Classifications

• • 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
  • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
  • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore

Definitions

• This invention relates to color photography and'particularly to color correction by incorporating in a silver halide emulsion a mixture of colored and uncolored couplers.
• colored photographic images may be formed by using a developer which produces a colored compound on development.
• the colored compound thus formed is deposited adjacent the silver grains of the silver image during development.
• a colored image may be formed by adding to certain developing solutions or by incorporating in the silver halide emulsion a compound which couples during development with the oxidation product of the developing agent and forms a colored compound which is likewise adjacent the silver grains of the silver image during development.
• a color forming compound or coupler Such a compound which is employed in conjunction with the developing agent for the "silver andwhich couples with the oxidation product of the developing agent during development is referred to herein as a color forming compound or coupler.
• the invention is, therefore, particularly adaptable to color photographic elements employing a plurality of superimposed silver halide emulsion layers wherein at least one layer or, if desired, all the layers contains a combination of at least one colored coupler and at least one uncolored coupler. 7
• an object of the invention to provide a new colorphotographic'element having a plurality of superimposed silver halide layers sensitized to different colors and wherein. atleast. one layer contains a combination of a colored coupler and an uncolored couplerc
• Another object is to provide a color photographic element of the above kind wherein color correction is attained by a new method of masking.
• Another object is to provide a process for preparing the said new element.
• I prepare color photographic elements by coating in any order two or more differently sensitized silver halide emulsions, for example, sensitized to the blue, green and red, over one another and, if desired, separated by inert or colored gelatin layers, onto a suitable.
• photographic supportmaterial such as films or sheets of cellulose acetate, cellulose mixed esters, cellulose nitrate, cellulose ether, synthetic resin materials such as polyesters, polyamides, etc.,. paper materials, glass plates, and the like.
• the preferred photographic color element contains three differently sensitized silver halide emulsion layers in the order of a bottom red-sensitized layer next to the support, a middle green-sensitized layer and a top blue:sensitize d layer. While suitable combinations of the colored and uncolored. couplers may be incorporated in any one or allot these layers, a preferred form of my invention is to include a suitable yellow colored coupler, together with a. suitable uncolored couplerin the green-sensitized layer, a suitable magenta colored-coupler with an uncolored coupler in the blue-sensitive layer and a suitable orange colored coupler with an uncolored coupler in the red sensitized layer.
• Suitable colored couplers which react with developers of the ph'enylene diamine type to give water-soluble dyes. include a wide variety of nondiffusing azo type yellow, orange and magentacolored couplers. Those which are particularly useful in this invention may be represented by the following generalformulas-L and OONHR;
• R1, R3 and R4 are simple or complex alkyl or aryl groups or combinations of these containing one or more solubilizing groups such as sulfo or carboxy groups, and R2 represents a ballasting group.
• R1, R3 and R4 are simple or complex alkyl or aryl groups or combinations of these containing one or more solubilizing groups such as sulfo or carboxy groups, and R2 represents a ballasting group.
• Vitturn is 1-p-sulfophenyl-3-methyl-4-p-laurylphenylazo-S-pyrazolone which coupler on incorporation into a silver halide emulsion, followed by exposure and development with a p-amino dirnethylaniline developing solution is converted in the exposed areas to a water-soluble, dit fusible azo methine dye which will wash out of the film.
• This soluble dye may be represented by the following structural formula:
• N G-NHC O 1-pheny1-3- (3-sulfobenzamido) 4-(4-octadecy1oxyphenylazo)- 5-pyrnzolone 1pheny1-3- (Z-carboxybenzamido) 4- (4-dodecyloxypheuylazo) o-pyrazolone 1 (4-su1fophenyl) -3-Inethyl- ⁇ 4- [4 (l-cert. buty1)phenoxy] pheny1azo ⁇ -5-pyrazo1one
• This compound can be prepared by the general procedure of above compound (2).
• Typical compou-ndssof structure II include those such as:
• the compounds furnishing the ballast group R2 are prepared, for example, as described in the following example:
• 3-amino-2-naphthoic acid is dissolved in an excess of n-amyl alcohol and dry hydrogen chloride is passed into the mixture. After refluxing several .hours, the excess alcohol is removed by vacuum distillation and the residue stirred in a sodium carbonate'sol-ution. The product is collected on a filter and dried.
• the compounds furnishing the ballast group, prepared according to Example 4 are diazotized and then coupled in a basic medium such as pyridine, sodium hydroxide or acetic acid-i-sodium acetate with the solubilized compounds prepared according to above Examples 1-3, and the azo dyes which form are collected and purified.
• a basic medium such as pyridine, sodium hydroxide or acetic acid-i-sodium acetate
• Suitable uncolored non-diffusing couplers for use in my invention include any of those described in United States Patent No. 2,298,443, dated October 13, 1942, of A. Weissberger.
• Example 4 parts by weight of an uncolored coupler, N-(pbenzoylacetaminobenzeiiesulfonyl)-N-( phenylpropyl)- p-toluidine, dissolved in 8 parts of di-n-butyl phthalate were dispersed in 17 parts by weight of a aqueous gelatin solution.
