US2860975A - Photographic color correction process using 2-azo-1-naphthol dyes - Google Patents

Photographic color correction process using 2-azo-1-naphthol dyes Download PDF

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Publication number
US2860975A
US2860975A US612681A US61268156A US2860975A US 2860975 A US2860975 A US 2860975A US 612681 A US612681 A US 612681A US 61268156 A US61268156 A US 61268156A US 2860975 A US2860975 A US 2860975A
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Prior art keywords
dye
coupler
azo
naphthol
color
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Expired - Lifetime
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US612681A
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English (en)
Inventor
Keith E Whitmore
Edward T Pesch
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US612681A priority Critical patent/US2860975A/en
Priority to GB26792/57A priority patent/GB850610A/en
Priority to FR1206641D priority patent/FR1206641A/fr
Priority to FR1192229D priority patent/FR1192229A/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • G03C7/18—Processes for the correction of the colour image in subtractive colour photography

Definitions

  • This invention relates to photography and more particularly to the preparation of color correction images in photographic emulsion layers by means of colored coupler compounds.
  • Typical colored couplers thus previously known are the 4-azo-l-naphthol couplers which have the property during color development of an exposed silver halide emulsion layer, of splitting at the azo linkage to release a phenolic fragment which reacts with the oxidation products of the color developing agent to produce a dye having a color different from the original colored coupler.
  • the original colored coupler retains its color in the unexposed regions of the emulsion layer and thus may serve as a color correction mask or image.
  • the colored coupler can be used as the sole coupler in an emulsion layer of a multilayer color film or as is the more usual practice, the colored coupler is supplemented by a colorless image-forming coupler, for example, as shown in U. S. Patent 2,428,054 above.
  • a yellow-colored coupler which forms a magenta dye on coupling with the developing agent, may be used together with a colorless magentaforming coupler in a green-sensitive emulsion layer of a film.
  • Color development of the locally exposed emulsion layer produces a composite magenta-dye image from the two couplers in the exposed areas, whereas in the unexposed area the yellow-colored coupler remains unchanged to serve as a color correction mask.
  • 2-azo-1-naphthol dyes can be used as colored couplers in colorfilms in conjunction with colorless couplers in the manner described.
  • the 2-azo-1-naphthol dyes do not function in the same manner as do the usual colored couplers such as the 4-a'zo-l-naphtho1 colored couplers, That is, the 2-azo-1-naphthol. couplers upon reaction with the oxidation products of the color developer, yield yellowish to brown or practically neutrally colored productsof low tinctorial power rather than cyan dyes which might be expected if the mechanism was the same as takes place with the 4-azo-l-naphthol couplers.
  • the mentioned property of the 2-azo-1-naphthol dyes can thus be utilized to provide masking images havinga naphthol nucleus.
  • N H OH OH IIIHI @N:N O
  • N N l S ;Na S 0 :Na
  • N 8 O S 0 3N8.
  • the color indicated following the above structural formulas corresponds to the color of the dye previous to color development.
  • dyes IV and VII during color development the azo dyes change in color to light yellow or brown.
  • Dye IV changes to an almost neutral (slightly magenta) color and dye VII changes to a definite yellow color.
  • the useful 2-azo-1-naphthol dyes can be classified structurally as follows:
  • Z represents the non-metallic atoms necessary to complete a naphthalene group the 3- and 4positions of which are free of substituents and R represents an aryl group of the benzene or naphthalene series substituted or not, as shown in the above dye formulas.
  • FIG. 1 A representative photographic element contemplated by our invention is shown in greatly enlarged cross-see tional view in Fig. 1 of the accompanying drawing.
  • layer 20 represents a film support carrying the silver halide emulsion layers 21, 22 and 23, respectively sensitized to the red, green, and blue regions of the visible spectrum, emulsions 22 and 23 being separated by a yellow filter layer 24in the conventional manner.
  • emulsion layer 21 contains a colorless cyan-forming coupler
  • emulsion 23 a colorless yellow-forming coupler
  • emulsion 22 contains the colorless magenta-forming coupler, a 4-azo-5-pyrazolone coupler and a 2-azo-l-naphthol coupler.
  • the 4-azo-5-pyrazolone coupler is a yellowcolored coupler which gives a magenta dye on color development and the Z-azo-l-naphthol coupler may be a coupler of the invention which is blue in color and gives an almost neutral color in the color development reaction. Accordingly, depending upon the nature and proportion of the 2-azo couplers present in emulsion layer 22, this layer would appear bluish, yellowish or greenish in color.
  • Fig. 2 illustrates the sensitometric characteristics of the dye images obtainable in an emulsion such as layer 22 containing the mixture of couplers.
  • curve 1 represents the green light absorption characteristics of the magenta dye image at various exposure levels
  • curve 2 the blue light absorption characteristics of the yellow masking image obtained from the 4-azo-5-pyrazolone coupler
  • curve 3 the red light absorption characteristics of the bluish masking image attributable to the 2- azo-1-naphthol coupler.
  • Example 3 The preparation of an emulsion layer capable of providing dye images having these characteristics is shown in Example 3 hereinafter.
  • the coating was then exposed in the normal manner for sensitometric evaluation and then processed at 70 F. as follows:
  • the above color developer had the following composition:
  • the above fixing baths were conventional acid-hypo fixers.
  • the above bleaching solution contained 50g. potassium ferricyanide and 20 g. potassium bromide per liter of water.
