US3201244A - Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products - Google Patents

Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products Download PDF

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Publication number
US3201244A
US3201244A US231587A US23158762A US3201244A US 3201244 A US3201244 A US 3201244A US 231587 A US231587 A US 231587A US 23158762 A US23158762 A US 23158762A US 3201244 A US3201244 A US 3201244A
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United States
Prior art keywords
photographic
color
carbohydrazide
dye
couplers
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Expired - Lifetime
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US231587A
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English (en)
Inventor
George W Larson
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority to BE638633D priority Critical patent/BE638633A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US231587A priority patent/US3201244A/en
Priority to US231557A priority patent/US3201243A/en
Priority to DEE25661A priority patent/DE1173802B/de
Priority to GB42314/66A priority patent/GB1057952A/en
Priority to GB40779/63A priority patent/GB1057951A/en
Priority to FR950895A priority patent/FR1371657A/fr
Application granted granted Critical
Publication of US3201244A publication Critical patent/US3201244A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • 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
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings

Definitions

  • This invention relates to color photography and more particularly to methods for preventing discoloration of photographic dye images.
  • the invention also includes photographic layers or elements stabilized against discoloration according to the new methods.
  • Photographic color images can be produced by a variety of processes. Perhaps the most common involves the formation of the desired color record by coupling between one or more color couplers and the oxidation products of an ordinary photographic color developing agent, such as a phenylenediamine.
  • the color coupler in such processes can be incorporated either within the photographic element itself, or within the color developer solution.
  • Another method of producing a color record involves the use of the well known dye bleach process, wherein a uniformly dyed layer is selectively bleached in accordance with a silver record produced through conventional photographic development. Bleaching occurs at the site of formation of the silver-image.
  • Still another means of producing a photographic color image is through a diffusion transfer process which uses a dye developer to effectphotographic development and to produce a diffusible dye, which then migrates imagewise to a receiving surface.
  • Thepresent invention provides a means of stabilizing all of these types of photographic dye images, although it is particularly useful in preserving dye images which have been produced by the conventional process of color development using a color developer containing the color-forming compound, or A coupler.
  • This latter process is a reversal type of process wherein the color development is preceded by a conventional black-and-white development operation which produces a negative silver image. After negative development, there is one or more exposures followed by color development in a developer containing the desired color-forming compound, or coupler.
  • an object of the present invention to provide an improved method for preventing the discoloration or decomposition of photographic layers containing dye images subject to fading, or print-out under the influence of actinic radiation. It is a further object to provide photographic color materials, including films, transparencies, or prints which have been stabilized by treatment with particular stabilizing compounds. Other objects will become apparent from a consideration of the following description and examples.
  • the system of three-color photography suggested by Fischer in US. Patent 1,055,155, issued March 4, 1913 forms the basis for a number of color photographic processes and products.
  • this process involves the incorporation of different color-forming coupler compounds in each of three superposed dilferently color-sensitized (red, green and blue) silver halide emulsion layers.
  • Each of the three couplers is capable of producing a color complementary to the sensitivity of the layer in whichis is incorporated by reaction with the oxidation products of certain types of photographic developing agents. In this way a developed silver image and a colored dye image are formed simultaneously in each of the three superposed emulsion layers.
  • the silver images and residual undeveloped silver halide may then be removed from the multilayer photographic element by bleaching, fixing and washing according to now wellknown methods.
  • the color-forming couplers can be incorporated in the developer rather than The couplers suggested by Fischer containing phenolic hydroxyl, or ketomethylene groups, react with the oxidation products of aromatic amine developing agents during photographic development to form indophenol, indamine, indoaniline or azomethine (including quinoneimine) dyes.
  • Dyes produced by developing with aminophenols in the presence of a phenol ornaphthol coupler are indophenol dyes, those produced by developing with a phenylenediamine type developer in the presenceof an aniline coupler, phenol or naphthol couplers, or reactive methylene compounds are indamine, indoaniline and azornethine dyes, respectively.
  • Azomethine and indoaniline dyes are present in many of the processed photographic color products produced by current photographic processes.
