US2322084A - Simultaneous bleaching and fixing bath - Google Patents
Simultaneous bleaching and fixing bath Download PDFInfo
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- US2322084A US2322084A US364548A US36454840A US2322084A US 2322084 A US2322084 A US 2322084A US 364548 A US364548 A US 364548A US 36454840 A US36454840 A US 36454840A US 2322084 A US2322084 A US 2322084A
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- United States
- Prior art keywords
- silver
- dye
- bleaching
- acid
- fixing
- 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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- 238000004061 bleaching Methods 0.000 title description 17
- 239000004332 silver Substances 0.000 description 52
- 229910052709 silver Inorganic materials 0.000 description 52
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 36
- 239000000975 dye Substances 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 239000007800 oxidant agent Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000000987 azo dye Substances 0.000 description 12
- 239000007844 bleaching agent Substances 0.000 description 12
- -1 silver halide Chemical class 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 7
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 5
- 229940116357 potassium thiocyanate Drugs 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 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 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 125000005287 vanadyl group Chemical group 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- RZSYLLSAWYUBPE-UHFFFAOYSA-L Fast green FCF Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC(O)=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 RZSYLLSAWYUBPE-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HSXUHWZMNJHFRV-UHFFFAOYSA-L disodium;6-oxido-5-phenyldiazenyl-4-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1N=NC1=CC=CC=C1 HSXUHWZMNJHFRV-UHFFFAOYSA-L 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
-
- 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
Definitions
- This invention relates to improvements in color photography and mor particularly in processes wherein dyes present in a silver halide emulsion are bleached in the vicinity of a ilver'image.
- the invention includes a bleach bath for use in a .dye bleach-out process containing a fixing agent, a strong acid and a mild oxidizing agent capable of oxidizing metallic silver to a silver salt.
- Any mineral acid may be usedas a strong acid
- t such as hydrochloric acid, hydrobromic acid, hy-
- dye images such as a solution of cupric chloride.
- the treatment of photographic elements by the bleaching-out process therefore generally involves five operations, apart from the necessary washing steps, namely: (1) development; (2) fixing out theundeveloped silver halide; (,3) dye-bleaching; (4) oxidation of the residual silver to a silver salt; (5) fixing out the silver salt.
- the dye in a photographic dye bleach-out process there is fixed out, the dye is bleached, the silver is oxidized and the oxidation product of the silver is fixed out in one operation, provided that a suitable quantity of the mild oxidizing agent is employed.
- the presence of the mild oxidizing agent also makes itpossible to efi'ect -control oi the gamma of the dye image since therelative con droiodic acid, nitric acid, and phosphoric acid.
- the thiocyanate ion is responsible for the fixing and for the formation of a soluble complex of silver when the silver becomes oxidized.
- The'complex'formed from the thiocyanate andferric ions acts as th mild oxidizing agent to oxidize the silver not oxidized by the bleaching of the image-forming dye.
- Th oxyaminophenazine and the dimethyl' quinoxaline act as a bleaching catalyst.
- Example 13 Potassium thiocyanate grams- 15.0 Thiocarbamide ..grams- A Hydrochloric acid (conc.) Hydrochloric acid (conc.) ....do 4.0
- a magenta dye which was prepared from Example .3 zegrgzotimed t2 h:5:2':5'-teet;amfii;1hyi-4i:gidnop eny me ane coup ace y g gf im g fi i j a
- a method of producing a colored photographic image in a gelatino-silver halide layer containing an azo dye capable of being declorized by reduction which comprises exposing and developing the layer to produce a metallic silver image therein, and then simultaneously bleaching the dye and fixing out the silver and silver halide in a bath containing an acid bleaching agent, an azo dye as an oxidizing agent for silver, and a fixing agent.
- a method of producing a colored photographic image in a gelatino-silver halide layer containing an azo dye capable of being decolorized by reduction which comprises exposing and developing the layer to produce a metallic silver imag therein, and then simultaneously bleaching the dye and fixing out the silver and silver halide in a bath containing hydrochloric acid as a bleaching agent, a mild oxidizing agent for silver, and a fixing agent.
