US3832179A - Inhibition of fog in photographic color development - Google Patents

Inhibition of fog in photographic color development Download PDF

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Publication number
US3832179A
US3832179A US00326353A US32635373A US3832179A US 3832179 A US3832179 A US 3832179A US 00326353 A US00326353 A US 00326353A US 32635373 A US32635373 A US 32635373A US 3832179 A US3832179 A US 3832179A
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United States
Prior art keywords
color
fog
photographic
acid
developer
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Expired - Lifetime
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US00326353A
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English (en)
Inventor
C Edens
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US00326353A priority Critical patent/US3832179A/en
Priority to CA188,047A priority patent/CA998279A/en
Priority to GB220474A priority patent/GB1444463A/en
Priority to IT19586/74A priority patent/IT1003451B/it
Priority to DE2402899A priority patent/DE2402899C2/de
Priority to FR7402170A priority patent/FR2214910B1/fr
Priority to JP978574A priority patent/JPS5712983B2/ja
Application granted granted Critical
Publication of US3832179A publication Critical patent/US3832179A/en
Anticipated expiration legal-status Critical
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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • 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
    • G03C7/413—Developers

Definitions

  • This invention relates in general to color photography and in particular to methods and compositions for color development. More specifically, this invention relates to the suppression of fog formation during development of multi-layer color photographic elements.
  • Photographic elements of this description may be designed to produce a color negative for use in making positive color prints or transparencies or may be designed to yield a positive transparency directly by a reversal process.
  • the photographic element is first developed with a black and white developing agent to form a negative silver image in each of the exposed emulsion layers.
  • the colors of the dye images are determined by selectively and individually fogging the three emulsion layers and then subjecting each layer to a separate color development operation with a developer solution containing an appropriate color-forming coupler, i.e. a coupler adapted to form a dye of a color complementary to the predominant color sensitivity of the particular emulsion layer being treated.
  • the red sensitive layer of a color photographic element is uniformly fogged, after black-and-white development, and then subjected to color development with a color developer containing a coupler compound capable of forming a cyan dye with the oxidation product of the color developing agent formed during development.
  • the blue sensitive emulsion layer is fogged and subjected to color development with a color developer containing a yellow dye-forming coupler
  • the green sensitive layer is uniformly fogged and subjected to color development with a developer containing a magenta dye-forming coupler.
  • the silver images and any residual silver halide in the several emulsion layers are then removed by bleaching and fixing to produce a natural color positive transparency comprising the three superposed dye images.
  • Another system of color photography employs the color development process to obtain a color negative.
  • a different color-forming coupler compound is incorporated in each of the emulsion layers of the color photographic element as originally suggested by Fischer in U.S. Pat. 1,055,155.
  • each of the three differently sensitized emulsion layers contains its own coupler adapted to form a dye complementary in color to the sensitivity of the emulsion layer, only one color development operation is needed to form the dye images in all of the emulsion layers simultaneously.
  • Typical processes of this type are disclosed in Mannes and Godowsky U.S. Pats. 2,304,939 and 2,304,940 issued Dec. 15, 1942.
  • nitro-substituted benzoicacids are effective as antifoggants for use in suppressing fog formation upon color development. They have been found to be especially effective in reducing magenta fog and yellow fog and, to a lesser extent, cyan fog.
  • the nitro-substituted benzoic acids can be utilized as antifog gants with photographic elements which are designed to be processed in color developers containing couplers or with photographic elements which contain the coupler in the silver halide emulsion layers or in layers contiguous thereto. In either case, they are incorporated in a foginhibiting amount in the color developer solution in order to provide the desired suppression of fog formation.
  • nitro-substituted benzoic acid antifoggants of this invention can contain one or more nitro group substituents. They can be represented by the formula:
  • n is an integer having a value of at least one and preferably a value of two.