• the developer composition was as follows:
• Example 6 This example was carried out the same as Example 5, except that the uncolored coupler, 1-hydroXy-2-[8(2',4'- di-tert. amylphenoxy)-n-butyl]-naphthamide (prepared according to U. S. Patent No. 2,474,293, dated June 28, 1949, of A. Weissberger et al.), which reacts with N- ethyl-N-(B-sulfonamidoethyl)*3-methyl-4-aminoaniline to produce a cyan dye having an appreciable amount of green and blue absorption, was substituted for the uncolored coupler employed in Example 5. The emulsion was coated and processed as in Example 5. Sensitometric tests indicated that this particular sample showed excellent color correction.
• the uncolored coupler 1-hydroXy-2-[8(2',4'- di-tert. amylphenoxy)-n-butyl]-naphthamide (prepared according to U. S.
• Example 7 This example illustrates a coating made with a solvent type of dispersion.
• An uncolored coupler, 1- (2',4',6-t'richlorophenyl) -3- 3 "- (2"',4'-di-te(rt. amylphenoxy-acet. amido)-benzamido]-5-pyrazolone (prepared according to U. S. Patent No. 2,600,788, dated June 17, 1952, of A.
• the coating was processed as in above Example 5. Sensitometric tests of the sample showed excellent color correction.
• Example 8 This example was carried out the same as Exam ner,
• amyl phenoxyacetamido) -benzamido]-5-pyrazol0ne an uncoloredcoupler yielding a magenta dye, dissolved in tricresyl phosphate, was added to the green-sensitive silver halide emulsion and coated as the middle layer, (3) a mixture of N-(p-benzoylacetaminobenzenesulfonyl) -N- (y-phenylpropyl)-p-toluidine, an uncolored coupler yielding a yellow dye and 1-hydroxy-4-(2-amyloxycarbonyl-3- naphthylazo')'-N- [fl(2-carboxybenzamido) ethyl] Z-naphthamide, a magenta-colored coupler yielding a soluble dye, dissolvedin di-n-butyl-phthalate, was added to an unsensitized silver halide emulsion and coated over a vellnw filterlayer.
• R1, R3 and R4 each represents a member selected from the group consisting of an alkyl group and an aryl group, said group having at least one solubilizing group attached thereto selected from the group consisting of a carboxy group, a sulfo group, an alkali metal carboxy group, an alkali metal sulfo group, an ammonium carboxy group and an ammonium sulfo group, and R2 represents an aromatic radical having attached thereto an alkyl group of from 4 to 15 carbon atoms, which comprises exposing said element and developing it to form color images from said uncolored and said colored colorforming couplers in the exposed portions and simultaneously to split said colored color former at the azo group, thus forming a soluble dye which is removed from the emulsion layer, leaving the uncoupled portion of
• the said uncolored color-forming coupler is l(2',4',6'-trichlorophenyl)-3-[3"-(2,4'di-tert. amido)-benzamido]-5-pyrazolone and the said colored amplphenoxy-acetcolor-forming coupler is the trimethylbenzyl ammonium salt of l-phenyl-3-(Z-carboxybenzamido)-4-(4dodecyloxyphenylazo -5-pyraz0lone.
• R1, R3 and R4 each represents a member selected from the group consisting of an alkyl group and an aryl group, said group having at least one solubilizing group attached thereto selected from the group consisting of a carboxy group, a sulfo group, an alkali metal carboxy group, an alkali metal sulfo group, an ammonium carboxy group and an ammonium sulfo group, and R2 epresents an aromatic radical containing an alkyl group of from 4 to 15 carbon atoms, which comprises exposing said element and developing it with a primary aromatic amine developing agent to form color images in the bluesensitized layer from said uncolored and said colored color-forming couplers in the exposed portions and simultaneously to split said colored color former at the azo group, thus forming a soluble dye which is removed from the blue-sensitized emulsion layer, leaving the uncoupled portion of said colored color-former as a mask in the said blue-sensitized emulsion
• a photographic element comprising a support having thereon at least one silver halide emulsion layer which contains at least one uncolored color-forming coupler which is reactive with the oxidation product of a primary aromatic amine developing agent to form a non-diffusible dye in the said layer and which further contains at least one colored color-forming coupler selected from the groups consisting of those represented by the following general formulas:
• R1, R3 and R4 each represents a member selected from the group consisting of an alkyl group and an aryl group, said group having at least one solubilizing group attached thereto selected from the group consisting of a carboxy group, a sulfo group, an alkali metal carboxy group, an alkali metal sulfo group, an ammonium carboxy group and an ammonium sulfo group, and R2 represents an aromatic radical containing an alkyl group of from 4 to l5 carbon atoms.

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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)

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• 0
  • BE BE540231D patent/BE540231A/xx unknown
  • NL NL113830D patent/NL113830C/xx active
  • BE BE550154D patent/BE550154A/xx unknown
  • NL NL202187D patent/NL202187A/xx unknown
• 1954
  • 1954-11-22 US US470499A patent/US2808329A/en not_active Expired - Lifetime
• 1955
  • 1955-07-26 FR FR1146556D patent/FR1146556A/fr not_active Expired
  • 1955-07-27 GB GB21652/55A patent/GB783730A/en not_active Expired
  • 1955-08-15 US US528516A patent/US2860974A/en not_active Expired - Lifetime
  • 1955-10-03 CH CH345532D patent/CH345532A/de unknown
  • 1955-11-22 DE DEE11571A patent/DE964655C/de not_active Expired
  • 1955-12-29 GB GB37198/55A patent/GB853922A/en not_active Expired
• 1956
  • 1956-08-10 DE DEE12808A patent/DE1008574B/de active Pending
  • 1956-08-14 FR FR72012D patent/FR72012E/fr not_active Expired
• 1958
  • 1958-07-08 FR FR769833A patent/FR73828E/fr not_active Expired

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