  • the developing agents useful for color development of emulsion layers containing couplers of the type described above or for the development of emulsion layers in the presence of these couplers include the well-known primary aromatic amine silver halide developing agents, such as the phenylenediamines, including the N-alkylphenylenediamines and N-alkyltolylenediamines. These developing agents are usually used in the salt form, such as the hydrochloride, or sulfate, which is more stable than the amine.
  • the p-aminophenols and their substitution products can also be used where the amino group is unsubstituted.
  • N-alkylsulfonamidoalkyl-p-phenylenediamine agents of Weissberger US. Patent 2,193,015, issued March 12,1940, are also very useful. All of the developing agents 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.
  • indophenol, indamine, indoaniline and azomethine dyes are relatively unstable to light with the result that dye images in finished commercial color pictures have a tendency to fade, especially when subjected to intense illumination for extended periods of time. This is true Whether the source of illumination is sunlight, tungsten or fluorescent lamps.
  • the cyan dyes are generally relatively less susceptible to fading than the other dyes commonly used in color photography.
  • magenta dye-forming con 'plers are generally more susceptible to print-out than others.
  • the methods of the present invention for preventing the discoloration of water permeable photographic layers containing dye images comprise treating such layers with aqueous solutions of certain organic compounds in order to introduce sutiicient quantities of these treating agents into the photographic layers to inhibit fading of the dye images or print-out of any residual dye-forming coupler therein.
  • the photographic element or layer containing the dye image is immersed in a bath comprising an aqueous solution of one of the treating agents of the invention.
  • the photographic layer is allowed to remain in the bath until it has absorbed sufiicient treating solution to inhibit discoloration.
  • the photographic layer is then removed from the bath and allowed to dry containing the absorbed treating agent.
  • surplus treating solution may be removed from the surface of the photographic element or layer by means of a squeegee, rapid water rinse or other suitable means prior to drying.
  • a water rinse When a water rinse is employed, however, care must be taken not to remove absorbed treating agent from the treated layer.
  • my invention is particularly useful in stabilizing photographic color images produced by a reversal color process wherein the color-forming components or couplers are incorporated Within the photographic color developer.
  • One of the most common of these processes is known as the Kodachrome Process.
  • Especially useful color-forming compounds or couplers which can be incorporated in color developers include the following:
  • Couplers producing cyan images 5-(p-amylphenoxybenzenesulfonamino) l-naphthol 5- (N-benzyl-N-naphthalenesulfonamino l-naphthol 5-(n-benzyl-N-n-valerylamino) -1-naphthol S-caproylamino-l-naphthol 2-chloro-5-(N-n-valeryl-N-p-isopropy1benzylamino) -1- naphthol 2,4-dichloro-5- (p-nitrobenzoyl-fl-o-hydroxyethylamino I-naphthol 2,4-dichloro-5-palmitylaminol-naphthol 2,2'-dihydroxy-5 ,5 -dibromostilbene 5-diphenylethersulfonamido- 1-naphthol 1-hydroxy-2-(N
  • amylphenyl naphthamide S-hydroxy-1-a-naphthoyl-1,2,3 ,4-tetrahydroquinoline 2-lauryl-4-chlorophenol 1-naphthol-2-carboxylic-a-naphthalide 1-naphthol-5-sulfo-cyclohexylamide 5 -phenoxyacetamin0- l-naphthol S-B-phenylpropionylaminol -naphthol M onochlor-S N-v-phenylpropyl-N -p-sec.-amylbenzoylamino) -1-naphthol 2-acety1amino-5 -methylphenol 2-henzoylamino-3 ,5 -dimethylphenol Z-cc (p-tert.
  • a buffering agent such as sodium citrate, sodium acetate, sodium tetraphosphate, etc.
  • a buffering agent such as sodium citrate, sodium acetate, sodium tetraphosphate, etc.
  • Such buffered solutions are substantially neutral, i.e., have a pH of about 7 ($1.0 pH units); No buffer is needed, however, when carbohydrazide base is employed.
  • Suitable acid-addition salts include those of acids, such as hydrochloric, hydrobromide, acetic, etc.
  • the carbohydrazide solutions used in my invention can vary in concentration, depending upon the hardness of the photographic layers undergoing treatment, the thickness of the layers, etc. In general, it has been found that the most useful treating solutions containfrom about 2 to about 20. percent by weight of carbohydrazide. A particularly useful range comprises from about to 10 percent by weight of the carbohydrazide.
  • concentration of the carbohydrazide will also depend somewhat upon the porosity of the photographic support, since porous supports, such as paper, will retain larger amounts of treating solutions than hydrophobic supports, such as film.
  • the temperature at which the treatments are carried out is not critical. As a matter of convenience, it may be desired to employ the treating solutions at room temperature. It is, of course, important that the temperature of the treating solutions should not be high enough to damage the photographic layer or element being treated, or to decompose or otherwise adversely effect the treating agent.
  • the treating time required in the present invention varies with the permeability to the treating solution of the photographic elements being treated. In general, a few minutes immersion in, or contact with (e.g., spraying, etc.), the treating bath is suflicient in most cases, although shorter or longer times may often be employed with success. It is, of course, essential that the photographic element be immersed long enough to absorb sufiicient treating agent to provide a significant improvement in the stability of the color element against discoloration.
