US3773510A - Additives to bleach/fix baths - Google Patents
Additives to bleach/fix baths Download PDFInfo
- Publication number
- US3773510A US3773510A US00153713A US3773510DA US3773510A US 3773510 A US3773510 A US 3773510A US 00153713 A US00153713 A US 00153713A US 3773510D A US3773510D A US 3773510DA US 3773510 A US3773510 A US 3773510A
- Authority
- US
- United States
- Prior art keywords
- bleach
- bath
- fix
- multivalent element
- fix bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000007844 bleaching agent Substances 0.000 title claims abstract description 47
- 239000000654 additive Substances 0.000 title description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000006872 improvement Effects 0.000 claims abstract description 4
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 4
- 238000009877 rendering Methods 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- -1 silver halide Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000011161 development Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 8
- 239000000975 dye Substances 0.000 description 21
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 11
- 235000010344 sodium nitrate Nutrition 0.000 description 8
- 239000004317 sodium nitrate Substances 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-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
- 230000008859 change Effects 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 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
- 239000012086 standard solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-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
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 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
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Images
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
- a developable silver salt image is developed with an aromatic primary amino developing agent of the paraphenylene diamine type (a so-called color developer") in the presence of a compound which will combine with the oxidation products of the color developer to form an azomethine or quinoneimine dye (a so-called color coupler).
- 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 only the dye image.
- a bleach/fix immediately follows the developer step there may be difficulty in effecting the full dye image. in detailing a technique to overcome such a deficiency, U.S. Pat. No.
- 3,189,452 describes the use of an additional oxidizing bath immediately following the bleach/fix bath to effect the formation of the full dye density available.
- additives to bleach/fix baths having a complexed or sequestered metal oxidizing agent can significantly improve the available dye density without the need for additional steps.
- These additives also make it possible to use pH values below 7.
- the additives of this invention are water soluble ionic compounds in which one of the ionic species is inorganic and contains at least one multivalent element at one of its higher valence states, which compounds increase the oxidation potential of such baths by at least 30, preferably 50, millivolts in a concentration not in excess of 50 gm/liter. The concentration used may vary greatly with the compound but obviously should not be large enough to render the bath unstable.
- the oxidation potential of the baths may be increased by lowering the pH, this technique by itself can lead to the loss of dye density (especially cyan), as mentioned earlier.
- the inclusion of the additives allows the formulation of bleach/fix baths with significantly increased oxidation potentials, above that of the bleach/fix alone at a given pH. This makes it possible to obtain the desired dye density without the necessity for additional processing baths or steps and further makes it possible to achieve this advantage independently of the pH of the bleach/fix bathywhich is prefer ably above pH 4..
- the preferred additives are inorganic compounds (including inorganic salts of organic acids) which contain at least one multivalent element at one of its higher valence states, including such multivalent elements as a heavy metal, oxygen, a halogen, nitrogen, sulfur, etc.
- Illustrative additives are the vanadates, chromates and persulfates which are soluble in and compatible with the bleach/fix baths. Examples of specific additive compounds are vanadium oxalate, cupric acetate, cupric chloride, vanadium pentoxide, potassium persulfate, sodium periodate, sodium dichromate, ceric ammonium nitrate, etc.
- Such bleach/fix baths contain, as the silver oxidizing agent, a complexed or sequestered metal oxidizing agent (e.g. the iron complex of ethylene diamine tetraacetic acid) and a silver solvent (usually sodium or ammonium thiosulfate, which are reducing agents).
- a complexed or sequestered metal oxidizing agent e.g. the iron complex of ethylene diamine tetraacetic acid
- a silver solvent usually sodium or ammonium thiosulfate, which are reducing agents.
- the oxidation potential of bleach baths may be measured with a millivolt measuring device utilizing a platinum indicating electrode and a saturated calomel electrode at 20C. As is illustrated in the examples below, dye density is seen to be directly related to the oxidation potential.
- a multilayer photosensitive material specifically a color print paper containing a ketomethylene yellow coupler, a pyrazolone magenta coupler and a phenolic cyan coupler (i.e. 3M Mark III RC Color Print Paper, a product of 3M Company, Saint Paul, Minn., U.S.A.) was exposed and-then processed at F. in the following sequence: color de used.