  • nitro-substituted benzoic acids are 2,4-dinitrobenzoic acid 3,4-dinitrobenzoic acid 2,5-dinitrobenzoic acid 3,5-dinitrobenzoic acid o-nitrobenzoic acid m-nitrobenzoic acid p-nitrobenzoic acid 2,4,6-trinitrobenzoic acid,
  • nitro-substituted benzoic acids can be used in any amount which is sufficient to inhibit fog formation. They are preferably employed in an amount of from about 0.01 to about 10 grams per liter of color developing solution and more preferably in an amount of from about 0.1 to about 1 gram per liter of color developing solution.
  • the developing agent included in the color developing solution is a primary aromatic amino color developing agent such as a p-phenylenediamine.
  • Developing agents of this type are usually used in the salt form, such as the hydrochloride or sulfate, as the salt form is more stable than the free amine, and are generally employed in concentrations of from about 0.1 to about 10 grams per liter of solution and more preferably from about 0.5 to about grams per liter of solution.
  • These developing agents include p-phenylenediamine and N,N- dialkyl p phenylenediamines wherein the alkyl groups or the aromatic nucleus may be substituted, for example:
  • Developing compositions containing nitro-substituted benzoic acids as antifoggants can also contain any of the various components that are ordinarily incorporated in color developing solutions, for example, materials such as alkalies, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal bromides, alkali metal iodides, thickening agents, water softening agents, and so forth.
  • the pH of the developing solution is ordinarily above 7 and most typically about 10 to about 13.
  • the photosensitive layers present in the photographic elements processed according to the method of this invention can contain any of the conventional silver halides as the photosensitive material, for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, and mixtures thereof.
  • the emulsion layers can contain conventional addenda and be coated on any of the photographic supports, such as, for
  • cellulose nitrate film cellulose acetate film
  • polyvinyl acetal film polycarbonate film
  • polystyrene film polyethylene terephthalate film
  • paper polymer-coated paper, and the like.
  • the antifoggants of this invention are especially useful because they can be employed over a wide range of concentrations with etfective results and thus the process in which they are employed need not be precisely regulated with respect to concentration of the antifoggant. Unlike many prior art antifoggants which adversely affect speed they provide efifective antifoggant activity without such undesirable results. They reduce fog inherent to the silver halide emulsion as well as preventing or counteracting fog caused by contaminants in the developer solution.
  • EXAMPLE 1 A multilayer color negative photographic film of composition and structure essentially as described in Example 5 of United States Pat. 2,860,974 and Example 2 of United States Pat. 3,034,892 was exposed through a multicolor 0.15 log E graduated-density step tablet and then processed at F. in the following sequence:
  • test sample A One portion of the film, designated test sample A, was processed in the above sequence using a color developer, bleach-fix and stabilizer of the following compositions:
  • test sample A Water to 1 liter A second portion of the film, designated test sample A, was processed under the same conditions and using the same processing solutions except that the color developer also contained 0.5 grams of 3,5-dinitrobenzoic acid per liter of solution.
  • test samples A and A were sensitometrically evaluated by recording the characteristic curves of the developed yellow, magenta and cyan dye images.
  • the characteristic curves for test sample A identified by the letters B, G, and R for the yellow, magenta and cyan dye images respectively, are shown in Figure 1 which is a plot of density versus exposure step number.
  • the exposure step numbers 1 to 27 represent the series of steps of the 0.15 log E graduated-density step tablet through which the test samples were exposed prior to processing, step No. 1
  • step No. 27 the lowest density levels in the step tablet.
  • the characteristic curves for test sample A are also shown in FIG. 1 and are identified by the letters B, G and R' for the yellow, magenta and cyan dye images respectively.
  • EXAMPLE 2 A multilayer color negative photographic film similar to that described in Example 1 except that the emulsion layers are of lesser thickness was processed in the same manner as described in Example 1 with the color developer solution containing varying amounts of 3,5-dinitrobenzoic acid.
  • the characteristic curve of the yellow developed dye image is shown in FIG. 2 which is a plot of density versus exposure step number similar to that of FIG. 1.
  • the curves designated by the letters A, B, C and D represent, respectively, zero, 0.2, 0.5- and 1.0 grams of 3,5-dinitrobenzoic acid per liter of color developing solution.
