US3189452A - Color-forming photographic process utilizing a bleach-fix followed by a bleach - Google Patents

Color-forming photographic process utilizing a bleach-fix followed by a bleach Download PDF

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Publication number
US3189452A
US3189452A US157096A US15709661A US3189452A US 3189452 A US3189452 A US 3189452A US 157096 A US157096 A US 157096A US 15709661 A US15709661 A US 15709661A US 3189452 A US3189452 A US 3189452A
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United States
Prior art keywords
color
bleach
silver
emulsion layer
photographic
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Expired - Lifetime
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US157096A
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English (en)
Inventor
Charleton C Bard
George P Varlan
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE625533D priority Critical patent/BE625533A/xx
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Priority to US157096A priority patent/US3189452A/en
Priority to DEE23937A priority patent/DE1202638B/de
Priority to FR917318A priority patent/FR1359125A/fr
Priority to GB459/62A priority patent/GB1026496A/en
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    • 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
    • G03C7/407—Development processes or agents therefor

Definitions

  • the present invention relates to photography and particularly to the processing of color photographic materials. Still more particularly, the invention relates to a shortened method for the processing of coupler-incorporating, colorforming photographic films and prints.
  • the color developer bath is usually followed by consecutive baths comprising a fix, a bleach, and a fix again with an intervening wash step between each of the baths indicated.
  • the fix bath is employed to remove the undeveloped silver halide from the developed emulsion layers while the bleach bath is employed to oxidize the metallic silver formed by development to silver halide.
  • the second fix is normally employed to remove the silver halide formed by the previous bleaching step so that the emulsion layers are cleared of residual silver and silver halide. This leaves essentially a colored image of cyan, magenta, and yellow dye densities as formed at the time of development by coupling of the incorporated couplers with oxidation products of a primary aromatic amino developing agent contained in the color developer bath.
  • FIG. 1 shows the colored image densities obtained in a standard photographic process
  • FIG. 2 shows the colored image densities obtained using the present shortened process.
  • Photographic materials of the type processed according to the present invention comprise materials having color-forming couplers contained in respective layers of a multilayer photographic element. Materials of this type have been described in a number of US. and foreign patents, for example, in US. Patents 2,322,027, Tune 15, 1943; 2,407,210, September 3, 1946; 2,474,293, June 28, 1949; 2,640,776, June 2, 1953; and 2,956,876, October 18, 1960. Color films of the invention include the so-called negative-positive type materials as well as reversal materials.
  • the photographic multilayer color materials of the invention comprise elements having usually three selectively sensitive emulsion layers coated on one side of a photographic support.
  • Sensitive layers of the elements of the present invention contain color-forming couplers to form the complementary dye to wmch a particular layer is sensitive.
  • the uppermost layer is generally blue-sensitive and normally in corporates a yellow-forming coupler.
  • the next layer generally comprises a filter layer which is yellow in color and blue absorbing and being placed under the top layer absorbs most of the blue light thus preventing unwanted blue exposure below the filter layer.
  • the next layer is generally green-sensitive and usually incorporates a magenta-dye forming coupler.
  • the emulsion layer adjacent to the support is generally red-sensitive and according to the present invention normally contains a cyan-dye forming coupler.
  • multilayer photographic elements as used in the present invention contain additional silver halide emulsion layers or other interlayers for specialized purposes.
  • the yellow filter layer is omitted and the arrangement of silver halide emulsion layers may be changed for the purpose of obtaining more accurate recording of the color negative.
  • the combined bleaching and fixing solution can be prepared by combining a number of silver bleaching agents and silver halide fixing agents.
  • a suitable bleaching agent can comprise an alkali metal dichromate (e.g., sodium dichromate, and potassium dichromate), an alkali metal ferricyanide (e.g., potassium ferricyanide, and sodium terricyanide), ferricyanide-bromide, permanganate (e.g., potassium permanganate), quinone, and the like.