- EXAMPLE 1 An aqueous bleach/fix bath was prepared using the following basic formula plus additives, shown in Table with a standard color densitometer.
- EXAMPLE 2 Sodium nitrate in amounts varying from 0 to 200 grams/liter were added to the bleach/fix formula, and the oxidation potential was measured. The following data describes the results.
- a bleach/fix bath for color photo-graphic processing said bath having a pH above 4 and having a sequestered metal oxidizing agent as the bleaching agent, the improvement which comprises a water soluble ionic compound in which one of the ionic species is inorganic and contains at least one multivalent element at one of its higher valence states, which compound increases the oxidation potential of said bath by at least 30 millivolts in a quantity not in excess of 50 grams per liter without rendering said bath unstable.
- a color photographic process including a development step in which an exposed silver halide image is developed with an aromatic primary amino developing agent in the presence of color coupler and a bleachhigher valence states, which compound increases the oxidation potential of said bath by at least 30 milli-volts in a quantity not in excess of 50 grams per liter without rendering said bath unstable.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
In a bleach/fix bath for color photographic processing, said bath having a complexed or sequestered metal oxidizing agent as the bleaching agent, the improvement which comprises a water soluble ionic compound in which one of the ionic species is inorganic and contains at least one multivalent element at one of its higher valence states, which compound increases the oxidation potential of said bath by at least 30 millivolts in a quantity not in excess of 50 grams per liter without rendering said bath unstable.
Description
United States Patent 1191 Fisch Nov. 20, 1973 4] ADDITIVES To BLEACH/FIX BATHS 3,619,188 11 1971 Alcock 96 60 BF [75] Inventor: Richard S. Fisch, St. Paul, Minn. Primary Examiner Norman G. Torchin [73] Assignee: Minnesota Mining and Assistant Examiner-M. F. Kelley Manufacturing Company, St. Paul, Attorney-Kinney, Alexander, Sell, Steldt & Delahunt Minn. 22 Filed: June 26, 1971 [571 ABSTRACT In a bleach/fix bath for color photographic processing, [21] Appl' 153713 said bath having a complexed or sequestered metal oxidizing agent as the bleaching agent, the improvement [52] US. Cl. 96/60 BF, 96/61 R which comprises a Water l le i nic compound in [51] Int. Cl G03c 5/32, G03c 5/38 which one of the ionic sp i s is in rganic and con- [58] Field of Search 96/60, 60 BF, 61 wins at least one multivalent element at one of its higher valence states, which compound increases the [56] References Cit d oxidation potential of said bath by at least 30 milli- UNITED STATES PATENTS volts in a quantity not in excess of 50 grams per liter 2,322,084 6/1943 Young et al. 96/53 wlthout rendermg bath unstable 3,335,004 8/1967 Wrisley et a1 96/22 10 Claims, 1 Drawing Figure OXIDAT/ON POTENTIAL (m. M)
Patented Nov. 20, 1973 OX/DAT/ON pOTENT/AL INVENTOR. i-P/cHARo 5. F/scH ATTORNEYS This invention relates to color photography and more particularly to the processing of photographic material 7 comprising silver halide emulsion layers and adapted for processing to yield color images, hereinafter referred to simply as color photographic material."
in the conventional processing of such color photographic material, such as color print paper, a developable silver salt image is developed with an aromatic primary amino developing agent of the paraphenylene diamine type (a so-called color developer") in the presence of a compound which will combine with the oxidation products of the color developer to form an azomethine or quinoneimine dye (a so-called color coupler). 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 only the dye image. However, when a bleach/fix immediately follows the developer step there may be difficulty in effecting the full dye image. in detailing a technique to overcome such a deficiency, U.S. Pat. No.
3,189,452 describes the use of an additional oxidizing bath immediately following the bleach/fix bath to effect the formation of the full dye density available.
