In the processing of colour photographic material comprising silver halide emulsion layers to yield material having colour dye images therein the step of treating the photographic material with a stable bleach-fix bath which comprises an aqueous solution of a mild oxidising agent and a silver halide solvent which is either a water-soluble thiosulphatc or a water-soluble thiocyanate in the presence of a bleach-fix accelerator which is water-soluble selenosulphate of the formula MSeSO where M is two sodium ions, said oxidising agent being one which is strong enough to bleach the silver but is not strong enough to oxidise the silver halide solvent.
2. A process according to claim 1 wherein the mild oxidising agent is a ferric chelate complex.
3. A process according to claim 2 wherein the ferric chelate complex is ferric ethylenediaminetetraacetic acid complex.
4. A process according to claim 1 wehrein the bleachfix accelerator is present in the bleach-fix bath.
5. A stable bleach-fix bath which comprises an aqueous solution of a mild oxidising agent, a silver halide solvent which is either a water-soluble thiosulphate or a water-soluble thiocyanate and a water-soluble bleach-fix accelerator which is a selenosulphate of the general formula MSeSO where M is two sodium ions, said oxidising agent being one which is strong enough to bleach the silver but is not strong enough to oxidise the silver halide solvent.
6. A stable bleach-fix bath according to claim 5 wherein the mild oxidising agent is a ferric chelate complex.
7. A stable bleach-fix bath according to claim 6 wherein the ferric chelate complex is ferric ethylenediaminetetraacetic acid complex.
8. A stable bleach-fix bath according to claim 5 wherein the concentration of bleach-fix accelerator is greater than 1 g. per litre of bleach-fix bath.
9. A stop-fix bath which comprises an aqueous acid solution of a silver halide solvent selected from a watersoluble thiosulphate or a water-soluble thiocyanate and a water-soluble bleach-fix accelerator which is a selenosulphate of the general formula MSeSO where M is two sodium ions.
References Cited UNITED STATES PATENTS 2,770,542 11/1956 Burt 9657 3,189,452 6/1965 Bard et al 9656 3,619,188 11/1971 Alcock et a1. 9660 BF J. TRAVIS BROWN, Primary Examiner U.S. Cl. X.R. 9660 BF, 61 R, 62
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB161670 | 1970-01-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3702247A true US3702247A (en) | 1972-11-07 |
Family
ID=9725038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US105955A Expired - Lifetime US3702247A (en) | 1970-01-13 | 1971-01-12 | Color photographic process using a bleach-fix solution containing a selenosulfate |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3702247A (en) |
| BE (1) | BE761509A (en) |
| CH (1) | CH554004A (en) |
| DE (1) | DE2101344A1 (en) |
| FR (1) | FR2075433A5 (en) |
| GB (1) | GB1297905A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847619A (en) * | 1972-11-20 | 1974-11-12 | Eastman Kodak Co | Ion-paired cobaltic complexes and photographic elements containing same |
| US4294914A (en) * | 1978-09-14 | 1981-10-13 | Eastman Kodak Company | Photographic bleach compositions and methods of photographic processing |
| US4748097A (en) * | 1985-06-25 | 1988-05-31 | Ciba-Geigy Ag | Method of preparing a hologram |
| WO2001050196A1 (en) * | 2000-01-06 | 2001-07-12 | Trebla Chemical Company | One-part bleach-fix liquid concentrates |
| US20040058283A1 (en) * | 2000-05-27 | 2004-03-25 | Gustav Tappe | Bleach-fixing concentrate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51101530A (en) * | 1975-03-05 | 1976-09-08 | Fuji Photo Film Co Ltd |
-
1970
- 1970-01-13 GB GB161670A patent/GB1297905A/en not_active Expired
-
1971
- 1971-01-12 FR FR7100761A patent/FR2075433A5/fr not_active Expired
- 1971-01-12 BE BE761509A patent/BE761509A/en unknown
- 1971-01-12 US US105955A patent/US3702247A/en not_active Expired - Lifetime
- 1971-01-13 CH CH48271A patent/CH554004A/en not_active IP Right Cessation
- 1971-01-13 DE DE19712101344 patent/DE2101344A1/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847619A (en) * | 1972-11-20 | 1974-11-12 | Eastman Kodak Co | Ion-paired cobaltic complexes and photographic elements containing same |
| US4294914A (en) * | 1978-09-14 | 1981-10-13 | Eastman Kodak Company | Photographic bleach compositions and methods of photographic processing |
| US4748097A (en) * | 1985-06-25 | 1988-05-31 | Ciba-Geigy Ag | Method of preparing a hologram |
| WO2001050196A1 (en) * | 2000-01-06 | 2001-07-12 | Trebla Chemical Company | One-part bleach-fix liquid concentrates |
| US20040058283A1 (en) * | 2000-05-27 | 2004-03-25 | Gustav Tappe | Bleach-fixing concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| BE761509A (en) | 1971-06-16 |
| FR2075433A5 (en) | 1971-10-08 |
| GB1297905A (en) | 1972-11-29 |
| CH554004A (en) | 1974-09-13 |
| DE2101344A1 (en) | 1971-07-22 |
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