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
  • G03C7/34—Couplers containing phenols
  • G03C7/344—Naphtholic couplers

Definitions

• the present invention relates to color photogand more particularly to the preparation :of dye images in a photographic element "while rutilizin'g in either the photographic emulsion or the developer 2- nap'hthy'l J-acid -'or a urethane thereof.
• J acid and its derivatives-are widely employed as dye intermediates, particularly .in the prepa- :ration of azo dyes.
• J acid has the following iiormula:
• theN-phenyl and acyl derivatives are characfteiiz'd theiact that they are capable (if -profinding deeply colored dyes or high tinctorial strength. Because of this pro erty and their "ability to form Iquinoneimih'e dyes, these compounds would normally recommend "themselves for use in color photography as 'colorffoimers.
• .It is accordingly :an object of the present invention to utilize Q-naphthyl J-acid and the urethanes thereof in the iformation of :colorimages in -col'or photography.
• *A' zfurther object of the present invention is to provide :a photographic silver halide emulsion with :color lformers which are urethanes of 2-- naph-thyl J -acid and which are non-difiusingin the emulsion.
• the urethanes when employing the urethanes, it is preferable to use them in the silver halide emulsion rather than in the developer. When so used, it is imperative that the urethanes do not migrate from the emulsion layer in which they are located. In this connec tion it is to be observed that the urethanes possess a nuclear hydroxyl group and asa consequence yield dyes of the cyan type upon conventional color development. This in turn means that in compounding color formers with the urethanes, the urethanes must be located in the red sensitive layer. 1
• R is an aliphatic chain of at least 12 carbon atoms such as dodecyl, lauryl, tetradecyl, hexadecyl, octadecyl, palmityl and the like.
• Z-naphthyl J-acid is produced by heating Z-naphthylamine, sodium meta-bisulfite and J-acid, preferably while adding the J-acid portionwise to the reaction mixture.
• the 2-naphthy1 J-acid thus obtained is converted into the urethanes by treating the same with the desired alkyl chlorocarbonate at low temperatures, preferably ranging from about 5 to 15 C. Desirably the reactants are vigorously agitated during the reaction. The desired low temperature is maintained by external cooling.
• an acid binding agent should be present and this may be either an inorganic acid binding agent such as sodium hydroxide, potassium hydroxide, sodium acetate and the like, or an organic binding agent such as pyridine, quinoline or the like.
• an inorganic acid binding agent is used, and particularly if a low molecular weight chloroformate is employed, the reaction is effected in an aqueous medium.
• a high molecular chloroformate it is preferable to work with an organic acid binding agent in an organic solvent such as dimethyl formamide.
• the urethanes containing a long aliphatic chain preferably one having at least 12 carbon atoms
• they are dispersed in a photographic silver halide emulsion.
• one gram of the urethane is dissolved in 7 cc. of ethyl alcohol.
• the solution is then diluted with distilled water, neutralized-with sodium hydroxide and added to the emulsion. This procedure is followed in the subsequent examples.
• Dye images are produced from the involved w 4 color formers by development with a conventional primary amine developer while using the color formers in non-difiusing form in a photographic emulsion or in diffusing form in said conventional developers.
• Example 1 Into a suitable vessel equipped with a rapid stirring apparatus, a refluxing condenser, and a heating element are placed 525 parts of 2- naphthylamine, 1400 parts of hot water and 665 parts of sodium metabisulfite. The mixture is heated to boiling and refluxed for 15 minutes. 100 parts of J -acid (the inner salt of commerce) .are introduced and the mixture is refluxed for 2 hours. Another 100 parts of J-acid are introduced and the mixture'is again refluxed for 2 hours. The addition-is repeated in the above fashion until a total of 500 parts of J -acid have been introduced. The resultant suspension is then refiuxedovernight. The hot mixture is filtered, taking on as much of the liquid as possible. The'wet press cake is returned to the vessel and extracted at 60-80" C. with a mixture of 2,000 parts water'and 500 parts 30% sodium chloride solution. The insoluble solid is collected by filtration and pressed as dry as possible.
• J -acid the inner salt of commerce
• the press cake is returned to the vessel and titurated with a mixture consisting of 3,000 parts of water and 2,000 parts of toluene at 7080 C.
• the phases are separated.
• the aqueous phase is reextracted with 1,000 parts of toluene and is then diluted to a total of 6,000 parts.
• Sodium chloride solution 1,000 parts of 30% is added and the clear liquid is neutralized with acetic acid and diluted to a total volume of 8,000 parts.