Great care has been taken in the past to remove unused color developer from the photographic material before the latter enters the bleach bath, usually by treatment with an acid stop bath and/or a washing operation. It is especially difficult to avoid color fogging when the stop bath is omitted, even if the pH of the bleach bath is kept below 7, except by use of a prolonged washing operation after development. Unfortunately at low pH values the cyan dyes formed by coupling of naphthol derivatives with p-phenylenediamine derivatives are converted to the" colorless leuco form, so bleach/fix baths of pH values about 7 have been recommended to avoid loss of cyan dye.
We have found that the inclusion of certain additives to bleach/fix baths having a complexed or sequestered metal oxidizing agent can significantly improve the available dye density without the need for additional steps. These additives also make it possible to use pH values below 7.The additives of this invention are water soluble ionic compounds in which one of the ionic species is inorganic and contains at least one multivalent element at one of its higher valence states, which compounds increase the oxidation potential of such baths by at least 30, preferably 50, millivolts in a concentration not in excess of 50 gm/liter. The concentration used may vary greatly with the compound but obviously should not be large enough to render the bath unstable. Although the oxidation potential of the baths may be increased by lowering the pH, this technique by itself can lead to the loss of dye density (especially cyan), as mentioned earlier. The inclusion of the additives allows the formulation of bleach/fix baths with significantly increased oxidation potentials, above that of the bleach/fix alone at a given pH. This makes it possible to obtain the desired dye density without the necessity for additional processing baths or steps and further makes it possible to achieve this advantage independently of the pH of the bleach/fix bathywhich is prefer ably above pH 4..
We have found that the preferred additives are inorganic compounds (including inorganic salts of organic acids) which contain at least one multivalent element at one of its higher valence states, including such multivalent elements as a heavy metal, oxygen, a halogen, nitrogen, sulfur, etc. Illustrative additives are the vanadates, chromates and persulfates which are soluble in and compatible with the bleach/fix baths. Examples of specific additive compounds are vanadium oxalate, cupric acetate, cupric chloride, vanadium pentoxide, potassium persulfate, sodium periodate, sodium dichromate, ceric ammonium nitrate, etc. Such bleach/fix baths contain, as the silver oxidizing agent, a complexed or sequestered metal oxidizing agent (e.g. the iron complex of ethylene diamine tetraacetic acid) and a silver solvent (usually sodium or ammonium thiosulfate, which are reducing agents).
Some of the additives encompassed by this-invention have been previously used in other processes. U.S. Pat. No. 2,322,084, for example, cites the use of ammonium vanadate in a simultaneous dye and silver bleaching and fixing bath for the silver dye bleach process, which is not a conventional bleach/fix bath having a complexed or sequestered metal oxidizing agent. That process also differs from the conventional color forming process described in this invention in the fact that the dye essentially making up the visible image is not formed in situ but rather is present during the exposing and processing and is destroyed imagewise by the action of the silver formed by development and the bleaching bath. Some bath additives have previously been mentioned as chemical toning agents for color materials, see History of Color Photography, J. S. Friedman (American Photography Co., Boston, 1944) pages 322 and 324. Other additives in bleach/fix baths have been used to minimize stain, accelerate fixing and accelerate bleaching. Among the reported additives are thiosemicarbizide (U.S. Pat. No. 3,293,036), thiocarbamide or ascorbic acid (British Pat. No. 777,635), sodium iodide (British Pat. No. 926,569), thiourea (British Pat. No. 991,412), mercaptotetrazole (British Pat. No. 1,138,813), and hydrazine sulfate (U.S. Pat. No. 3,293,036).
For the purpose of this invention and its examples the oxidation potential of bleach baths may be measured with a millivolt measuring device utilizing a platinum indicating electrode and a saturated calomel electrode at 20C. As is illustrated in the examples below, dye density is seen to be directly related to the oxidation potential.
In all of the following examples a multilayer photosensitive material, specifically a color print paper containing a ketomethylene yellow coupler, a pyrazolone magenta coupler and a phenolic cyan coupler (i.e. 3M Mark III RC Color Print Paper, a product of 3M Company, Saint Paul, Minn., U.S.A.) was exposed and-then processed at F. in the following sequence: color de used.
