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
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers

Definitions

• PROCESS FOR DEVELOPMENT OF MULTILAYER COLOR PHOTOGRAPI'IIC MATERIALS BACKGROUND OF THE INVENTION 1.
• This invention relates to a method of developing a color photographic material, in particular, by the use of a compound available in a high temperature rapid processing.
• Multilayer color photographic material generally has at least three kinds of silver halide emulsion layers, each differing in color sensitivity, superimposed on a support, for example, a blue-sensitive emulsion as uppermost layer, yellow filter layer, green-sensitive emulsion layer and red-sensitive emulsion layer.
• the method of developing color-sensitive materials has undergone a change, particularly in that the developing temperature has been raised to shorten the developing time. This is ordinarily called the high temperature rapidprocessing method.
• the overdevelopment which is caused primarily by the excessive concentration of the developer in the uppermost layer, results in disproportionate image density in that layer as compared to the remaining layers.
• a mercaptotriazole compound is added to a developing solution or to a preprocessing solution prior to development, whereby to suppress selectively the progress of development of only the uppermost layer of multilayer color-sensitive material, to inhibit overdevelopment of the uppermost layer, thereby improving the color balance and image quality ob tained.
• a particular advantage of the present invention lies in the ability to process at a temperature of from 30 to 70 C. when using a compound of the invention.
• the above preprocessing solution is usually a prehardening bath consisting of an aqueous solution containing one or more aldehydes having the ability to harden gelatin, a component of the photographic emulsion.
• aldehydes having the ability to harden gelatin, a component of the photographic emulsion.
• This solution also would normally contain a salt such as sodium sulfate, a buffering agent such as borax, acetic acid, sodium acetate, sodium hydroxide, sodium carbonate, sulfuric acid or boric acid and a fog inhibitor such as an alkali metal halide.
• the first developing solution of a color reversal film is an aqueous solution containing one or more developing agents such as hydroquinone, l-phenyl-3-pyrazolidone or N-methylp-aminophenol, to which may be added a salt such as sodium sulfate, a buffering agent such as borax, boric acid, sodium hydroxide or sodium carbonate and a fog inhibitor such as an alkali metal halide.
• developing agents such as hydroquinone, l-phenyl-3-pyrazolidone or N-methylp-aminophenol
• a salt such as sodium sulfate
• a buffering agent such as borax, boric acid, sodium hydroxide or sodium carbonate
• a fog inhibitor such as an alkali metal halide.
• the color-developing solution of a color negative film or color paper is an alkaline aqueous solution containing one or more p-phenylenediamine derivatives such as N,N-diethyl-pphenylenediamine sulfite, N,N-diethyl-Ii-methyl-p-phenylenediamine hydrochloride, 4-amino-3-methyl-N-ethyl-N- methanesulfonamideethylaniline sulfate, 4-amino-3-methyl- N-ethyl-N-hydroxyethylaniline sulfate or N-ethyl-N-hydroxyethyl-p-phenylenediamine sulfate, to which may ordinarily be added a salt such as sodium sulfate, a buffering agent such as sodium hydroxide, sodium carbonate or sodium phosphate and the usual fog inhibitor such as an alkali metal halide.
• the object of the invention can be achieved by adding, to one or more of the above processing solutions, a mercaptotriazole compound represented by the following formula (wherein R represents hydrogen, amino or wherein R represents alkyl such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and the like).
• R represents hydrogen, amino or wherein R represents alkyl such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl,
• the compounds of the present invention are used in connection with the color processing of multilayer photographic materials well known in the art.
• Such materials generally comprise a support of cellulose ester, paper or other suitable base having coated thereon a red-sensitive emulsion layer containing a cyan-forming coupler, a green-sensitive emulsion layer containing a magenta-forming coupler and a bluesensitive emulsion layer containing a yellow-forming coupler.
• the couplers may be incorporated in any manner known in the art.
• the compounds of the present invention are, however, not limited in their use to the above-described multilayer material.
