US2476544A - Antistain agents for silver bleach solutions - Google Patents
Antistain agents for silver bleach solutions Download PDFInfo
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- US2476544A US2476544A US563996A US56399644A US2476544A US 2476544 A US2476544 A US 2476544A US 563996 A US563996 A US 563996A US 56399644 A US56399644 A US 56399644A US 2476544 A US2476544 A US 2476544A
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- silver
- bleaching
- color
- solution
- film
- Prior art date
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- Expired - Lifetime
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- 229910052709 silver Inorganic materials 0.000 title description 16
- 239000004332 silver Substances 0.000 title description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 15
- 239000007844 bleaching agent Substances 0.000 title description 11
- 239000003795 chemical substances by application Substances 0.000 title description 11
- 238000004061 bleaching Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000007800 oxidant agent Substances 0.000 description 12
- -1 silver halides Chemical class 0.000 description 12
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 238000010186 staining Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 4
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 4
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 description 4
- 235000019800 disodium phosphate Nutrition 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 3
- 235000010265 sodium sulphite Nutrition 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
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement 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
- G03C7/30—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 photographic bleaching baths, particularly to bleaching baths employed in multicolor photography, and especially to non-staining baths for the bleaching of the silver image in a multicolor film following color coupling development.
- the exposed film is first developed with a normal black and white developer to produce a negative. After development the black and white negative film, without being fixed, is then exposed to general illumination followed by a second development with a color forming developer. During the first and second development the silver halides in all the layers are reduced to metallic silver. After the second development the film is cleared in running water for a period of from 15 seconds to 2 minutes, hardened in an aqueous solution consisting of either alum or potassium chrome alum for 5 minutes and then washed in running water from to 20 minutes.
- the silver present in all the layers formed during the first and second development is converted into a salt by any of the known silver-salt formers, commonly known as bleaching baths, and the silver-salt thus formed is then removed by solution in a silversalt solvent such as, for example, hypo.
- a silversalt solvent such as, for example, hypo.
- the principal object of the present invention is to eliminate excessive washingtimes of a color developed multicolor film and to provide an improved bleaching bath which prevents the formation of stain.
- aliphatic aldehydes such as formaldehyde, paraformaldehyde (trioxymethylene), acetaldehyde (paraldehyde) aldol, crotonaldehyde, propionaldehyde and the like.
- concentration of the aliphatic aldehyde required may vary considerably. For instance, as little as 5 cc. of an aliphatic aldehyde per liter of bleach solution has been found to eliminate stain, and as much as cc.
- bleach solutions contain an oxidizing agent dissolved in a suitable solvent, such as, for example, water, with or without the presence of other adjuvants.
- a suitable solvent such as, for example, water
- a typical bleach solution consists of grams of an oxidizing agent per liter of solution, and may contain one or more of the following ingredients:
- an oxidizing agent we mean an inorganic compound such as potassium bromide or sodium thiocyanate which by reason of a difierence in solubility will replace the silver ferrocyanide formed in the bleaching reaction (when ferricyanide is used as the oxidizing agent) to form silver bromide or silver thiooyanate and: thus impel the bleaching reactionto-completion.
- Con verting agents are sometimes called halogenizing agents.
- buffering agents we mean any substance that is added to bring the bleach solution to a specified pH and to maintain this pH even though small amounts of acids or alkali may be carried into the: bleach by the filma
- the pI-Is used in bleaching color films are generally maintained between 3 and 9-.
- solvent we refer to the liquid in which the above materials are dissolved which is usually water.
- the films were Washed for 2" minutes in running water, and thengiven a second exposure-
- the color developed films were rinsed for 1 minute in running water, and hardened for 5 minutes in a 3% aqueous solution of chrome alum.