  • Such bleaching agents can be combined in freshly prepared solutions with such fixing agents as alkali metal thiocyanates (e.g., sodium thiocyanate and potassium thiocyanate), ammonium thiocyanate, alkali metal thiosulfate (e.g., sodium thiosulfate and potassium thiosulfate), ammonium thiosulfate, thioureas, and alkali metal selenocyanates (e.g., sodium selenocy anate and potassium selenocyanate).
  • alkali metal thiocyanates e.g., sodium thiocyanate and potassium thiocyanate
  • alkali metal thiosulfate e.g., sodium thiosulfate and potassium thiosulfate
  • ammonium thiosulfate e.g., sodium thiosulfate and potassium thiosulfate
  • ammonium thiosulfate
  • a thicken-ing agent which results in the formation of a viscous solution.
  • Such viscous solutions can be applied as a surface layer on the photographic material to be processed.
  • Suitable thickening agents for this purpose include a wide variety of materials, such as carboxymethylcellulose, ethylcelluiose, gelatin, poly-vinyl alcohol, collod-ion, polyvinyl acetals, cellulose esters, and the like.
  • More stable combined bleaching and fixing solutions comprise, for example, a ferric chloride solution containing a sequestering agent such as ethylene diamine tetra-v acetic acid tetnasoclium salt, and a fixing agent such as sodium thiosulfate.
  • a sequestering agent such as ethylene diamine tetra-v acetic acid tetnasoclium salt
  • a fixing agent such as sodium thiosulfate.
  • Other combined solutions of the j can be prepared by dissolving an appropriate amount of a silver bleaching agent of the type mentioned baths have been described, for example, in US. Patents 2,745: ,000, May 29, 1 956; 2,113,329, April 5, 1938; and 2,252,718, August 19, 1941.
  • Photographic silver halide emulsions useful in the process of the present invention can be prepared according to known methods such as those described in Hewit- -s on and McClintock, US. Patent 2,618,556, November '18, 1952. Emulsions prepared by other methods can also 1 ganic and have boiling points above about 175 C.
  • cellulose nitrate, etc. water-insoluble, but Water-permeable cellulose ethers, Water-insoluble but water-penneable natural and'synthetic resins, high-boiling, substantially Water-insoluble crystalloidal materials, such as N-n-aniylphthalimide, tetrahydrofurfuryl benzoate, triphenyl phosphate, n-butyl phthalate, and the like (see also U.S.
  • Photographic elements of the present invention can be prepared by employing any of the emulsions previously described. Emulsions of the present type can be coated as separate layers on typical supports as used in preparzing such photographic elements, such as cellulose acetate film, resin film, paper etc. elements of the invention which contain separate layers and are therefore referred to as multilayer materials have been described in such US. Patents as 1,055,155, 2 March 4, 1913; 2,304,940, December 15, 1942; and 2,322,- 027, June 15, 1943. The present invention is also applicable to color photo- 'g-naphic emulsion materials wherein the emulsions are 1 mixed instead of disposed in separate layers.
  • emulsions can be employed in the invention which comprise single emulsions containing color tormers for making component color pictures.
  • the emulsions of the present invention in addition to containing color- 1 formers (couplers) as previously indicated, can also con- ;tain sensitizing dyes in addition to the usual addenda' j employed in emulsions of the present type.
  • crystalloidal materials such as Water-insoluble but water color-formers and for the dyes formed therefrom andare permeable to photographic processing solutions.
  • These crystalloidal materials have been referred to as oil formers because they have the property of producing an oily or liquid solution when mixed with the coupler, even though the cou ler is a solid.
  • the crystalloidalmaterials. are generally liquid'at ordinary temperatures or low melting solids (below 100 C.),
  • the most useful compounds contain one or more polar groups such as'halogen, hydroxyl, carboxylic acid, amide, ketone, etc.
  • the emulsions of the present photographic elements a permeable cellulose esters, e.g., Water-insoluble, but waterpermeable cellulose acetate, cellulose acetate-phthalate,
  • developers having two primary amino groups as Well as those having one of the amino groups substituted or having substituents in the ring, such as the alkyl phenylene diarnines.
  • These compounds are usually used in the salt form, such as the hydrochloride or the sulfate which are more stable than the amines themselves.
  • the suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-pphenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, and Z-amino-S-diethylaminotoluene hydrochloride.
  • the p-amino phenols and their substitution products may also be used where the amino group is unsubstituted. All of these developers have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color-forming compounds to form a dye image.