  • Quadrafos 1 g 0.6 Sodium sulfite g 12.0 p-N-methylaminophenol sulfate g 5.0
  • the photographic element was then spray washed with water for about /2 minute and given an exposure to red illumination of 1100 ft. candle seconds.
  • the exposed material was then developed in a cyan developer having. the following formula:
  • the photographic element was then washed for about /2 minute with water and exposed to blue light of 300 ft. candle seconds intensity and developed in atyellow color developer containing a phenylenediamine color-developing agent, such as 4-amino-N,N-diethylaniline hydrochloride and a yellow coupler, such as coupler No. 47' from column 4 of U.S. Patent 2,956,876.
  • a phenylenediamine color-developing agent such as 4-amino-N,N-diethylaniline hydrochloride and a yellow coupler, such as coupler No. 47' from column 4 of U.S. Patent 2,956,876.
  • the photo graphic element was then Washed and fogged chemically by treatment with a sodium borohydride solution, as described in Henn et a1.
  • U.S. Patent 2,984,567 issued May 16, 1961.
  • magenta color developer containing a color developing agent, such as 4-amino-N,N-diethyl-3-methylaniline hydrochloride and a magenta coupler, such as coupler No. 30 in column 4 of U.S. Patent 2,956,876.
  • a color developing agent such as 4-amino-N,N-diethyl-3-methylaniline hydrochloride
  • magenta coupler such as coupler No. 30 in column 4 of U.S. Patent 2,956,876.
  • One of the remaining pieces was immersed in a 5% aqueous solution of urea for 10 minutes, While the remaining strip was immersed for the same period of time in a 5% aqueous solution of carbohydrazide.
  • the strips were then removed from the solutions, dipped once in wash water and allowed to dry.
  • the two treated strips and the strip serving as a control were then exposed to 300,000 footcandle-hours of tungsten illumination and the density loss for the red, green and blue layers compared before and after treatment.
  • the following table shows the density loss for each of the three strips where the original densities had been 1.0.
  • carbohydrazide had properties substantially superior to urea in stabilizing the dye in the green ⁇ terial of outstanding stability.
  • a buffering agent can be added to the treating solution, especially where an acid-addition salt of the carbohydrazide is employed.
  • Metal sequestering agents such as ethylenediamine tetracetic acid tetrasoclium salt can be added to eliminate iron staining.
  • the processed photographic elements should be treated after complete photographic processing with the treating solutions of the present invention in order that a significant quantity of the carbohydrazide remains in the finished photographic color element.
  • the optional rapid water washing of the material treated according to the invention should be carried out in such a Way that only surplus treating agent is removed from the surface of the element and no substantial amount of carbohydrazide is removed from the photographic layers containing the coupled dye images. If the carbohydrazide is merely included in the conventional photographic processing, such as developer, etc., it is obvious that it will be completely removed from the photographic element and the processed image will not have desirable stability.
  • a method of inhibiting discoloration in a photographic element which has been exposed, processed to a photographic record comprising at least one dye image and in which residual silver and silver salts have been removed from said. element which comprises dispersing in the dye image areas of said photographic element an aqueous solution comprising carbohydrazide and drying said photographic element without substantial removal of said carbohydrazide.
  • a method of stabilizing a photographic element which has been processed to a photographic dye image by a reversal processing technique wherein the colorforming components are incorporated within a photographic color developer, and in which residual silver and silver halide are removed from said element, comprising dispersing throughout the dye image areas of said processed photographic element an aqueous solution comprising carbohydrazide and drying said photographic element Without substantial removal of said carbohydrazide.
  • said photographic dye image comprises a dye selected from the class consisting of azomethine dyes, indoaniline dyes, indophenol dyes and indamine dyes.
  • a photographic color element which has been exposed, processed to a photographic record comprising a 1 layer containing at least one dye image and in which residual silver and silver salts have been removed from said element, said element having been stabilized by the method of claim 1.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US231587A 1962-10-18 1962-10-18 Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products Expired - Lifetime US3201244A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE638633D BE638633A (en(2012)) 1962-10-18
US231587A US3201244A (en) 1962-10-18 1962-10-18 Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products
US231557A US3201243A (en) 1962-10-18 1962-10-18 Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products
DEE25661A DE1173802B (de) 1962-10-18 1963-10-10 Verfahren zum Stabilisieren von farbenphotographischen Bildern
GB42314/66A GB1057952A (en) 1962-10-18 1963-10-16 Improvements in photographic colour processes
GB40779/63A GB1057951A (en) 1962-10-18 1963-10-16 Improvements in photographic colour processes
FR950895A FR1371657A (fr) 1962-10-18 1963-10-17 Procédé de stabilisation d'images photographiques en couleurs

