US3157504A - 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
US3157504A
US3157504A US184494A US18449462A US3157504A US 3157504 A US3157504 A US 3157504A US 184494 A US184494 A US 184494A US 18449462 A US18449462 A US 18449462A US 3157504 A US3157504 A US 3157504A
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Prior art keywords
photographic
color
couplers
dye
dye images
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US184494A
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English (en)
Inventor
Charleston C Bard
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE630430D priority Critical patent/BE630430A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US184494A priority patent/US3157504A/en
Priority to FR929970A priority patent/FR1352523A/fr
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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
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings

Definitions

  • 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 phenylened-iamine.
  • 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 evelopment- 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 effect photographic development and to produce a didusible dye, which then migrates imagewise to a receiving surface.
  • the present 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 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 colorforming 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.
  • M represents a hydrogen atom or a water-solubilizing cation, such as ammonium, alkali metal (e.g., sodium, potassium, etc.), or organic ammonium (e.g., triethanol ammonium, pyridiniurn, etc.).
  • alkali metal e.g., sodium, potassium, etc.
  • organic ammonium e.g., triethanol ammonium, pyridiniurn, etc.
  • a particularly useful treating agent is sodium a-glucoheptonate dihydra'te.
  • this process involves the incorporation of different color-iorrnin g coupler compounds in each of three superposed differently colorsensitized (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 which it 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 well-known methods.
  • the color-forming couplers can be incorporated in the developer rather than in the emulsion layers as disclosed in Fischer U.S. Patent 1,102,028, issued June 30, 1914.
  • 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 quinone-imine) dyes.
  • Dyes produced by developing with aminophenols in the presence of a phenol or naphthol coupler are indophenol dyes, those produced by developing with a phenylenediamine type developer in the presence of an aniline coupler, phenol or naphthol couplers, or reactive methylene compounds are indamine, indoaniline and azomethine dyes, respectively.
  • Azomethine and indoaniline dyes are present in many of the processed photographic color products produced by current photographic processes.
  • Patent 2,269,158 issued January 6, 1942, and in Mannes and Godowsky U.S. Patents 2,304,939 and 2,304,940, issued December 15, 1942.
  • These patents also disclose specific couplers adapted to be dispersed in emulsionlayers as just described.
  • Other couplers are disclosed in Jelley et al. U.S. Patent 2,322,027, issued. June 15, 1943, Fierke et a1.
  • the developing agents useful for color development of f 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 hyd'rochloride, or sulfate, Whichfis more stable than the amine.
  • the p-aminophenols and their substitution products can also be used where the aminogroup is unsubstituted.
  • N-alkylsulfonamidoalkyl-p-phenylenediamine agents of Weissberger U.S. 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 into the photographic layers to inhibit fading ofthe dye images or print-out of any residual dye-forming coupler dye images in finished commercial colorpictures have a tendency to fade, especially when subjected to intense i1- lumination for extended periods of time. This isrtrue Whether the isource of illumination is sunlight, tungsten, or fluorescent lamps.
  • the cyan dyes are generally relatively less susceptible to fading than the other dyes com monly usedin color photography.
  • the other method referred to above comprises treatment of photographic layers containing dye images with certain chemical compounds, particularly organic reducing agents or antioxidants, in order to stabilize the dye images and V any residual coupler in the photographic layer.
  • certain chemical compounds particularly organic reducing agents or antioxidants
  • 'Methods of this type are disclosed in Vittum U.S. Patent2,384,658, issued September 11, 1955, and Macke'y U.S. Patent 2,579,435, issued December 18, 1951. Methods of .the latter type have been found to be mostly empirical. For example, although the reducing agents of the Vittum pat ent are useful, others of similar reducing properties have 7 no effect on the stability of photographic dye images;
  • the photographic element or layer containing the dye image is im-.
  • aqueous solution of one of the treating agents of the' invention 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 sufficient treating solution to inhibit discoloration.
  • the photographic layer is then removed from the bath and allowed to dry containing the absorbed treating agent.
  • surplus treatingsolution may be rem moved from the surface of the photographic element or. layer by means of a squeegee, rapid Water rinse or other suitable means prior to drying. 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 photo graphic colo developer,
  • One of the most common of these processes is known as the Kodachrome Process.
  • Especially useful color-formin compounds or couplers 7 which can be incorporated in color developers include the following: 7
  • S-phenoxyacetamino-l-naphthol 5-,8-phenylpropionylamino-l-naphthol Monochlor-S-(N-v-phenylpropyl-N-p-sec.-amylbenzoyl- 'amino)-l-naphtho1 V 2-acetylamino-5-methylphenol 2-benzoylamino-3,S-dimethylphenol 2-:1 (p-tert.
  • the methods of the present invention for preventing the discoloration ofwater permeable photographic layers containing dye images comprise treating such layers with aqueous solutions of certain organic compounds in order to introduce sufficient quantitiesofthese treating agents 2-anilinoacetylamino-4-chloro-S-methyIphenOl a 1 2 ⁇ 4'-[a-(4"-tert.
  • amylbenzamino)-4-chl0ro-5 rnethylphenol I" 7 2(4-n-amyloxyhenzamino)-4-chloro-imethylphenol 2(4f-phenoxybenzoylamino ⁇ phenol are particularly useful.
  • the concentration of glucoheptonate in the aqueous treating solutions of the invention can range from a lower limit below which insufiicient treating agent is absorbed by the'treated photographic layer to provide a substantial increase in the stability of anydye image, or residual coupler therein, to an upper limit above which additional glucoheptonatehas little beneficial eifect. Most useful of treating agent by weight.
  • the optimum concentration of the treating solution varies with the particular treating agent employed, and with the particular dyes and couplers treated, as Well as other factors. In general,
  • concentrations of treating agent from about 5 to 16% It should also be recognized effect upon the optimum concentration.
  • porous photographic elements such as photographic paper,
  • the temperature at which the treatments are carried As a matter of convenience, it may he desired to employ the treating solutions at room tem perature. It is, of course, important that the temperature of the treating solutions should not be high enough to damagethe 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 thetreating solution of the photographic elements being treated.
  • a few-minutes immersion in, or contact with (e.g., spray- Sodium sulfate treating solutions contain from about 2 to about 20%
  • 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: I
  • the photographic element was thedwashed for about i /2 minute-with water and exposed to blue light 'of 301 ⁇ .
  • a phenylenediamine colordeveloping agent such as 4-aminol,N-diethylaniline hy-,
  • Coupler No. l 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 l-lenn et al. US. Patent 2,984,567, iss ed" May 16, 1961.
  • the photographic element was then developed in a magenta color developer containing a color developing agent, suchas 4-amino-N,N,-diejd1yl-3- methylanilinehydrochloride and a magenta coupler, such I as Coupler No. in column4 of US. Patent 2,956,876.
  • treatment of the processed photographic color elements should be made in such a manner that a significant quantity of the glucoheptonate remains in the finished photographic color element in order to secure the desired stabilization of the dye image, or residual coupler, if this remains in the element.
  • the optional rapid water washing of the materials treated according to the invention should be carried out in such a way that only surplus glucobeptonate is removed from the surface of the element, and a sufficient amount of this chemical remains within the finished photographic element.
  • glucoheptonate is an alkali metal salt of a-glucoheptonic acid
  • a method of stabilizing the dye image of a photographic element comprising a support and a plurality of photographic emulsion layers wherein said dye image comprises a dye selected from the class consisting of azomethine dyes, indoaniline dyes, indophenol dyes and indamine dyes, comprising dispersing throughout said dye image an aqueous solution containing a water-soluble glucoheptonate.
  • glucoheptonate is an alkali metal salt of m-glucoheptonic acid.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US184494A 1962-04-02 1962-04-02 Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products Expired - Lifetime US3157504A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BE630430D BE630430A (is") 1962-04-02
US184494A US3157504A (en) 1962-04-02 1962-04-02 Method of inhibiting discoloration of color photographic layers containing dye images and resulting photographic products
FR929970A FR1352523A (fr) 1962-04-02 1963-04-01 Procédé pour éviter les colorations parasites sur les produits photographiques encouleurs