  • the image was found to comprise a yellow negative image of varying density and a positive magenta masking image compensating for the improper green light absorption of the yellow image.
  • a ratio of the colored to colorless couplers in such emulsions By varying the ratio of the colored to colorless couplers in such emulsions, the improper absorptions of other yellow dyes can be compensated for in the same manner.
  • EXAMPLE 2 In the manner of Example 1, an emulsion was prepared and coated containing a dibutyl phthalate dispersion of a mixture of (1) the cyan-forming coupler: 1- hydroxy 2 [6 (2',4' di tert. amylphenoxy) n butyll-naphthamide (Weissberger et al. U. S. Patent 2,474,293, granted June 28, 1949), which yields cyan dyes having unwanted blue and green light absorptions, and (2) the magenta coupler I. Processing in the manner of Example 1 produced a negative cyan dye image in the emulsion layer and a positive magenta mask compensating primarily for the unwanted green light absorption of the cyan dye image. 1
  • EXAMPLE 3 An emulsion was prepared similar to that shown in layer 22 of Fig. 1 of the drawing by dispersing in aqueous gelatin solution by means of dibutyl phthalate the three couplers (1) the magenta-forming coupler: 1- (2.,4',6 trichlorophenyl) 3 [3" (2"',4"' di-tert. amylphenoxyacetamido) benzamido] 5 -pyrazolone (Loria etal. U. S. Patent 2,600,788, granted June 17,
  • a coating of the resulting emulsion processed as described in Example 1 yielded a composite negative magenta dye image from the two magenta couplers above and a composite positive dye masking image composed of the residual yellow-colored pyrazolone coupler and the residual blue-colored 2-azo-1-naphtho1 coupler which composite masking image compensated for unwanted blue and red light absorptions of the negative magenta dye image.
  • EXAMPLE 4 A multilayer color film similar to that shown in Fig. 1 of the drawing can be prepared by coating a cellulose ester film base with the following:
  • Example land A blue-sensitive gelatino-bromoiodide emulsion prepared as in Example land containing the yellow dyeforming coupler and the magenta-colored coupler I of the invention.
  • the resulting film processed as described in Example 1 yields yellow and cyan images in which unwanted green light absorptions are compensated for by magenta masks obtained from coupler I, and magenta dye images in which unwanted blue and red light absorptions are compensated for by a composite mask obtained from the yellow coupler and the blue coupler IV.
  • the photographic emulsions containing the azo dye couplers of the invention in conjunction with colorless couplers and, if desired, other colored couplers comprise the usual silver halides and mixtures of silver halides such as silver bromide, chloride, bromoiodide and chlorobromidc emulsions.
  • the emulsion vehicles include the usual hydrophilic colloids such as gelatin, polyvinyl alcohol, hydrolyzed cellulose esters and other natural and synthetic hydrophilic colloids.
  • the emulsions containing the coupler compounds can be used in both negative and reversal processes of color photography contemplated by the claims hereinafter.
  • color development takes place following image exposure.
  • reversal process color development follows image exposure, black-and-white development and reversal exposure steps.
  • Coupler compounds of the invention can be incorporated into the emulsions by use of organic solvents or aqueous solutions depending upon the solubility of the alkali metal salts of the couplers containing sulfonic acid groups.
  • Coupler solvents can be used as shown in U. S. Patents 2,304,940 and 2,322,027 to facilitate the incorporation of the couplers into emulsions.
  • the color developing agents useful for the development of the emulsions and carrying out the processes of the invention are those Well known in the art, particularly the p-phenylenediamine and aminophenol compounds having a primary aromatic amino group which enables the oxidation product of the color developer to couple with the mentioned coupler compounds.
  • a multilayer photographic color film comprising a plurality of superposed differentially light-sensitive silver halide emulsion layers containing colorless coupler compounds capable of reaction with the oxidation products of a primary aromatic amino silver halide developing agent for the formation of subtractively colored dye images in the respective emulsion layers, at least one of said emulsion layers containing in addition to said colorless coupler compound a 2-azo-l-naphthol dye the 3- and 4-positions of which are free of substituents.
  • a multilayer photographic color film comprising a plurality of superposed differentially light-sensitive silver halide emulsion layerscont'aining colorless coupler compounds capable of reaction with the oxidation products of a primary aromatic amino silver halide developing agent for the formation of subtractively colored dye images in the respective emulsion layers, at least one of said emulsion layers containing in addition to said colorless coupler compound a Z-aZo-l-naphthol dye the 3- and 4-positions of which are free of substituents, and a colored coupler compound capable of forming a dye image of substantially the same color as said colorless coupler.
  • the emulsion layer contains in addition to the specified colorless coupler and the Z-azo-l-naphthol dye, a colored coupler compound capable of reaction with the oxidation products of a primary aromatic amino silver halide developing agent to form a dye image of substantially the same color as formed by said colorless coupler.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US612681A 1956-09-28 1956-09-28 Photographic color correction process using 2-azo-1-naphthol dyes Expired - Lifetime US2860975A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US612681A US2860975A (en) 1956-09-28 1956-09-28 Photographic color correction process using 2-azo-1-naphthol dyes
GB26792/57A GB850610A (en) 1956-09-28 1957-08-26 Silver halide emulsions containing colour couplers and processes of forming colour-corrected photographic images
FR1206641D FR1206641A (fr) 1956-09-28 1957-09-25 Nouveaux tétraazaindènes et leurs applications, notamment à la photographie
FR1192229D FR1192229A (fr) 1956-09-28 1957-09-27 Nouvelle émulsion photographique et produits pour la photographie en couleurs contenant cette émulsion