- a method of producing a colored photographic image in a gelatino-silver halide layer containingan azo dye capable of being decolorized by reduction which comprises exposing and developing the layer to produce a metallic silver image therein, and then simultaneously bleaching the dye and fixing out the silver and silver halide in a bath containing an acid bleaching agent, ferric ions as an ozidizing'agent for silver, and potassium thlocyanat as a fixing agent.
- a method of producing a colored photographic image in a gelatino-silver halide layer containing an azo dye capable of being decolorized by reduction which comprises exposing anddeveloping the layer to produce a metallic silver image therein, and then simultaneously bleaching the dye and fixing out the silver and silver halide in a bath containing an acid bleaching agent, an azo dye as an oxidizing agent for silver, and potassium thiocyanate as a fixing agent.
- a method of producing a colored photographic image in a gelatino-silver halide layer containing an azo dye capable of being decolorized by reduction which comprises exposing and developing the layer to produce a metallic silver image therein, and then simultaneously bleaching th dye and fixing out the silver and silver halide in a bath containing hydrochloric acid as a bleaching agent, a mild oxidizing agent for silver, and potassium thiocyanate as a fixing agent.
- a bleach and fixing bath for use in a bleachout process of color photography containing a fixing agent, a strong acid, and an azo dye as a mild oxidizing agent capable of oxidizing metallic silver to silver ion.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Patented June 15, 1943 2,322,084 SIMULTANEOUS BLmcniNG AND FIXING.
BATH
Richard V. Young and Merrill -W. Seymour, Rochester, N. Y.,- assignors toEastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 0,1940, Serial 1 In Great Britain January 11,
8 Claims. (01. 95-6) This invention relates to improvements in color photography and mor particularly in processes wherein dyes present in a silver halide emulsion are bleached in the vicinity of a ilver'image.
It is known that the bleaching of dyes selectively in the neighborhood of a silver image can be accomplished by reagents such as acid thiourea. It is possible'to control the contrast of the dye images by the addition of azo dyes or other mild oxidizing agents to the bleaching solutions which cause less image-forming dye to be reduced by a given amount of silver for the available reducing agent because they compete with the azo dyes present in the emulsion, as described in our application Serial No. 355,098 filed August 31, 1940. This lowers the contrast of the dye im- 8.868.
in the processes of thebleaching-out has hitherto been customary to fix out the un developed silver salts before treatment with the bleach baths. In such bleaching-out processes, moreover, there is generally some excess of silver left behind after the bleaching of the dye has been carried to the desired point. This residual silver has to be removed after oxidation with some reagent which does not destroy the yp it centrations of the oxidizing agent and of the other constituents. of the bleach bath may be altered as requiredto bleach the desired amount of dye in thetime necessary to oxidize all of the silver to a soluble silver complex.
The invention includes a bleach bath for use in a .dye bleach-out process containing a fixing agent, a strong acid and a mild oxidizing agent capable of oxidizing metallic silver to a silver salt.
Any mineral acid may be usedas a strong acid,
t such as hydrochloric acid, hydrobromic acid, hy-
dye images, such as a solution of cupric chloride.
The treatment of photographic elements by the bleaching-out process therefore generally involves five operations, apart from the necessary washing steps, namely: (1) development; (2) fixing out theundeveloped silver halide; (,3) dye-bleaching; (4) oxidation of the residual silver to a silver salt; (5) fixing out the silver salt.
It has now been foimd possible to employ a bleach bath which will simultaneously accomplish operationsi2), (3) {(4) "and (5),renderingunnecessary any separate operation for fixing out residual silver halide and for removing unused silver. By reduction in the number-of chemical operations it is also possible to reduce the num-' ber of washes andthis accomplishes a great saving in time.