- the first washed film was treated in solution No. 1 and the second washed film was treated in solution No. 2 of the following compositions:
- Disodium mono potassium ferricyanide gramss 100 100 Potassium bromide do 10 10 Sodium tetra phosphate do.. 20 20 Disodium phosphate do 40 40 Sodium bisulfate do 25 Formalin (35-40% solution of formaldel-iyde ingwater) cc 20 Water to make up liters 1 1
- the two bleached film sheets were then washed in water for 5 minutes, fixed for 5 minutes in a 20% aqueous hypo solution, washed for an additional 5 minutes and then dried.
- the film bleached in solution No. 1 showed objectionable bluish stains, whereas the film bleached in solution No. 2 containing formalin was clear and unstained.
- the first washed film wastreated in solution No. '1 and the second washed film was treated in solution No. 2 of the following compositions:
- Example III Example IV Example II was repeated with the exception that bleach bath No. 2 contained cc. of croton- 3. The method of preventing the staining action of a bleaching bath during the bleaching of aldehyde instead of paraformaldehyde. The film bleached in the solution containing no crotonaldehyde showed objectionable bluish stains,
- organic hardening agents such as the hydroxy aldehydes described in Sheppard and I-Iouch, United States Patent 2,059,817, and the dialkyl diketones described in Staud and Briggs, United States Patent 2,963,351, may also be employed.
- the method of preventing the staining action of a bleaching bath during the bleaching of silver in an exposed and color-developed photographic emulsion containing a residual color coupler and a residual aromatic primary amino developing agent which comprises treating the said emulsion with a silver bleaching bath containing as the only oxidizing agent a Watersoluble inorganic oxidizing agent, selected from the class consisting of alkali metal ferricyanides and persulfates, and a carbonyl compound selected from the class consisting of aliphatic aldehydes and dialkyl di-ketones.
- silver in an exposed and color-developed photographic emulsion containing a residual color coupler and a residual aromatic primary amino developing agent which comprises treating the said emulsion with a silver bleaching bath containing as the only oxidizing agent a watersoluble inorganic oxidizing agent selected from the class consisting of alkali metal ferricyanides and persulfates, and acetaldehyde;
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Patented July 19, 1949 ANTISTAIN AGENTS FOR, SILVER BLEACH SOLUTIONS Harold C. Harsh and James E. Bates, Binghamton,
Corporation, New York, N. Y.,
Delaware N. Y., assignors to General Aniline & Film a corporation of N Drawing. Application November 17, 1944,
Serial No. 563,996
Claims. (Cl. 9588) This invention relates to photographic bleaching baths, particularly to bleaching baths employed in multicolor photography, and especially to non-staining baths for the bleaching of the silver image in a multicolor film following color coupling development.
It is known that in the processing of multicolor reversal film, the exposed film is first developed with a normal black and white developer to produce a negative. After development the black and white negative film, without being fixed, is then exposed to general illumination followed by a second development with a color forming developer. During the first and second development the silver halides in all the layers are reduced to metallic silver. After the second development the film is cleared in running water for a period of from 15 seconds to 2 minutes, hardened in an aqueous solution consisting of either alum or potassium chrome alum for 5 minutes and then washed in running water from to 20 minutes. After the latter treatment, the silver present in all the layers formed during the first and second development is converted into a salt by any of the known silver-salt formers, commonly known as bleaching baths, and the silver-salt thus formed is then removed by solution in a silversalt solvent such as, for example, hypo.
Prior to the bleaching operation it is essential that all traces of residual second or color developer be removed, otherwise stains will be formed during the bleaching operation by the oxidation of the residual developing agent and subsequent coupling with unreacted color former, particularly noticeable in the highlight areas. In order to convert the difficultly soluble color developing agent to its salt and to wash it from the film so as to prevent staining, rinses in acid hardening solutions such as, for example:
(1) 5% potassium chrome alum (2) 3% potassium alum+1% acetic acid (3) 3% potassium alum+3% sodium acetate+ 1 sodium bisulfate (4) 2% potassium chrome alum+2 sodium acetate+2% sodium citrate and short stop baths such as, for example:
(1) 1% acetic acid (2) 1% sodium bisulfite (3) 3% sodium acetate-14% sodium bisulfate (4) 5% potassium acid phthalate together with extended washing times in running water from 15 minutes to 120 minutes have been proposed. Despite these proposals and the time 55 chemical compound that will oxidize a metallicconsuming washing step, stains are nevertheless formed during the bleaching operation. It is believed that the staining results from the oxidation of traces of the color developing compounds retained in the layers of the film following color forming development which then react with the usused color former.