  • the color-formers can be incorporated in the emulsions in the customary manner, e.g., by adding a dispersion of the coupler in a water-insoluble but waterpermeable material to the emulsion as indicated previously, or by adding a dispersion of the alkali metal of the coupler in water. Couplers can also be added to the emulsion in crystalloidal materials such as oil-boiling organic crystalloidal materials to produce an oil-like misture which can then be dispersed in water or a binder of colloidal character as well known in the art. (See for example U.S.
  • Dispersion of the coupler in a binder can be efiected with the aid of a homogenizer, a colloid mill, or the like; and dispersions can be stabilized by the addition of emulsifying agents also well known in the art.
  • sensitizing dyes of the type previously indicated normally are added to the emulsion before the coupler or coupier dispersion is added.
  • Typical sensitizing dyes for use in emulsions of the invent-ion have been described in a number of U18. and foreign patents, for example, US. Patents 2,478,366, August 9, 1949; 2,213,238, September 3, 1940; 2,231,658, February 11, 1941; and 2,515,- 913, July 18, 1950.
  • EXAMPLE I A multilayer photographic element of the type described in Jelley and Vittum U.S. Patent 2,322,027, issued June 15, 1943, was used as the multilayer sensitive element. Separate elements of the type described were given a like exposure to a colored image in theusual manner and processed according to the following procedures in which one of said elements was processed in a conventional manner (Process A) and the second element was processed according to the present invention (Process B).
  • pvhereas processing according to the present invention required25 minutes, 47 seconds and employed eight steps.
  • the process of the present invention in effect, reverses the normal processing order by employ ing a bleach bath'subsequent to a fixing bath to clear the photographic material of silver and silver halide from the emulsion layers.
  • FIG. 1 shows the sensitornetric curves obtained from the material processed according to Process A
  • 'FIG. 2 shows the sensitometnic curves obtained in a comparable element processed according to Process B.
  • sensitometric curve shows the integral cyan dye density of the prowssed element as measured in a Well known manner on an Eastman Electronic densitometer using a tungsten light source and red-light transmitting filter.
  • Sen-sitometric curves 11 and 112 show the integral magenta and yellow dye densities,-
  • sensitometric curves 13, 14, and show, respectively, the cyan, magenta and yellow integral dye densities obtained in like manner in the element processed according to Process B.
  • the density measurements were made employing, respectively, red-, greenand blue-light (transmitting sources as in the 'FIG. 1 determination.
  • the retention of silver in the elements processed in l the present example was in each' case 1 mg. or less p r square foot for theelements processed according to either of Processes A or B as determined in a well known manner, for example, by X-ray'fiuorescence analysis.
  • the ele- .rnents .usedin the present example contained in excess of 200 mg. of silver per square foot prior to processing.
  • 6-nitrobenzimidazole nitrate (0.5% solution) ml 12. Water to 1.0 liter. pH 10.03 at 75 F.
  • the process time in the present example was shortened from 75 minutes to 54 minutes and resulted in reduced stain density according to the following data.
  • the stain densities were measured in a well known manner by reflection densitometry in which the integral dye densities in the cyan, magenta, and yellow were determined using red-, greenand blue-transmitting filters, respectively.
  • photographic materials of the previous examples contained in excess of 200 mg. of silver per square foot.
  • the silver retained after processing was equal to or less than the silver retention in conventionally processed elements which involved more time and a greater number of steps.
  • Photographic materials having from 200 to about 600 mg. of silver per square foot can be processed to an optimum photographic result by way of the present invention.
  • the improvemnt which comprises treating the said color developed emulsion layer with an aqueous solution containing ferric chloride and an alkali metal thiosulfate and thereby solubilizing and removing silver and silver halide from said emulsion layer, and thereafter further treating the resulting emulsion layer with an aqueous solution containing an alkali metal ferricyanide and thereby oxidizing leuco dye in said emulsion layer to the full color intensity of the dye.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US157096A 1961-12-05 1961-12-05 Color-forming photographic process utilizing a bleach-fix followed by a bleach Expired - Lifetime US3189452A (en)