According to the present invention, therefore, in a photographic dye bleach-out process there is fixed out, the dye is bleached, the silver is oxidized and the oxidation product of the silver is fixed out in one operation, provided that a suitable quantity of the mild oxidizing agent is employed. The presence of the mild oxidizing agent also makes itpossible to efi'ect -control oi the gamma of the dye image since therelative con droiodic acid, nitric acid, and phosphoric acid. Among oxidizing agents which can be used may be mentioned ferric chloride, ammonium vanadate, vanadyl chloride, potassium ferricyanide, potassium nitrate and organic compounds such as soluble nitro and nitroso compounds and azo dyes which can rapidly difluse into and'out of an emulsion. I
Examples willnow be given of suitable bleaching baths for carrying out the present inventions:
In this solution, the thiocyanate ion is responsible for the fixing and for the formation of a soluble complex of silver when the silver becomes oxidized. The'complex'formed from the thiocyanate andferric ions acts as th mild oxidizing agent to oxidize the silver not oxidized by the bleaching of the image-forming dye. Th oxyaminophenazine and the dimethyl' quinoxaline act as a bleaching catalyst.
r I Erample 2 v 2 Potassium thiooyanate "grams" 14.0 H1804 (cone) &cubic centimeters; 1.0
2-hydroxy-3-amiriophenazinegrams 0.004 2:3-dimethylquinoxaline do. 0.02 v d0 v 0'1 I 11:0, to cubic-centimeters Example 3 Potassium thiocyanatens gr ams 14.0 H2804 (conc.) cubic centimeters; 1.0 2-hydroxy-3-aminophenazinegrams 0.004
2:3-dimethylquinoxaline do 0.02
Du-Pont Qrange G, Schultz No. 39
H2O, to cubiocentimeters Example 4 Example 13 Potassium thiocyanate grams- 15.0 Thiocarbamide ..grams- A Hydrochloric acid (conc.) Hydrochloric acid (conc.) ....do 4.0
' cubic centimeters 5.0 2:3-dimethylquinoxaline do 0.03 2-hydroxy-3-aminophenazinegrams 0.004 Ferric ammonium sulphate ..do 0.1 2:3-dimethylquinoxaline do 0.03 H2O, to -..cubic centimeters 100 Ferric chloride do 0.05 H3O, to cubic centimeters 100 Example- Thiocarbamide grams..- 5.0 Example 5 Sulphuric acid (conc.) Potassium thiocyanate grams 10.0 cu i entim e Phosphoric acid (cone) 2:8-dimethylqu1noxaiine grams 0.04
cubic centlmeters 1,0 Ammonium vanadate--. ..d0-- 0.025 2-hydroxy-3-aminophenazineL grams 0.004 H20. cu cent Ferric ammonium sulphate do- 0.1 I Example 15 2:3-dimethylquinoxaline ..d0 0.02 Potassium aluminum sulphate do 3.0 Potassium tmocyanate"? 1M 20, to cu'bic centimeters 10o Hydrochloric acid (1301100 cubic centimeters--. 4.0 Example 5 -2:a-dimethylquinoxaline grams 0.03 I Potassium thiocyanatee grams 12.0 os et y 'a i Hydrochloric acid (cone) H20. to --cubic centimeters" 100 (millimeters-w In Examples 13 or 14, the thiourea serves the 2:3 -dimethylquinoxaline "grams" 4.04 same purpose as potassium m Ferric ammonium The bleaching baths of the foregoing examples to centimeters-10o may be used, for example, for the production Example 7 of dye images in a three-layer him, the emulsion Potassium thiocyanate grams 10.0 izg g gggg respectively contaml me l l fiydmhloric acid mom") A yellow dye which was prepared fromtetrazotized tolidinedisulphonic acid coupled with 2- Potassium ferricyanide do 0.1 h1 o-5 hydr0xyto1uene. to centimeters" A magenta dye which was prepared from Example .3 zegrgzotimed t2 h:5:2':5'-teet;amfii;1hyi-4i:gidnop eny me ane coup ace y g gf im g fi i j a A cyan dye, Pontamine Fast Green 58L, manudim 0 factured by E. I. du Pont de Nemours and Comethylquinoxaline do 0.03 pany io-Nitman-mne In the foregoing examp s the concentrations T "cubic centimeters" 40 of each component may varied within wide Example liniits witmkilut gsglougly afiectiagn the bleacdr:
aconof e ,utpermi gthera Pot ssi m thiocyanate --,-8 bleaching and contrast 01 the dye ima es to he Hydrochloric acid (cone) -do 4.0 4 adjusted as desired msmmethylqumoxalme 093 5 The invention is not limited to th above Ammnogium vtainadate (or an equivamples which illustrate the use of numerous g ty of vanadyl ch10 oxidizing agents for oxidizing the excess of metale) 032 116 silver, e. g., the ferric, vanadyl, fern-cyanide 'T' b centimeters" or nitrate ions or an az dye or 9, nitro or nitroso Example 10 compound. Our invention comprises all modifications included within the scope of the appended Potassium thiocymte "grams. 12.0 c1aims Hydrochloric acid (conc.) We claim:. cubic centimeter! 51! 1. A method of producing a colored photo- 2:3'dimethy1qum1$a1ine "E 3. graphic image in a gelatino-silver halide layer m containing a dye capable of being decolorized by phone reduction, which comprises exposing and devel-- to Feubic cmctlmetel'su oping the layer to produce a metallic silver image therein, and then'simultaneously bleaching Exam, ,8 11 the dye and fixing out the silver and silver halide KC'NB "grams" L20 in a bath containing an acid bleaching agent. Hydrochloric acid (conc. a a mild oxidizing agent for silver, and a fixing cubic centimeters" 4.0 agent, I 2:3-dlmethylquinoxaline -grains 0.03 2. A method of producing a colored photooor m-nitrobenzene sulphonic acid ..do 0.1 graphic imag in a gelatino-silver halide layer HaQto cubic.centimeters-- 100 containing an azo dye capable of being declor- Example 12 ized by reduction. which comprises exposing and I developing the layer to produce a metallic silver P ta m tmocymte grgmg 101 image therein, and then simultaneously bleach- Hydrochloric acid cubic centimeters..- 5.0 ing the dye a fixing ut the'si ve and si v r 2z3-dimethylquinoumli e; gramg i103 halide in a bath cohtaininglan acid bleaching i-nitroanthraquinone-a-sulphonic v n ferric ions as an oxidizing agent for silver,
acid.- -.-.do-.'-.. 0.05 and a fixing agent.
to --cubic centimeters" 3. A method of producing a colored photographic image in a gelatino-silver halide layer containing an azo dye capable of being declorized by reduction, which comprises exposing and developing the layer to produce a metallic silver image therein, and then simultaneously bleaching the dye and fixing out the silver and silver halide in a bath containing an acid bleaching agent, an azo dye as an oxidizing agent for silver, and a fixing agent.
4. A method of producing a colored photographic image in a gelatino-silver halide layer containing an azo dye capable of being decolorized by reduction, which comprises exposing and developing the layer to produce a metallic silver imag therein, and then simultaneously bleaching the dye and fixing out the silver and silver halide in a bath containing hydrochloric acid as a bleaching agent, a mild oxidizing agent for silver, and a fixing agent.
5. A method of producing a colored photographic image in a gelatino-silver halide layer containingan azo dye capable of being decolorized by reduction,-which comprises exposing and developing the layer to produce a metallic silver image therein, and then simultaneously bleaching the dye and fixing out the silver and silver halide in a bath containing an acid bleaching agent, ferric ions as an ozidizing'agent for silver, and potassium thlocyanat as a fixing agent.
6. A method of producing a colored photographic image in a gelatino-silver halide layer containing an azo dye capable of being decolorized by reduction, which comprises exposing anddeveloping the layer to produce a metallic silver image therein, and then simultaneously bleaching the dye and fixing out the silver and silver halide in a bath containing an acid bleaching agent, an azo dye as an oxidizing agent for silver, and potassium thiocyanate as a fixing agent.