The principal object of the present invention is to eliminate excessive washingtimes of a color developed multicolor film and to provide an improved bleaching bath which prevents the formation of stain.
Other objects and features of the invention will become more apparent as the description proceeds.
We have found that the above objects are accomplished by incorporating into a bleach solution commonly known and used in color photography one of the aliphatic aldehydes, such as formaldehyde, paraformaldehyde (trioxymethylene), acetaldehyde (paraldehyde) aldol, crotonaldehyde, propionaldehyde and the like. This discovery makes it possible to considerably reduce the washing time between color development and the bleaching operation. The concentration of the aliphatic aldehyde required may vary considerably. For instance, as little as 5 cc. of an aliphatic aldehyde per liter of bleach solution has been found to eliminate stain, and as much as cc. per liter can be used without interference with the properties of the bleaching solution. Amounts higher than 80 cc. per liter can be employed, but there seems to be little improvement in stain prevention above a concentration of 40 cc. per liter. For practical purposes, however, concentrations ranging between 10 cc. and 40 cc. per liter are most desirable. Inorganic hardeners such as alum and potassium chrome alum can also be employed instead of the organic gelatin hardeners. The stain reduction obtained, however, with the former is considerably less than that obtained with the latter.
As is well-known, all bleach solutions contain an oxidizing agent dissolved in a suitable solvent, such as, for example, water, with or without the presence of other adjuvants. A typical bleach solution consists of grams of an oxidizing agent per liter of solution, and may contain one or more of the following ingredients:
By an oxidizing agent we mean an inorganic compound such as potassium bromide or sodium thiocyanate which by reason of a difierence in solubility will replace the silver ferrocyanide formed in the bleaching reaction (when ferricyanide is used as the oxidizing agent) to form silver bromide or silver thiooyanate and: thus impel the bleaching reactionto-completion. Con verting agents are sometimes called halogenizing agents.
By buffering agents we mean any substance that is added to bring the bleach solution to a specified pH and to maintain this pH even though small amounts of acids or alkali may be carried into the: bleach by the filma The pI-Is used in bleaching color films are generally maintained between 3 and 9-.
By corrosionpreventiveswe refer to thosecompounds Which retardthe' corrosive efiect of the bleach solution on ,developing tanks, trays, etc. Large quantities (20-80 grams-per liter) of alkali metal phosphates such as disodium phosphate, sodium tetraphosphate and the like, as well as the dialkylamino alcohols'desoribed in United States Patent 2 ,327,813,'have been found to prevent corrosion effectively.
By solvent we refer to the liquid in which the above materials are dissolved which is usually water.
The following examplesdeseribe in detailmetheds for accomplishing the above objects, but it is to be understood that they are inserted merely for purposes of illustration and are not to be construed as limiting the'scope'of the invention.
Eilid'm'pl I Two exposed 4 x5" multilayer color film sheets of the reversal type'were developed for minutes at 68 F. in a-developer of the following composition:
l-Iydroquinone 'do s 4 Sodium carbonate '1 1 ;do 80 sodium thiocya-nate l1 1 do 5 Potassium bromide -1 11 1- do 4 Water to make up- 1 Tisha-liters 1 The developed firms were short Stopped for 3 minutes in a 3% aqueous solution-of acetic acid or other acid ester.
The films were Washed for 2" minutes in running water, and thengiven a second exposure- The color developed films were rinsed for 1 minute in running water, and hardened for 5 minutes in a 3% aqueous solution of chrome alum.
