US2998312A - New process for colour photography - Google Patents

New process for colour photography Download PDF

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Publication number
US2998312A
US2998312A US560883A US56088356A US2998312A US 2998312 A US2998312 A US 2998312A US 560883 A US560883 A US 560883A US 56088356 A US56088356 A US 56088356A US 2998312 A US2998312 A US 2998312A
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United States
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colour
magenta
parts
yellow
image
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Expired - Lifetime
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US560883A
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English (en)
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Macdonald Eric
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C07D231/26—1-Phenyl-3-methyl-5- pyrazolones, unsubstituted or substituted on the phenyl ring
    • 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
    • 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
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • an improved process for colour photography which comprises developing with a colour forming developer, an exposed multilayer photographic element comprising a base and superimposed thereon 3 diiferently sensitised silver halide emulsion layers containing respectively a cyan colour former which does not react with aldehydes to give coloured compounds, a magenta colour former which contains in its molecular structure a reactive methylene group, and a yellow colour former which does not react with aldehydes to give coloured compounds, and subsequently treating the photographic element with an aromatic aldehyde of the benzene or naphthalene series which contains at least one auxochromic group, or with a functional derivative thereof, for example an aldehyde of the formula RNHC H -CHO or Where R, R and R are alkyl, aryl, or aralkyl, hydroxyalkyl, halogenoalkyl, cyanoalkyl, nitroal'kyl, carboxyaling certain reactive methylene compounds with
  • the derivatives of reactive methylene compounds used in the process of our invention are the colour-less or substantially colourless compounds of the formula A-CH(Aryl)B where CH(Aryl) is the residue of an aromatic aldehyde of the benzene or naphthalene series which contains at least one auxochromic group, where A and B, which may be the same or different, are the residues of reactive methylene compounds which themselves are kyl or sulphoalkyl, or where R and R together with the nitrogen atom form part of a 5- or 6-membered ring, and where the benzene nucleus may carry substituents such as nitro, alkyl, halogen, sulphonic acid or carboxylic acid groups.
  • magenta colour couplers the colourless or substantially colourless derivatives of reactive methylene compounds formed by treatmagenta colour formers (that is to say compounds which yield magenta dyestuffs when exposed photographic ele ments containing them are developed with a colour forming developer, for example p-NsN-diethylaminoaniline) and where A, B or the aryl radical contains at least one sulphonic acid or carboxylic acid group.
  • a colour forming developer for example p-NsN-diethylaminoaniline
  • A, B or the aryl radical contains at least one sulphonic acid or carboxylic acid group.
  • the compounds obtained from an oxime of an aromatic aldehyde and a substituted pyrazolone may be represented by the formula R3 R4 3 Aryl fi l I N CH-OE-OH N Rail-60 (Bo-lea.
  • Aryl is an aryl nucleus of the benzene or naphthalene series which contains at least one auxochromic group
  • R and R are hydrogen or aryl
  • R and R are alkyl, aryl, amino or substituted amino radicals and where-- in R R R R or the Aryl radical contains at least one carboxylic or sulphonic acid group.
  • the compounds may also be made by treating 2 molecular proportions of the reactive methylene compound with 1 molecular proportion of the aldehyde or by heating 1 molecular proportion of the corresponding styryl dyestutt (itself made from equimolecular proportions of the reactive methylene compound and the aldehyde) with 1 molecular proportion of the reactive methylene compound.
  • a new process for colour photography which comprises developing with a colour forming developer, an exposed multilayer photographic material comprising three differently sensitised gelatino-silverlhalide emulsion layers, one such layer containing 'a yellow colour coupler another such layer containing a magenta colour coupler and the other such layer containing a cyan color coupler, wherein the magenta colour coupler is a derivative of a reactive methylene compound as hereinbefore defined, and subsequently treating the photographic material with formaldehyde, or nitrous acid.
  • pyrazolones for example 1-(4-phenoxy-3-sulphophenyl 3 heptadecyl-S- pyrazolone, l-(3-carboxyphenyl) 3 (4"-stearylaminophenyl)-5-pyrazolone, 1-(3-sulphomethyl-phenyl)-3-heptadecyl-S-pyrazolone, 1-(4-sulphophenyl)-3-octadecylamino- S-pyrazolone; oxindoles, for example oxindole itself and N-amyloxindole; rhodamines, for example N-ethyl rhodamine; diketopyrazolidines, for example 1:2-diphenyl or 1 :2-di(p-ch1orophenyl)-3 S-diketopyrazolidine, coumaranones, thi
  • the aromatic aldehydes of the benzene or naphthalene series must contain at least one auxochromic group, for example a hydroxy or amino group or a substituted hydroxy o'r amino group.