7. A method of producing a colored photographic image in a gelatino-silver halide layer containing an azo dye capable of being decolorized by reduction, which comprises exposing and developing the layer to produce a metallic silver image therein, and then simultaneously bleaching th dye and fixing out the silver and silver halide in a bath containing hydrochloric acid as a bleaching agent, a mild oxidizing agent for silver, and potassium thiocyanate as a fixing agent.
8. A bleach and fixing bath for use in a bleachout process of color photography, containing a fixing agent, a strong acid, and an azo dye as a mild oxidizing agent capable of oxidizing metallic silver to silver ion.
RICHARD V. YOUNG. MERRILL W. SEYMOUR.
CERTIFICATE OF CORRECTION. Patent vm. 2522,081 June 15, 1915.
RICHARD v: YOUNG, E'" AL.
It is hereby certified that error appears in the printed specification of the above nuinbered patent requiring correction as follows: P a-5e 2 first column, line 21;, for "14.01;." read 0,01 and that the said Letters Patentshould be read with this correction therein that the Same may conform to the record of the case in the Patent Office.
Signed and sealed this 51st day of g A. 9 1-5- Henry Van Arsdale, Acting Commissioner of Patents.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB602/40A GB539509A (en) | 1940-01-11 | 1940-01-11 | Improvements in or relating to the production of colour photographs |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2322084A true US2322084A (en) | 1943-06-15 |
Family
ID=9707267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US364548A Expired - Lifetime US2322084A (en) | 1940-01-11 | 1940-11-06 | Simultaneous bleaching and fixing bath |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2322084A (en) |
| DE (1) | DE735672C (en) |
| FR (1) | FR876360A (en) |
| GB (1) | GB539509A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2425363A (en) * | 1943-06-23 | 1947-08-12 | Eastman Kodak Co | Procedure for fixing nongelating emulsions and improved nongelatin emulsion fixing baths |
| US2434272A (en) * | 1944-05-03 | 1948-01-13 | Eastman Kodak Co | Color photography with azosubstituted couplers |
| US2494765A (en) * | 1944-11-10 | 1950-01-17 | Keuffel & Esser Co | Chemical erasing of photographic silver images |
| US2756151A (en) * | 1952-08-01 | 1956-07-24 | Eastman Kodak Co | Reduction of dye stain in processed photographic papers containing dyes |
| US3278303A (en) * | 1961-12-20 | 1966-10-11 | Ciba Ltd | Process for the preparation of multicolored images by the silver dyestuff bleaching method |
| US3520688A (en) * | 1967-05-25 | 1970-07-14 | Itek Corp | Photographic process comprising improved dye bleaching step |
| US3716362A (en) * | 1969-07-30 | 1973-02-13 | Ciba Geigy Ag | Process for the removal of metallic silver from photographic material |
| US3773510A (en) * | 1971-06-26 | 1973-11-20 | Minnesota Mining & Mfg | Additives to bleach/fix baths |
| DE2448433A1 (en) * | 1973-10-12 | 1975-04-24 | Ciba Geigy Ag | PROCESS FOR THE PROCESSING OF SILVER PAINT MATERIALS |
| DE2530469A1 (en) * | 1974-07-10 | 1976-01-29 | Ciba Geigy Ag | PROCESS FOR THE PROCESSING OF SILVER PAINT MATERIALS |
| US4070188A (en) * | 1975-06-23 | 1978-01-24 | Fuji Photo Film Co., Ltd. | One bath type silver dye bleaching and silver bleaching |
| US4125402A (en) * | 1976-08-19 | 1978-11-14 | Ciba-Geigy Ag | Method of processing silver dye bleaching materials and preparations suitable for the dye and silver bleaching |