The hardened: films were washed for '5 minutes in running water; V
The first washed film was treated in solution No. 1 and the second washed film was treated in solution No. 2 of the following compositions:
N0. 1 No. 2
Disodium mono potassium ferricyanide gramss 100 100 Potassium bromide do 10 10 Sodium tetra phosphate do.. 20 20 Disodium phosphate do 40 40 Sodium bisulfate do 25 Formalin (35-40% solution of formaldel-iyde ingwater) cc 20 Water to make up liters 1 1 The two bleached film sheets were then washed in water for 5 minutes, fixed for 5 minutes in a 20% aqueous hypo solution, washed for an additional 5 minutes and then dried. The film bleached in solution No. 1 showed objectionable bluish stains, whereas the film bleached in solution No. 2 containing formalin was clear and unstained.
Ezcample II Two exposed 1" x 5" multilayer color film sheets of the negative type were developed for 10 minutes at 68 F. in a developer of thefollowing composition:
Sodium sulfite grams 0.5 2-arnino-5-diethylamino toluene hydrochloride g'rams 2.5 Hydroxylamine I-ICl do 1 Sodium carbonate d0 65 Potassium bromide do' 2.5 Water to make up liters 1 The developed films were short stopped for 5 minutes in a solutionoi the following composition:
Mono potassium phosphate grams 8O Disodium phosphate do 20 Water to make up 111 liters 1 The films we're hardened for 3 minutes in a 3% chrome alum solution, and washed for 5 minutes in running water.
The first washed film wastreated in solution No. '1 and the second washed film was treated in solution No. 2 of the following compositions:
7 No. 1 N0. 2 Potassium ferricyanide -grains 100 Disodium phosphate 11 do 4.3 4.3 Mono potassium phosphate do 5.8 5.8 Potassium bromide 1 do 10 10 Sodium sulfite do 0.5 Paraformaldehyde d0' 16 Water to make up liters 1 1 The paraiormal'dehyde in the above formula is relatively difficult to dissolve unless a small amount of alkali or sodium sulfite is first added to the water. We have found that 16 grams of p'araformaldeh'yde dissolved with the aid of 0.5 grams of sodium 's'ulfite to be the equivalent of 40-50 cc. of formalin.
The two bleached sheet films were then washed for 5. minutes, fixed for 5 minutes in a 20% aqueous solution of hypo, washed an additional 15 minutes and then dried. Asin Example]; the film bleached in solution No. 1, containing no paraformaldehyde, showed-bluish stains, whereas the film bleachedin solution No.2 was clear and unstained.
Example III Example IV Example II was repeated with the exception that bleach bath No. 2 contained cc. of croton- 3. The method of preventing the staining action of a bleaching bath during the bleaching of aldehyde instead of paraformaldehyde. The film bleached in the solution containing no crotonaldehyde showed objectionable bluish stains,
while the film bleached with the solution con-' taining crotonaldehyde was clear and unstained.
In place of aliphatic aldehydes referred to above, organic hardening agents such as the hydroxy aldehydes described in Sheppard and I-Iouch, United States Patent 2,059,817, and the dialkyl diketones described in Staud and Briggs, United States Patent 2,963,351, may also be employed.
The above specific examples are to be regarded as merely illustrative of the invention, and not in any sense restrictive. It will be obvious to anyone skilled in the art that many modifications such as substituting equivalent materials and varying the proportions of materials used are within the spirit and scope of the invention as defined in the appended claims.
We claim:
1. The method of preventing the staining action of a bleaching bath during the bleaching of silver in an exposed and color-developed photographic emulsion containing a residual color coupler and a residual aromatic primary amino developing agent which comprises treating the said emulsion with a silver bleaching bath containing as the only oxidizing agent a Watersoluble inorganic oxidizing agent, selected from the class consisting of alkali metal ferricyanides and persulfates, and a carbonyl compound selected from the class consisting of aliphatic aldehydes and dialkyl di-ketones.