  • auxochromic group for example a hydroxy or amino group or a substituted hydroxy o'r amino group.
  • R, R and R are alkyl, aryl, aralkyl, hydroxyalkyl, alkoxyalkyl, halogenoalkyl, cyanoalkyl, nitroalkyl, carboalkyl or suphoalkyl, or Where R and R" together with the nitrogen atom form part of a 5- or 6-membered ring, and where the benzene nucleus may carry substitutents such as for example, nitro, alkyl, alkoxy
  • a masking colour can be obtained which possesses the required absorption characteristics to compensate for the undesired blue absorption of the magenta azomethine dyestuff obtained by colour development with the aromatic amine such as p-diethylaminoaniline.
  • the oximes of the aldehydes may be made by heating the parent aldehyde in ethanolic solution with hydroxylamine, concentrating the solution, extracting with ether, drying and distilling off the ether.
  • I provide a process for the manufacture of a magneta colour coupler which comprises treating a magenta colour coupler containing a reactive methylene group with an oxime of an aromatic aldehyde of the benzene or naphthalene series containing at least one auxochromic group.
  • the reaction of the reactive methylene compound and the oxime may be conveniently carried out by heating the reagents together in aqueous alcoholic solution, for example aqueous methanolic solution and the product may be isolated by evaporating the solution to dryness.
  • aqueous alcoholic solution for example aqueous methanolic solution
  • the product may be isolated by evaporating the solution to dryness.
  • this reactive methylene compound or aldehyde is preferably used in the form of a water-soluble salt for example an alkali-metal salt and the new colour coupler is obtained in the form of a salt.
  • one molecular proportion of aldehyde oxime is required for each two molecular proportions of reactive methylene compound but an excess of oxime can be used if desired, and the excess can then be recovered from the reaction mixture.
  • the new colour couplers may contain substituents which render them non-diifusible in gelatine for example an alkyl chain of at least 5 carbon atoms or they may be rendered non-diffusible by any other method used in practice or known from the literature fro preventing the diffusion of colour formers in gelatino-silver halide emulsion layers.
  • the new colour couplers of my invention may be used as the magneta colour couplers in colour photographic processes in which there are employed differently sensitised silver halide emulsion layers containing different colour couplers or a layer containing a mixture of grains of differently sensitised emulsions containing different colour couplers.
  • the new colour couplers may be used as the magenta colour coupler in a colourphotographic negative in which the top layer which is sensitive to blue light (that is to say is not spectrally sensitised) and contains a yellow colour coupler is separated by a yellow filter layer from a green-sensitive layer containing a magenta colour coupler and a red-sensitive layer containing a cyan colour coupler.
  • yellow colour couplers there may be used for example compounds of the acylacetylarylamide series and as cyan colour couplers there may be used for example compounds of the l-napththol series.
  • a silver halide emulsion containing one of the new colour couplers of our invention When a silver halide emulsion containing one of the new colour couplers of our invention is exposed to light and then colour developed with a p-dialkylaminoaniline a magenta image is obtained.
  • the residual colour coupler in the emulsion is colourless and accordingly has no masking effect but by treatment with formaldehyde or nitrous acid at any stage subsequent to the colour development step, the residual colour coupler is converted to a yellow styryl dyestuff which forms the reverse masking image which corrects for the undesired blue absorption of the primary magenta image.
  • the formaldehyde or nitrous acid treatment may be carried out as a separate operation if desired, at any stage after colour development, but to avoid complication of the processing operations the formaldehyde or nitrous acid may be added to the stop-bath used after colour development, and the photographic material may then be bleached, and fixed.
  • the treatment of a colour developed photographic material with formaldehyde or nitrous acid to develop the yellow styryl dyestutf masking image from residual colour coupler can be conveniently arranged to serve also for forming the leuco derivative of a red dyestutf masking image from residual cyan colour coupler by the process of British specification No. 723,171 and this leuco compound may then be oxidised in the bleaching bath to form the red masking dyestuff.
  • Example 1 A multilayer light sensitive photographic material is made up as follows:
  • a layer of colloidal silver in gelatin is coated on to act as yellow filter layer and finally a stop layer a blue sensitive gelatino-silver halide emulsion containing grams per litre of p-stearyl-aminobenzoylacetaniline-p-carboxylic acid sodium salt (the yellow colour forming component described in Example 3 of British specification No. 486,848) is coated.
  • the film is exposed to the light from a coloured object and then developed in a solution of the following composition:
  • the film is washed and transferred to a bleaching bath solution of the following composition:
  • This processed material contains in the first layer a cyan dyestuff negative image, in the second layer a magenta dyestuff negative image and a yellow dyestuff positive image (formed by reaction of the unused colour former with the formaldehyde of the stop bath) which serves to correct the undesirable absorption of blue light by the magenta dyestuff, and in the top layer a yellow dyestuif negative image.
  • a cyan dyestuff negative image in the second layer a magenta dyestuff negative image and a yellow dyestuff positive image (formed by reaction of the unused colour former with the formaldehyde of the stop bath) which serves to correct the undesirable absorption of blue light by the magenta dyestuff, and in the top layer a yellow dyestuif negative image.
  • the multilayer material prepared as described in this example when bleached and fixed without exposure to light is found to contain substantially colourless clear gelatin layers.
  • the stop-bath containing no formaldehyde is used, the final magenta negative image is ob tained without a compensating yellow mask.
  • the yellow mask may then be introduced after the fixing step by treating the material with a solution of the following composition:
  • the pyraZolone-aldehyde oxime reaction product used in the above example may be prepared as follows:
  • the oxime is completely soluble in dilute sodium hydroxide. solution.
  • Example 2 A multilayer light sensitive material is made up as follows:
  • a transparent support material is coated with a layer of red sensitive gelatino-silver halide emulsion containing 10 grams per litre of the sodium salt of l-hydroxy- 2 naphthoylamino 2 (N methyl N octadecylamino)benzene-5-carboxylic acid.
  • a green-sensitive emulsion containing 10 grams per litre of the pyrazolonealdehyde oxime reaction prodnot used in Example 1.
  • a layer of colloidal silver in gelatine is coated on to act as a yellow filter layer and finally as the top layer there is coated a blue sensitive gelatino-silver halide emulsion containing 10 grams per litre of 3-(p-anisoylacetamido)-4-(N-methyloctadecylamino)-benzoic acid, sodium salt.
  • the film is exposed to the light from a coloured object and then developed in a solution of the following composition:
  • the film contains the first developed silver, the azomethine dyestuif negative images in the three layers, a yellow dyestuif positive masking image produced by the formaldehyde in the middle magenta forming layer, and a colourless leuco form of a red dyestufi positive masking image in the cyan layer.
  • the material is thoroughly washed and the silver is bleached and fixed as described in Example 1.
  • the leuco dyestuif of the bottom layer is converted to the red dyestulf masking image.
  • the final material contains in the bottom layer a cyan dyestutf negative image and a red dyestutf positive image (which serves as a mask to correct for the undesired blue and green absorption of the cyan dyestutf), in the second layer, a magenta dyestutf negative image and a yellow dyestuif positive image (which serves as a mask to correct for the undesired blue absorption of the magenta dyestuif), and in the top layer a yellow dyestufi negative image.
  • Example 4 In place of the green-sensitive gelatino-silver halide emulsion used in Example 2 containing 10 grams of the pyrazolone-aldehyde oxime reaction product per liter of emulsion there is used a green sensitive gelatino-silver halide emulsion containing 10 grams of the colour coupler described in Example 3 per liter of emulsion together with 0.1 gram of hydroxylamine per litre of emulsion.
  • Example 5 In place of the green-sensitive gelatino-silver halide emulsion containing grams of the pyrazolone-aldehyde oxime reaction productper litre of emulsion used in Example 1, there is used a green sensitive gelatinosilver halide emulsion containing 10' grams of the colour coupler made as described below per litre of emulsion together with 0.1 gram of hydroxylamine per litre of emulsion.
  • the colour coupler used in this example is prepared as follows:
  • a process for color photography which comprises developing with a color forming developer, an exposed multilayer photographic material comprising three differently sensitized gelatino-silver halide emulsion layers, said layers containing color formers adapted to yield, upon exposure and development, yellow, cyan and magenta colored images in separate layers, the color former yielding the magenta colored image being an at least substantially colorless compound of the formula:
  • (Aryl) is selected from the group consisting of phenyl and naphthyl containing at least one auxochromic group selected from the class consisting of hydroxy, alkoxy, and secondary and tertiary amino groups
  • A is a reactive methylene magenta color former group coupled through the carbon of the reactive methylene
  • B is a magenta color forming pyrazolonyl-4 group and one of A
  • B and (Aryl) contains at least one member of the class consisting of sulfonic acid and carboxylic acid groups, and treating the photographic material after development with a member of the group consisting of formaldehyde and nitrous acid.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US560883A 1955-01-28 1956-01-23 New process for colour photography Expired - Lifetime US2998312A (en)