• the precipitate which separates on standing and cooling, is collected by filtration and washed with a little ice water.
• the wet press cake is dissolved in 8,000 parts of boiling water and decolorized with activated charcoal.
• the filtrate is treated with 200 parts of concentrated hydrochloric acid while being maintained at the boiling point.
• the resulting suspension is kept hot for one-half hour and is then filtered.
• the solid so obtained is washed with water until the wash water no longer runs soapy and is then dried. This is crude 2- naphthyl J-acid.
• the crude Z-naphthyl J-acid obtained above is suspended in 2,000 parts of boiling glacial acetic acid and 800 parts of USP pyridine are added.
• the resulting hot solution is maintained at -100 C. for a period of 1 to 2 hours during which time the. crystalline pyridine salt of 2- naphthyl J-acid separates as a pale. yellow solid. .
• the material is collected by filtration, washed with acetic acid, and dried. If desired, the pyridine salt may be reconverted to the free acid by solution in sodium hydroxide and the addition of hydrochloric acid. There is obtained in the above manner a yield of 240 parts of pure dry pyridine salt of 2-naphthyl J-acid.
• An exposed photographic silver bromide emulsion is developed in a conventional color forming developer containing about 1 gram of the 2- an'd'th'en' treated" with'iapart's; of ethylchlorof" carbonate.
• ethyl urethane of2-naphthyFJ-acid. brilliant dye image is obtained upon working up the developed emulsion.
• Example 3 The procedure is the same as in Example 2 excepting that the ethyl chloroformate is replaced by butyl chloroformate and the resulting butyl urethane of Z-naphthyl J -acid is employed in the developer in place of the ethyl urethane of 2-naphthyl J-acid.
• Example 4 Into a suitable vessel equipped with a water separator and an agitator are placed 360 parts of dry dimethylformamide and 360 parts of dry benzene. The mixture is refluxed for a period of 2 to 5 hours, until no more water is obtained in the water separator. The mixture is then distilled until 1'70 parts of distillate have been obtained. 75 parts of the pure dry pyridine salt of 2-naphthyl J-acid (obtained in Example 1) is introduced and the mixture is heated with stirring until complete solution has taken place. The vessel is now equipped with a thermometer and means for the slow introduction of liquids and the content is cooled to 6 C. 2-hexadecylchloroformate (75 parts) is cautiously introduced, maintaining the temperature below 10 C.
• pyridine 55 parts is slowly added with good agitation, maintaining the temperature below 10 C.
• the resulting dark brownish red solution is stirred at 5 to 10 C. for a period of 2 hours.
• the temperature is then raised to 18-25 C. and the mixture is stirred for 16 to 24 hours.
• the resulting suspension is evaporated to dryness with the aid of a good vacuum.
• the residue is extracted with 750 parts of dry benzene.
• the insoluble material is removed by filtration and discarded.
• the clear benzene filtrate is evaporated at 100 C. and 22 mm. pressure.
• the residue is dissolved in 1,000 parts of hot glacial acetic acid and the solution is cooled to 25 C.
• the insoluble waxy material which separates at this point is removed by filtration and discarded.
• Lithium carbonate 50 parts is added, and the mixture is stirred ffor one-half ness.
• the residue consists of the lithium salt of the 2-hexadecyl urethane 0f Z-naphthyl J -acid.
• the color formers for the production of quinoneimine dyestufif images in the color forming development method, they may also be employed to produce azo dyestuff images by the silver dye bleaching method.
• the film After exposure, the film is developed in a black and White developer and is then bathed for a few minutes in a solution containing the tetrazo compound of benzidine-2.2'-disulfonic acid. A dyestuff is thereby evenly formed throughout the emulsion.
• the film is then treated in a conventional azo dye bleach bath to effect destruction of the dye at the silver image, whereupon the film is worked up according to the usual practice. A positive dyestufi image is thereby obtained in the film.
• R is selected from the class consisting of hydrogen and o -a'-on' B. being alkyl
• M is a member selected from the class consisting of hydrogen and a salt forming radical and the brominated derivatives of the aforestated urethanes.
• a photographic silver halide emulsion containlng a color former fast to diffusion comprising a urethane of 2,-naphthyl J-acid of the following formula:

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (3)

• 0
  • BE BE488697D patent/BE488697A/xx unknown
• 1948
  • 1948-05-06 US US25534A patent/US2480815A/en not_active Expired - Lifetime
• 1949
  • 1949-04-12 GB GB9889/49A patent/GB659128A/en not_active Expired
  • 1949-05-03 FR FR985640D patent/FR985640A/fr not_active Expired
  • 1949-05-06 CH CH286148D patent/CH286148A/fr unknown

Patent Citations (3)

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