2. The method of preventing the staining action of a bleaching bath during the bleaching of silver in an exposed and color-developed photographic emulsion containing a residual color coupler and a residual aromatic primary amino developing agent which comprises treating the said emulsion with a silver bleaching bath containing as the only oxidizing agent a watersoluble inorganic oxidizing agent selected from the class consisting of alkali metal ferricyanides and persulfates, and formaldehyde. 4
silver in an exposed and color-developed photographic emulsion containing a residual color coupler and a residual aromatic primary amino developing agent which comprises treating the said emulsion with a silver bleaching bath containing as the only oxidizing agent a watersoluble inorganic oxidizing agent selected from the class consisting of alkali metal ferricyanides and persulfates, and acetaldehyde;
4. The method of preventing the staining action of a bleaching bath during the bleaching of silver in an exposed and color-developed photographic emulsion containing a residual color coupler and a residual aromatic primary amino developing agent which comprises treating the said emulsion with a silver bleaching bath containing as the only oxidizing agent a watersoluble inorganic oxidizing agent selected from the class consisting of alkali metal ferricyanides and persulfates; and crotonaldehyde.
5. The method according to claim 1 wherein the concentration of the aliphatic aldehyde and dialkyl di-ketone ranges from 5 to parts per liter of bleach.
HAROLD O. I-IARSI-I.
JAMES E. BATES.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,214,940 Miller Feb. 6, 1917 1,697,194 Leventhal Jan. 1, 1929 1,939,026 Spencer et al. Dec. 12, 1933 1,969,479 Seymour Augc 7, 1934 2,018,195 Thornton Oct. 22, 1935 2,171,609 Snyder et a1 Sept. 5, 1939 2,331,492 Michaelis Oct. 12, 1943 2,356,477 Staud 'et al Aug. 22, 1944 2,356,486 Weissberger et a1. Aug. 22, 1944 2,367,548 Vittum A Jan. 16, 1945 2,378,265 Vittum June 12, 1945 2,384,658 Vittum ..Sept. 11, 1945 FOREIGN PATENTS Number Country Date 261,201 Great Britain Nov. 18, 1926 OTHER REFERENCES Warburg, Brit. J. Phot. Monthly Supplement on Colour Phot., volume 25, page 9, March 6, 1931. (Copy in Patent Office Library.)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US563996A US2476544A (en) | 1944-11-17 | 1944-11-17 | Antistain agents for silver bleach solutions |
GB28465/45A GB603121A (en) | 1944-11-17 | 1945-10-27 | Improvements in photographic solutions for coverting silver images to silver salt images |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US563996A US2476544A (en) | 1944-11-17 | 1944-11-17 | Antistain agents for silver bleach solutions |
Publications (1)
Publication Number | Publication Date |
---|---|
US2476544A true US2476544A (en) | 1949-07-19 |
Family
ID=24252744
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US563996A Expired - Lifetime US2476544A (en) | 1944-11-17 | 1944-11-17 | Antistain agents for silver bleach solutions |
Country Status (2)
Country | Link |
---|---|
US (1) | US2476544A (en) |
GB (1) | GB603121A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2885288A (en) * | 1954-07-21 | 1959-05-05 | Ici Ltd | Colour photographic process |
US2980536A (en) * | 1956-07-02 | 1961-04-18 | Morton Chemical Co | Photographic shortstop compositions |
US4960682A (en) * | 1988-12-19 | 1990-10-02 | Eastman Kodak Company | Bleaching compositions containing a dye-stabilizing agent and use thereof in photographic color processing |
US5795681A (en) * | 1994-07-09 | 1998-08-18 | Mueller; Helmut | Stabilization of holograms formed in gelatin |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2626215A (en) * | 1950-03-03 | 1953-01-20 | Miracol R Ltd | Method of developing multilayer color films |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1214940A (en) * | 1915-02-26 | 1917-02-06 | Brewster Film Corp | Coloring or dyeing photographic images. |