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US612681A US2860975A (en) 1956-09-28 1956-09-28 Photographic color correction process using 2-azo-1-naphthol dyes

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GB (1) GB850610A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468665A (en) * 1964-09-29 1969-09-23 Fuji Photo Film Co Ltd Color photographic silver halide emulsion
US3476560A (en) * 1964-07-28 1969-11-04 Fuji Photo Film Co Ltd Inhibiting fogging action during color development
US3859095A (en) * 1969-12-13 1975-01-07 Agfa Gevaert Ag Color-photographic material with improved color reproduction

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2286714A (en) * 1941-03-22 1942-06-16 Eastman Kodak Co Photographic element containing a trisazo dye
US2304884A (en) * 1940-04-09 1942-12-15 Eastman Kodak Co Color photography
US2428054A (en) * 1945-08-30 1947-09-30 Eastman Kodak Co Photographic color correction using colored couplers
US2694636A (en) * 1951-08-16 1954-11-16 Geigy Ag J R Light-sensitive element for color photography

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2304884A (en) * 1940-04-09 1942-12-15 Eastman Kodak Co Color photography
US2286714A (en) * 1941-03-22 1942-06-16 Eastman Kodak Co Photographic element containing a trisazo dye
US2428054A (en) * 1945-08-30 1947-09-30 Eastman Kodak Co Photographic color correction using colored couplers
US2694636A (en) * 1951-08-16 1954-11-16 Geigy Ag J R Light-sensitive element for color photography

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3476560A (en) * 1964-07-28 1969-11-04 Fuji Photo Film Co Ltd Inhibiting fogging action during color development
US3468665A (en) * 1964-09-29 1969-09-23 Fuji Photo Film Co Ltd Color photographic silver halide emulsion
US3859095A (en) * 1969-12-13 1975-01-07 Agfa Gevaert Ag Color-photographic material with improved color reproduction

Also Published As

Publication number Publication date
FR1206641A (fr) 1960-02-10
FR1192229A (fr) 1959-10-23
GB850610A (en) 1960-10-05

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