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US231587A US3201244A (en) 1962-10-18 1962-10-18 Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products
US231557A US3201243A (en) 1962-10-18 1962-10-18 Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products

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US231557A Expired - Lifetime US3201243A (en) 1962-10-18 1962-10-18 Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859574A (en) * 1988-03-15 1989-08-22 Eastman Kodak Company Process for stabilizing photographic elements using a solution comprising a water-soluble N-methylol compound and a buffering agent

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291606A (en) * 1963-04-23 1966-12-13 Eastman Kodak Co Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products
GB1145540A (en) * 1966-06-17 1969-03-19 Fuji Photo Film Co Ltd Process for development of photographic silver halide colour materials
US3628955A (en) * 1968-02-27 1971-12-21 Eastman Kodak Co Inhibition of silvering in photographic solutions
DE2802016C2 (de) * 1978-01-18 1985-05-09 Du Pont de Nemours (Deutschland) GmbH, 4000 Düsseldorf Photographisches Aufzeichnungsmaterial vom Lith-Typ

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2245236A (en) * 1939-04-28 1941-06-10 Eastman Kodak Co Method of increasing infrared sensitivity
US2311098A (en) * 1941-11-13 1943-02-16 Eastman Kodak Co Photographic film comprising nitrocellulose film base stabilized by a dihydrazide of an aliphatic dicarboxylic acid
US2487446A (en) * 1945-12-08 1949-11-08 Gen Aniline & Film Corp Process for preventing stains on photographic color material during drying following exposure, bleaching, and fixing treatment
US2772973A (en) * 1955-02-02 1956-12-04 Gen Aniline & Film Corp Stabilized color developers
US2788274A (en) * 1954-04-14 1957-04-09 Gen Aniline & Film Corp Process of inhibiting the discoloration of photographic color images
US2875049A (en) * 1956-11-05 1959-02-24 Eastman Kodak Co Stabilized photographic developers for color photography

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA488157A (en) * 1952-11-18 D. Russell Harold Stabilization of processed photographic emulsions to high temperatures and humidities
BE403307A (en(2012)) * 1933-05-24
US2955036A (en) * 1958-04-25 1960-10-04 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
BE610270A (en(2012)) * 1960-11-14

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2245236A (en) * 1939-04-28 1941-06-10 Eastman Kodak Co Method of increasing infrared sensitivity
US2311098A (en) * 1941-11-13 1943-02-16 Eastman Kodak Co Photographic film comprising nitrocellulose film base stabilized by a dihydrazide of an aliphatic dicarboxylic acid
US2487446A (en) * 1945-12-08 1949-11-08 Gen Aniline & Film Corp Process for preventing stains on photographic color material during drying following exposure, bleaching, and fixing treatment
US2788274A (en) * 1954-04-14 1957-04-09 Gen Aniline & Film Corp Process of inhibiting the discoloration of photographic color images
US2772973A (en) * 1955-02-02 1956-12-04 Gen Aniline & Film Corp Stabilized color developers
US2875049A (en) * 1956-11-05 1959-02-24 Eastman Kodak Co Stabilized photographic developers for color photography

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859574A (en) * 1988-03-15 1989-08-22 Eastman Kodak Company Process for stabilizing photographic elements using a solution comprising a water-soluble N-methylol compound and a buffering agent

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GB1057951A (en) 1967-02-08
DE1173802B (de) 1964-07-09
US3201243A (en) 1965-08-17
FR1371657A (fr) 1964-09-04
BE638633A (en(2012))
GB1057952A (en) 1967-02-08

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