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Application Number Priority Date Filing Date Title
BE625533D BE625533A (is") 1961-12-05
US157096A US3189452A (en) 1961-12-05 1961-12-05 Color-forming photographic process utilizing a bleach-fix followed by a bleach
DEE23937A DE1202638B (de) 1961-12-05 1962-11-30 Photographisches Entwicklungsverfahren zur Herstellung von Farbbildern nach dem Farbentwicklungsverfahren
FR917318A FR1359125A (fr) 1961-12-05 1962-12-03 Nouveau procédé de traitement photographique en couleurs
GB459/62A GB1026496A (en) 1961-12-05 1962-12-05 Method of photographic processing

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3335004A (en) * 1963-12-09 1967-08-08 Eastman Kodak Co Method for stabilization processing of color emulsions
US3607277A (en) * 1967-10-14 1971-09-21 Agfa Gevaert Ag Photographic viscous processing
US3617283A (en) * 1966-05-06 1971-11-02 Fuji Photo Film Co Ltd Simultaneous bleach-fixing method in color photography
US3642472A (en) * 1967-08-30 1972-02-15 Holotron Corp Bleaching of holograms
US3833376A (en) * 1972-11-24 1974-09-03 Minnesota Mining & Mfg Color development process and compositions
US3879203A (en) * 1972-04-12 1975-04-22 Agfa Gevaert Ag Process for bleach-fixing color photographic silver halide material
US3942984A (en) * 1972-03-17 1976-03-09 Agfa-Gevaert Aktiengesellschaft Process for bleach-fixing chromogenically color photographic silver halide material
US4293638A (en) * 1979-05-30 1981-10-06 Eastman Kodak Company Method for alleviating partial inactivation of color couplers
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380809A (en) * 1939-12-11 1945-07-31 Verkinderen Honore Color couplers for photographic color development
US2506622A (en) * 1944-03-11 1950-05-09 Technicolor Motion Picture Elimination of preservative sulfite from photographic developers prior to use in color development
US2737457A (en) * 1952-11-22 1956-03-06 Jerome Flax Photographic method of tonal scale compensation
US2752244A (en) * 1955-02-23 1956-06-26 Gen Aniline & Film Corp Method and compounds for discharging filter dyes in photographic film
DE1051117B (de) * 1957-09-03 1959-02-19 Agfa Ag Verfahren zum gleichzeitigen Bleichen und Fixieren eines photographischen Farbbildes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE23348C (de) * H. J. KOLK, C. A. J. GURSCH und C. H. J. KLEMM, letztere Beiden in Firma GURSCH & KLEMM in Berlin Verfahren zur Erhöhung der Dauerhaftigkeit der Matrizen und Patrizen zu Giefszwecken im Allgemeinen und für Typengiefszwecke im Besonderen
DE866605C (de) * 1944-11-27 1953-02-12 Bayer Ag Verfahren zur Herstellung photographischer Abschwaecher- und Bleichfixierbaeder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380809A (en) * 1939-12-11 1945-07-31 Verkinderen Honore Color couplers for photographic color development
US2506622A (en) * 1944-03-11 1950-05-09 Technicolor Motion Picture Elimination of preservative sulfite from photographic developers prior to use in color development
US2737457A (en) * 1952-11-22 1956-03-06 Jerome Flax Photographic method of tonal scale compensation
US2752244A (en) * 1955-02-23 1956-06-26 Gen Aniline & Film Corp Method and compounds for discharging filter dyes in photographic film
DE1051117B (de) * 1957-09-03 1959-02-19 Agfa Ag Verfahren zum gleichzeitigen Bleichen und Fixieren eines photographischen Farbbildes

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3335004A (en) * 1963-12-09 1967-08-08 Eastman Kodak Co Method for stabilization processing of color emulsions
US3617283A (en) * 1966-05-06 1971-11-02 Fuji Photo Film Co Ltd Simultaneous bleach-fixing method in color photography
US3642472A (en) * 1967-08-30 1972-02-15 Holotron Corp Bleaching of holograms
US3607277A (en) * 1967-10-14 1971-09-21 Agfa Gevaert Ag Photographic viscous processing
US3942984A (en) * 1972-03-17 1976-03-09 Agfa-Gevaert Aktiengesellschaft Process for bleach-fixing chromogenically color photographic silver halide material
US3879203A (en) * 1972-04-12 1975-04-22 Agfa Gevaert Ag Process for bleach-fixing color photographic silver halide material
US3833376A (en) * 1972-11-24 1974-09-03 Minnesota Mining & Mfg Color development process and compositions
US4293638A (en) * 1979-05-30 1981-10-06 Eastman Kodak Company Method for alleviating partial inactivation of color couplers
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

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BE625533A (is")
DE1202638B (de) 1965-10-07

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