| US4304846A (en) * | 1979-02-09 | 1981-12-08 | Ciba-Geigy Ag | Method for processing silver dye-bleach materials |
| US6455236B1 (en) * | 2000-01-06 | 2002-09-24 | Trebla Chemical Company | One-part bleach-fix liquid concentrates |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE947221C (en) * | 1944-03-03 | 1956-08-09 | Agfa Ag Fuer Photofabrikation | Process for the simultaneous bleaching and fixing of chromogenically developed color images |
| DE1039839B (en) * | 1957-07-04 | 1958-09-25 | Agfa Ag | Process for the production of color images by the silver dye bleaching process using azo dyes |
| DE1041355B (en) * | 1957-07-05 | 1958-10-16 | Agfa Ag | Process for the production of color images by the silver dye bleaching process using azo dyes |
| DE1039840B (en) * | 1957-07-13 | 1958-09-25 | Agfa Ag | Process for the production of color images by the silver dye bleaching process using azo dyes |
| BE579274A (en) * | 1958-06-03 | |||
| CH627006A5 (en) * | 1977-03-23 | 1981-12-15 | Ciba Geigy Ag |
-
1940
- 1940-01-11 GB GB602/40A patent/GB539509A/en not_active Expired
- 1940-11-06 US US364548A patent/US2322084A/en not_active Expired - Lifetime
-
1941
- 1941-02-05 DE DEK160042D patent/DE735672C/en not_active Expired
- 1941-10-27 FR FR876360D patent/FR876360A/en not_active Expired
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2425363A (en) * | 1943-06-23 | 1947-08-12 | Eastman Kodak Co | Procedure for fixing nongelating emulsions and improved nongelatin emulsion fixing baths |
| US2434272A (en) * | 1944-05-03 | 1948-01-13 | Eastman Kodak Co | Color photography with azosubstituted couplers |
| US2494765A (en) * | 1944-11-10 | 1950-01-17 | Keuffel & Esser Co | Chemical erasing of photographic silver images |
| US2756151A (en) * | 1952-08-01 | 1956-07-24 | Eastman Kodak Co | Reduction of dye stain in processed photographic papers containing dyes |
| US3278303A (en) * | 1961-12-20 | 1966-10-11 | Ciba Ltd | Process for the preparation of multicolored images by the silver dyestuff bleaching method |
| US3520688A (en) * | 1967-05-25 | 1970-07-14 | Itek Corp | Photographic process comprising improved dye bleaching step |
| US3716362A (en) * | 1969-07-30 | 1973-02-13 | Ciba Geigy Ag | Process for the removal of metallic silver from photographic material |
| US3773510A (en) * | 1971-06-26 | 1973-11-20 | Minnesota Mining & Mfg | Additives to bleach/fix baths |
| DE2448433A1 (en) * | 1973-10-12 | 1975-04-24 | Ciba Geigy Ag | PROCESS FOR THE PROCESSING OF SILVER PAINT MATERIALS |
| US3963492A (en) * | 1973-10-12 | 1976-06-15 | Ciba-Geigy Ag | Method for processing silver dye bleach materials |
| DE2530469A1 (en) * | 1974-07-10 | 1976-01-29 | Ciba Geigy Ag | PROCESS FOR THE PROCESSING OF SILVER PAINT MATERIALS |
| US4070188A (en) * | 1975-06-23 | 1978-01-24 | Fuji Photo Film Co., Ltd. | One bath type silver dye bleaching and silver bleaching |
| US4125402A (en) * | 1976-08-19 | 1978-11-14 | Ciba-Geigy Ag | Method of processing silver dye bleaching materials and preparations suitable for the dye and silver bleaching |
| US4304846A (en) * | 1979-02-09 | 1981-12-08 | Ciba-Geigy Ag | Method for processing silver dye-bleach materials |
| US6455236B1 (en) * | 2000-01-06 | 2002-09-24 | Trebla Chemical Company | One-part bleach-fix liquid concentrates |
Also Published As
| Publication number | Publication date |
|---|---|
| DE735672C (en) | 1943-05-24 |
| FR876360A (en) | 1942-11-04 |
| GB539509A (en) | 1941-09-15 |
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