  • the characteristic curve of the magenta dye image is shown in FIG.
  • EXAMPLE 3 A two-week keeping test was carried out in which a multilayer color negative photographic film similar to that described in Example 1 was processed in the same manner as that described in Example 1 with 3,5-dinitrobenzoic acid in the color developer at a concentration of 0.5 grams per liter. In carrying out this test, the film was processed in fresh developer solution and in developer solution that had been kept for 14 days (referred to herein as aged developer). For control purposes, a test was also carried out using fresh developer that did not contain 3,5-dinitrobenzoic acid. The D values that were obtained for red density (cyan dye image), green density (magenta dye image) and blue density (yellow dye image) are as follows:
  • the prebath was a carbonate solution designed for the removal of the antihalation rem jet backing from the film;
  • the color developer solution was essentially the same as that described in Example 1 except that it contained no benzyl alcohol and had a pH of 10.2;
  • the stop bath was a 3% solution of acetic acid;
  • the bleach was a conventional ferric ethylenediaminetetraacetic acid bleach bath;
  • the fix was a conventional thiosulfate fixing solution; and the stabilizer was the same as that described in Example 1.
  • Characteristic curves for the developed yellow, magenta and cyan dye images were recorded for a film sample processed in color developer that contained no 3,5-dinitrobenzoic acid and for a film sample processed in color developer that contained 0.2 grams of 3,5-dinitrobenzoic acid per liter of solution. These curves are shown in FIG. 4 with the curves identified by the letters B, G and R representing the yellow, magenta and cyan dye images respectively for processing with no 3,5-dinitrobenzoic acid in the developer solution and the curves identified by the letters B, G and R' representing the yellow, magenta and cyan dye images respectively for processing with 0.2 grams of 3,5-dinitrobenzoic acid per liter of developer solution.
  • EXAMPLE 5 The photographic film described in Example 4 was processed under the same conditions as described in Example 4 except that the color developing solution had been stored for five days at room temperature.
  • the characteristic curves for this test are shown in FIG. 5 with curves B, G and R representing the yellow, magenta and cyan dye images for processing with color developer that contained no 3,5-dinitrobenzoic acid and had been stored five days and curves B, G and R representing the yellow, magenta and cyan dye images for processing with color developer that contained 0.2 grams per liter of 3,5-dinitrobenzoic acid and had been stored five days.
  • the results shown in FIG. 5 illustrate the effectiveness of the antifoggants of this invention in stabilizing a color developing solution during storage.
  • a method of suppressing the formation of fog in the color development of a silver halide multilayer photographic element which comprises color developing said element with a color developer solution containing a primary aromatic amino color developing agent and a foginhibiting amount of a nitro-substituted benzoic acid.
  • a method as claimed in claim 1 wherein the amount of said nitro-substituted benzoic acid in said color developing solution is from about 0.01 to about 10 grams per liter of solution.
  • a method as claimed in claim 1 wherein the amount of said nitro-substituted benzoic acid in said color developing solution is from about 0.1 to about 1 gram per liter of solution.
  • An aqueous alkaline photographic developing solution comprising a primary aromatic amino color developing agent and a fog-inhibiting amount of a nitro-substituted benzoic acid.
  • An aqueous alkaline photographic developing solution comprising a primary aromatic amino color developing agent and a fog-inhibiting amount of 3,.5-dinitrobenzoic acid.
  • a developing solution as claimed in claim 5 wherein said color developing agent is 4-amino-3-methyl-N-ethyl- N-fl- (methanesulfonamido) ethylaniline.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00326353A 1973-01-24 1973-01-24 Inhibition of fog in photographic color development Expired - Lifetime US3832179A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00326353A US3832179A (en) 1973-01-24 1973-01-24 Inhibition of fog in photographic color development
CA188,047A CA998279A (en) 1973-01-24 1973-12-12 Inhibition of fog in photographic color development
GB220474A GB1444463A (en) 1973-01-24 1974-01-17 Photographic silver halide colour development process
IT19586/74A IT1003451B (it) 1973-01-24 1974-01-18 Inibizione dell annebbiamento nello sviluppo della fotografia a colori
DE2402899A DE2402899C2 (de) 1973-01-24 1974-01-22 Verfahren zum Unterdrücken der Schleierbildung in mehrschichtigen farbphotographischen Aufzeichnungsmaterialien bei der Farbentwicklung
FR7402170A FR2214910B1 (enExample) 1973-01-24 1974-01-23
JP978574A JPS5712983B2 (enExample) 1973-01-24 1974-01-24