GB261201A (en) * | 1924-08-15 | 1926-11-18 | Karl Emil Taeschner | Improved method of and means for reducing photographic negatives, positives, films, bromide and gaslight prints |
US1697194A (en) * | 1923-01-31 | 1929-01-01 | Jacob F Leventhal | Method of color photography |
US1939026A (en) * | 1931-04-23 | 1933-12-12 | Spencer | Colored gelatine relief image |
US1969479A (en) * | 1931-05-11 | 1934-08-07 | Eastman Kodak Co | Method of producing color photographic images by development |
US2018195A (en) * | 1934-03-29 | 1935-10-22 | Thornton John Edward | Production of photographic and cinematograph mosaic color positives |
US2171609A (en) * | 1936-01-18 | 1939-09-05 | Technico Inc | Toning photographic prints |
US2331492A (en) * | 1938-06-13 | 1943-10-12 | Chromogen Inc | Process and material for printing photographic images |
US2356486A (en) * | 1943-04-15 | 1944-08-22 | Eastman Kodak Co | Stain prevention in color photography |
US2356477A (en) * | 1941-03-25 | 1944-08-22 | Eastman Kodak Co | Hardeners for photographic processing solutions |
US2367548A (en) * | 1942-09-04 | 1945-01-16 | Eastman Kodak Co | Hardening and stain prevention process in color photography |
US2378265A (en) * | 1941-01-17 | 1945-06-12 | Eastman Kodak Co | Color photography |
US2384658A (en) * | 1943-07-10 | 1945-09-11 | Eastman Kodak Co | Color photography |
-
1944
- 1944-11-17 US US563996A patent/US2476544A/en not_active Expired - Lifetime
-
1945
- 1945-10-27 GB GB28465/45A patent/GB603121A/en not_active Expired
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1214940A (en) * | 1915-02-26 | 1917-02-06 | Brewster Film Corp | Coloring or dyeing photographic images. |
US1697194A (en) * | 1923-01-31 | 1929-01-01 | Jacob F Leventhal | Method of color photography |
GB261201A (en) * | 1924-08-15 | 1926-11-18 | Karl Emil Taeschner | Improved method of and means for reducing photographic negatives, positives, films, bromide and gaslight prints |
US1939026A (en) * | 1931-04-23 | 1933-12-12 | Spencer | Colored gelatine relief image |
US1969479A (en) * | 1931-05-11 | 1934-08-07 | Eastman Kodak Co | Method of producing color photographic images by development |
US2018195A (en) * | 1934-03-29 | 1935-10-22 | Thornton John Edward | Production of photographic and cinematograph mosaic color positives |
US2171609A (en) * | 1936-01-18 | 1939-09-05 | Technico Inc | Toning photographic prints |
US2331492A (en) * | 1938-06-13 | 1943-10-12 | Chromogen Inc | Process and material for printing photographic images |
US2378265A (en) * | 1941-01-17 | 1945-06-12 | Eastman Kodak Co | Color photography |
US2356477A (en) * | 1941-03-25 | 1944-08-22 | Eastman Kodak Co | Hardeners for photographic processing solutions |
US2367548A (en) * | 1942-09-04 | 1945-01-16 | Eastman Kodak Co | Hardening and stain prevention process in color photography |
US2356486A (en) * | 1943-04-15 | 1944-08-22 | Eastman Kodak Co | Stain prevention in color photography |
US2384658A (en) * | 1943-07-10 | 1945-09-11 | Eastman Kodak Co | Color photography |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2885288A (en) * | 1954-07-21 | 1959-05-05 | Ici Ltd | Colour photographic process |
US2980536A (en) * | 1956-07-02 | 1961-04-18 | Morton Chemical Co | Photographic shortstop compositions |
US4960682A (en) * | 1988-12-19 | 1990-10-02 | Eastman Kodak Company | Bleaching compositions containing a dye-stabilizing agent and use thereof in photographic color processing |
US5795681A (en) * | 1994-07-09 | 1998-08-18 | Mueller; Helmut | Stabilization of holograms formed in gelatin |
Also Published As
Publication number | Publication date |
---|---|
GB603121A (en) | 1948-06-09 |
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