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GB2607/55A GB786859A (en) 1955-01-28 1955-01-28 New process for colour photography

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468666A (en) * 1966-05-05 1969-09-23 Fuji Photo Film Co Ltd Color photographic silver halide light-sensitive materials containing bis-pyrazolone couplers

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE634930A (en)) * 1959-11-13
EP0711804A3 (de) 1994-11-14 1999-09-22 Ciba SC Holding AG Kryptolichtschutzmittel

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB513596A (en) * 1938-04-08 1939-10-17 John David Kendall Improvements in and relating to the production of coloured photographic images by colour development
US2294909A (en) * 1939-02-13 1942-09-08 Du Pont Chemical process and composition
US2367531A (en) * 1942-06-12 1945-01-16 Eastman Kodak Co Acylaminophenol photographic couplers
US2369929A (en) * 1943-03-18 1945-02-20 Eastman Kodak Co Acylamino phenol couplers
US2515160A (en) * 1950-07-11 Production of pyrazoles
US2525518A (en) * 1946-05-15 1950-10-10 Rhone Poulenc Sa Production of dimethylaminoantipyrines
US2688541A (en) * 1950-11-20 1954-09-07 Ici Ltd Light-sensitive color photographic material
US2688540A (en) * 1950-11-20 1954-09-07 Ici Ltd Process for color photography
US2706683A (en) * 1951-12-15 1955-04-19 Eastman Kodak Co Bis-pyrazolone for color photography
US2884325A (en) * 1954-03-05 1959-04-28 Agfa Ag Process for the production of a yellow mask image in magenta-colored photographic images

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2515160A (en) * 1950-07-11 Production of pyrazoles
GB513596A (en) * 1938-04-08 1939-10-17 John David Kendall Improvements in and relating to the production of coloured photographic images by colour development
US2294909A (en) * 1939-02-13 1942-09-08 Du Pont Chemical process and composition
US2367531A (en) * 1942-06-12 1945-01-16 Eastman Kodak Co Acylaminophenol photographic couplers
US2369929A (en) * 1943-03-18 1945-02-20 Eastman Kodak Co Acylamino phenol couplers
US2525518A (en) * 1946-05-15 1950-10-10 Rhone Poulenc Sa Production of dimethylaminoantipyrines
US2688541A (en) * 1950-11-20 1954-09-07 Ici Ltd Light-sensitive color photographic material
US2688540A (en) * 1950-11-20 1954-09-07 Ici Ltd Process for color photography
US2706683A (en) * 1951-12-15 1955-04-19 Eastman Kodak Co Bis-pyrazolone for color photography
US2884325A (en) * 1954-03-05 1959-04-28 Agfa Ag Process for the production of a yellow mask image in magenta-colored photographic images

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468666A (en) * 1966-05-05 1969-09-23 Fuji Photo Film Co Ltd Color photographic silver halide light-sensitive materials containing bis-pyrazolone couplers

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DE1013514B (de) 1957-08-08
FR1152106A (fr) 1958-02-12
GB786859A (en) 1957-11-27
BE544737A (en))

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