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Application Number Priority Date Filing Date Title
US00326353A US3832179A (en) 1973-01-24 1973-01-24 Inhibition of fog in photographic color development

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US3832179A true US3832179A (en) 1974-08-27

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US00326353A Expired - Lifetime US3832179A (en) 1973-01-24 1973-01-24 Inhibition of fog in photographic color development

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US (1) US3832179A (enExample)
JP (1) JPS5712983B2 (enExample)
CA (1) CA998279A (enExample)
DE (1) DE2402899C2 (enExample)
FR (1) FR2214910B1 (enExample)
GB (1) GB1444463A (enExample)
IT (1) IT1003451B (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4132551A (en) * 1971-09-17 1979-01-02 Agfa-Gevaert N.V. High temperature processing of photographic silver halide material
US4171976A (en) * 1978-03-10 1979-10-23 Eastman Kodak Company Homopolymerization inhibition of photographic hardeners
US4256826A (en) * 1978-08-14 1981-03-17 Eastman Kodak Company Bleach-fix sheets
US6312878B1 (en) 1999-03-08 2001-11-06 Eastman Kodak Company Color photographic developer kit

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08272060A (ja) * 1996-03-25 1996-10-18 Konica Corp ハロゲン化銀カラー写真感光材料用発色現像液
FR2777094B1 (fr) * 1998-04-03 2000-06-09 Eastman Kodak Co Kit pour revelateur photographique chromogene
FR2790841B1 (fr) * 1999-03-08 2003-11-07 Eastman Kodak Co Procede pour renouveler un revelateur photographique chromogene

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1952253C3 (de) * 1968-10-22 1979-03-22 Fuji Photo Film Co., Ltd., Ashigara, Kanagawa (Japan) Verfahren zum Entwickeln farbphotographischer Aufzeichnungsmaterialien
BE788687A (nl) * 1971-09-17 1973-03-12 Agfa Gevaert Nv Ontwikkeling van zilverhalogenide-materiaal bij verhoogde temperatuur

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4132551A (en) * 1971-09-17 1979-01-02 Agfa-Gevaert N.V. High temperature processing of photographic silver halide material
US4171976A (en) * 1978-03-10 1979-10-23 Eastman Kodak Company Homopolymerization inhibition of photographic hardeners
US4256826A (en) * 1978-08-14 1981-03-17 Eastman Kodak Company Bleach-fix sheets
US6312878B1 (en) 1999-03-08 2001-11-06 Eastman Kodak Company Color photographic developer kit
AU769374B2 (en) * 1999-03-08 2004-01-22 Eastman Kodak Company New color photographic developer kit

Also Published As

Publication number Publication date
FR2214910B1 (enExample) 1977-06-10
FR2214910A1 (enExample) 1974-08-19
JPS49106832A (enExample) 1974-10-09
DE2402899A1 (de) 1974-07-25
GB1444463A (en) 1976-07-28
DE2402899C2 (de) 1982-12-30
JPS5712983B2 (enExample) 1982-03-13
CA998279A (en) 1976-10-12
IT1003451B (it) 1976-06-10

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