EXAMPLE 1 An aqueous bleach/fix bath was prepared using the following basic formula plus additives, shown in Table with a standard color densitometer.
40 grams/liter l5 grams/liter TABLE I Quantity of Cyan additive Oxidation Dye Additive (grams/liter) Potential Density None 94 m.v. 0.74 Magnesium Sulfate 5 31 94 m.v. 0.75 Sodium Nitrate 200 7| m.v. 0.78 Cupric Chloride 5 62 m.v. 1.25 Sodium Dichromate 2 22 m.v. l.6l Potassium Persulfate 2 4 m.v. 1.78 yanadium Pentoxide 5 +110 m.v. 2.38
Using the same millivolt measuring device described above the bleach/fix formula, various other chemical compounds were incorporated into this standard solution, the resultant oxidation values were measured and recorded (the pH of each of the samples was adjusted to pH 4.5 by the use of citric acid or potassium hydroxide as needed before measuring the oxidation potential). Results are presented in Table ll.
TABLE ll Quantity of Change in additive Oxidation Sample Additive grams/liter Potential Control no additive, standard screening hath A thiourca 5 B magnesium sulfate O C 5 phenyl mercaptatctrazole 2 O D hydroxylamine sulfate 5 0 E thiosemicarbizide 3 0 F ethylene thiourea 5 O G ceric ammonium nitrate 30 42 H cupric chloride 5 32 l sodium periodatc 25 30 .l m-dinitrobenzene 2 O K sodium dichromate 2 72 L potassium persulfate 2 90 M vanadium pentoxide 5 +204 N sodium nitrate 200 25 The oxidation potentials were measured with a platinum indicating electrode and a saturated calomel electrode at 20C. In all instances those baths which contained the additives that raised the oxidation potential at least 30 m.v. were highly effective in developing the full dye density, especially of the cyan dye. No significant increase in oxidation potential occurs when additives A F and J were used in higher concentrations up to 50 grams/liter. The direct relationship between oxidation potential and dye density is immediately apparent from these data.
EXAMPLE 2 Sodium nitrate in amounts varying from 0 to 200 grams/liter were added to the bleach/fix formula, and the oxidation potential was measured. The following data describes the results.
TABLE III Sodium nitrate concentration Oxidation Potential 200 grams/liter 70 m.v. 125 grams/liter 70 m.v. 80 grams/liter 75 m.v.
30 grams/liter 82 m.v. l0 grams/liter 90 m.v. 0 grams/liter 94 m.v.
As can be seen from Table III, increasing quantities of this compound did not change the oxidation potential greatly, and the oxidation potential never increased more than 24 m.v. above that of the starting standard solution. Using the same procedures with vanadium pentoxide additive instead of sodium nitrate, the oxidation data in Table IV and the cyan dye density relationship to oxidation potential in the FIGURE, were obtained.
TABLE IV Vanadium pentoxide concentration Oxidation Potential l0 grams/liter +100 m.v. 5 grams/liter 30 m.v. 2 grams/liter 47 m.v. 0.5 grams/liter 37 m.v. 0 grams/liter 95 m.v.
A comparison of the effect of sodium nitrate and vanadium pentoxide on dye density at different concentration levels is presented in Table V.
TABLE V Quantity of additive Oxidation Cyan Dye Additive grams/liter Potential Density (control) 95 m.v. 0.75 sodium nitrate 70 m.v. 0.75 sodium nitrate 200 70 m.v. 0.75 vanadium pentoxide 2 47 2.10 vanadium pentoxide 5 +l l0 m.v. 2.38
With the additives of this invention the effect of increasing additive concentration on oxidation potential continues until a maximum dye density is achieved or until the solution solubility limit of the additive is reached.
What is claimed is:
1. In a bleach/fix bath for color photo-graphic processing, said bath having a pH above 4 and having a sequestered metal oxidizing agent as the bleaching agent, the improvement which comprises a water soluble ionic compound in which one of the ionic species is inorganic and contains at least one multivalent element at one of its higher valence states, which compound increases the oxidation potential of said bath by at least 30 millivolts in a quantity not in excess of 50 grams per liter without rendering said bath unstable.