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3473929A (en) * 1965-09-09 1969-10-21 Eastman Kodak Co Method of inhibiting discoloration of color photographs
US4939073A (en) * 1981-07-21 1990-07-03 Konishiroku Photo Industry Co., Ltd. Stablized method of light sensitive silver halide color photographic material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2214216A (en) * 1939-09-11 1940-09-10 Defender Photo Supply Co Inc Chemical composition for acid hardening photographic fixing baths
US2384663A (en) * 1943-08-21 1945-09-11 Eastman Kodak Co Method of preventing aerial oxidation and color stain
US2515122A (en) * 1945-12-03 1950-07-11 Gen Aniline & Film Corp Process for preventing stains in photographic color material by the use of a fixing bath-consisting of water, an alkali sulfite, and a fixing agent
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid
US2656272A (en) * 1950-11-30 1953-10-20 Gen Aniline & Film Corp Stabilized azine photographic developers containing sodium metaborate as the sole alkali
US2852372A (en) * 1955-04-04 1958-09-16 Polaroid Corp Process of washing and protecting photographic silver images

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2214216A (en) * 1939-09-11 1940-09-10 Defender Photo Supply Co Inc Chemical composition for acid hardening photographic fixing baths
US2384663A (en) * 1943-08-21 1945-09-11 Eastman Kodak Co Method of preventing aerial oxidation and color stain
US2515122A (en) * 1945-12-03 1950-07-11 Gen Aniline & Film Corp Process for preventing stains in photographic color material by the use of a fixing bath-consisting of water, an alkali sulfite, and a fixing agent
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid
US2656272A (en) * 1950-11-30 1953-10-20 Gen Aniline & Film Corp Stabilized azine photographic developers containing sodium metaborate as the sole alkali
US2852372A (en) * 1955-04-04 1958-09-16 Polaroid Corp Process of washing and protecting photographic silver images

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3473929A (en) * 1965-09-09 1969-10-21 Eastman Kodak Co Method of inhibiting discoloration of color photographs
US4939073A (en) * 1981-07-21 1990-07-03 Konishiroku Photo Industry Co., Ltd. Stablized method of light sensitive silver halide color photographic material

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