2. The bleach/fix bath of claim 1 in which said multivalent element is a heavy metal.
3. The bleach/fix bath of claim 1 in which said multivalent element is chromium.
4. The bleach/fix bath of claim 1 in which said multivalent element is sulfur.
5. The bleach/fix bath of claim 1 in which said multi' valent element is copper.
6. The bleach/fix bath of claim 1 in which said multivalent element is a halogen.
7. The bleach/fix bath of claim 1 in which said multivalent element is a nitrogen.
' 8. The bleach/fix bath of claim 1 in which said multivalent element is vanadium.
9. The bleach/fix bath of claim 1 in which said multivalent element is oxygen.
10. In a color photographic process including a development step in which an exposed silver halide image is developed with an aromatic primary amino developing agent in the presence of color coupler and a bleachhigher valence states, which compound increases the oxidation potential of said bath by at least 30 milli-volts in a quantity not in excess of 50 grams per liter without rendering said bath unstable.
7 um'mb 53m ns QATENT OFFICE CERTIFICATE (9F CORRECTION Patent No, "3,773,510 Dated ovember 20, 1973 Inventor) RICHARD S. F ISCH It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 3, Table I, under column headed Oxidation Potential, second item: "31 9M m.v.", should be:
Column l, Table IV, under column headed Oxidation Potential, seconditem: "3O 7O m.v.",. should be: 70 m.v.
Signed and sealed this 1st day of October 1974.
(SEAL) Attest:
MCCOY M. GIBSON JR. c. MARSHALL DANN Attesting Officer I Commissioner of Patents FORM P0-1D50 (10-69) a n u s ouvnnmzm nmnna ornc: nu 0-16-31
Claims (9)
- 2. The bleach/fix bath of claim 1 in which said multivalent element is a heavy metal.
- 3. The bleach/fix bath of claim 1 in which said multivalent element is chromium.
- 4. The bleach/fix bath of claim 1 in which said multivalent element is sulfur.
- 5. The bleach/fix bath of claim 1 in which said multivalent element is copper.
- 6. The bleach/fix bath of claim 1 in which said multivalent element is a halogen.
- 7. The bleach/fix bath of claim 1 in which said multivalent element is a nitrogen.
- 8. The bleach/fix bath of claim 1 in which said multivalent element is vanadium.
- 9. The bleach/fix bath of claim 1 in which said multivalent element is oxygen.
- 10. In a color photographic process including a development step in which an exposed silver halide image is developed with an aromatic primary amino developing agent in the presence of color coupler and a bleach/fix step in which a sequestered metal oxidizing agent is used as the bleaching agent, the improvement which comprises the use of a bleach fix bath having a pH above 4 and containing a water soluble ionic compound in which one of the ionic species is inorganic and contains at least one multivalent element at one of its higher valence states, which compound increases the oxidation potential of said bath by at least 30 milli-volts in a quantity not in excess of 50 grams per liter without rendering said bath unstable.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15371371A | 1971-06-26 | 1971-06-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3773510A true US3773510A (en) | 1973-11-20 |
Family
ID=22548417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00153713A Expired - Lifetime US3773510A (en) | 1971-06-26 | 1971-06-26 | Additives to bleach/fix baths |
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| Country | Link |
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| US (1) | US3773510A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040838A (en) * | 1975-03-05 | 1977-08-09 | Fuji Photo Film Co., Ltd. | Processing color photographic materials |
| US4088486A (en) * | 1975-08-06 | 1978-05-09 | Eastman Kodak Company | Process of bleaching silver images to form dye images using cobalt complexes and peroxides |
| US4097278A (en) * | 1975-09-02 | 1978-06-27 | Eastman Kodak Company | Redox amplification process employing a combination of oxidizing agents |
| US4277556A (en) * | 1976-08-18 | 1981-07-07 | Konishiroku Photo Industry Co., Ltd. | Process for treating light-sensitive silver halide color photographic materials |
| DE3423100A1 (en) * | 1983-06-23 | 1985-01-03 | Konishiroku Photo Industry Co., Ltd., Tokio/Tokyo | TREATMENT BATH WITH BLEACH TO LIGHT-SENSITIVE (COLOR) PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIALS |
| US4812389A (en) * | 1985-09-25 | 1989-03-14 | Fuji Photo Film Co., Ltd. | Process for processing silver halide color photographic material containing DIR coupler having a group functioning as a development inhibitor |
| US5264332A (en) * | 1990-10-08 | 1993-11-23 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| WO1997008287A2 (en) * | 1995-08-30 | 1997-03-06 | The Dow Chemical Company | Polyamino monosuccinic acid derivative degradable chelants, uses and compositions thereof |
| EP0762203A1 (en) * | 1995-08-30 | 1997-03-12 | Eastman Kodak Company | Succinic acid derivative degradable chelants, uses and compositions thereof |
| US6022680A (en) * | 1996-06-11 | 2000-02-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2322084A (en) * | 1940-01-11 | 1943-06-15 | Eastman Kodak Co | Simultaneous bleaching and fixing bath |
| US3335004A (en) * | 1963-12-09 | 1967-08-08 | Eastman Kodak Co | Method for stabilization processing of color emulsions |
| US3619188A (en) * | 1968-07-24 | 1971-11-09 | Ilford Ltd | Bleach-fix processing |
-
1971
- 1971-06-26 US US00153713A patent/US3773510A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2322084A (en) * | 1940-01-11 | 1943-06-15 | Eastman Kodak Co | Simultaneous bleaching and fixing bath |
| US3335004A (en) * | 1963-12-09 | 1967-08-08 | Eastman Kodak Co | Method for stabilization processing of color emulsions |
| US3619188A (en) * | 1968-07-24 | 1971-11-09 | Ilford Ltd | Bleach-fix processing |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040838A (en) * | 1975-03-05 | 1977-08-09 | Fuji Photo Film Co., Ltd. | Processing color photographic materials |
| US4088486A (en) * | 1975-08-06 | 1978-05-09 | Eastman Kodak Company | Process of bleaching silver images to form dye images using cobalt complexes and peroxides |
| US4097278A (en) * | 1975-09-02 | 1978-06-27 | Eastman Kodak Company | Redox amplification process employing a combination of oxidizing agents |
| US4277556A (en) * | 1976-08-18 | 1981-07-07 | Konishiroku Photo Industry Co., Ltd. | Process for treating light-sensitive silver halide color photographic materials |
| DE3423100A1 (en) * | 1983-06-23 | 1985-01-03 | Konishiroku Photo Industry Co., Ltd., Tokio/Tokyo | TREATMENT BATH WITH BLEACH TO LIGHT-SENSITIVE (COLOR) PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIALS |
| US4563405A (en) * | 1983-06-23 | 1986-01-07 | Konishiroku Photo Industry Co., Ltd. | Processing solution having bleaching ability for light-sensitive silver halide color photographic material |
| US4812389A (en) * | 1985-09-25 | 1989-03-14 | Fuji Photo Film Co., Ltd. | Process for processing silver halide color photographic material containing DIR coupler having a group functioning as a development inhibitor |
| EP0452984A1 (en) | 1985-09-25 | 1991-10-23 | Fuji Photo Film Co., Ltd. | Process for processing silver halide color photographic material for photographing use |
| US5264332A (en) * | 1990-10-08 | 1993-11-23 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| WO1997008287A2 (en) * | 1995-08-30 | 1997-03-06 | The Dow Chemical Company | Polyamino monosuccinic acid derivative degradable chelants, uses and compositions thereof |
| EP0762203A1 (en) * | 1995-08-30 | 1997-03-12 | Eastman Kodak Company | Succinic acid derivative degradable chelants, uses and compositions thereof |
| WO1997008287A3 (en) * | 1995-08-30 | 1997-05-15 | Dow Chemical Co | Polyamino monosuccinic acid derivative degradable chelants, uses and compositions thereof |
| US6022680A (en) * | 1996-06-11 | 2000-02-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
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