• the photographic material may contain fewer or more sensitive emulsion layers and may also contain conventional filter layers, inter layers, subbing layers, backing layers and overcoating layers. Further, for example, one or more of the emulsion layers may be free of incorporated couplers, the coupler or couplers for these layers being contained in the color developing solution.
• the mercaptotriazole compound is applied during processing to the image-exposed multilayer color photographic material so that this compound is present in the top silver emulsion layer (but not in the middle or bottom layers) during the negative development step of the color process.
• the above compounds can easily be synthesized by reaction of 4-substituted thiosemicarbazide and an acid anhydride (cf. British Pat. No. 766,380) or acid chloride (cf. Ohta and Toshima, Nippon Yakugaku Zasshi (Japan Pharmacology Journal)" Vol. 72, p. 376 (1952)), or by the reaction ofa substituted benzoyl hydrazine with a thioisocyanate.
• anhydride cf. British Pat. No. 766,380
• acid chloride cf. Ohta and Toshima, Nippon Yakugaku Zasshi (Japan Pharmacology Journal)" Vol. 72, p. 376 (1952)
• EXAMPLE lll-4,5-diethyl-S-mercapto-l ,2,4-triazole 9 g. of 4-ethylthiosemicarbazide was dissolved in 50 ml. of pyridine and cooled .with ice while stirring. 10 g. of propionyl chloride was then gradually added to this solution in drops. The reaction mixture was then processed as in example I and the resulting crystals recrystallized from water to obtain 6 g. of the product as needles, melting at 148' C.
• EXAMPLE lV-4-ethyl-3mercapto-S-phenyll ,2,4-triazole 9 g. of 4-ethylthiosemicarbazide was dissolved in 50 ml. of pyridine and cooled with ice while stirring. g. of benzoyl chloride was then gradually added to this solution in drops. The reaction mixture was then processed as in example I and the resulting crystals recrystallized from a mixed solvent of water and ethanol to obtain 9 g. of the product as needles, melting at 145C.
• the compounds of this invention may be employed in a wide range of concentrations, i.e., from about 1X10" mol/liter to about 1X10 mol/liter.
• concentrations i.e., from about 1X10" mol/liter to about 1X10 mol/liter.
• the optimum concentration depends upon a number of factors, for example, the particular compound used, composition of the treating solution, the activity of the developing solution, the treating temperature, the particular characteristics of the multilayer color-sensitive material, etc.
• the optimum concentration to be employed in any particular circumstance can be readily determined by methods well known in the art.
• EXAMPLE Vl A multilayer color film prepared by successively applying to a cellulose acetate support a gelatino iodobromide emulsion sensitive to red light, a gelatino iodobromide emulsion sensitive to green light, a yellow filter layer containing colloidal silver capable of absorbing blue light, and a gelatino iodobromide emulsion sensitive to blue light, was exposed on a sensitometer and then subjected to the following processes:
• Prehardening solution sodium hexametaphosphate l.0 g. sodium bisulfite 5.0 g. sodium pyrophosphate I50 g. sodium sulfate l50.0 g. potassium bromide 2.0 g. sodium hydroxide 0.l g. formalin (37%) I50 ml. water to make L000 ml.
• First developing solution N-methyl-p-aminophenol 5.0 g. sodium sulfite 70.0 g. hydroquinone 2.0 g. sodium carbonate monohydrate 41.0 g. potassium bromide 4.0 g. potassium thiocyanate Lo g. potassium iodide (0.l% aqueous solution) 10.0 ml. water to make 1,000 ml.
• Cyan color developing solution potassium bromide 3.0 g. -nitrobenzimidazole 0.03 g. potassium iodide (01% aqueous solution) l0.0 ml. sodium sulfite l0.0 g. sodium sulfate 60.0 potassium thiocyanate l.0 g. 4-amino-S-methyl-N-ethyl-N- hydroxyethylaniline sulfate 25 g. sodium hydroxide 3.0 g. l,S-dihydroxy-Z,6-dibromonaphthalene 2.0 g. monobenzyl-p-aminophenol 0.4 g. p-aminophenol hydrochloride 0.! g. water to make L000 ml.
• EXAMPLE VIII A multilayer reversal color film having silver halide emulsion layers containing a color coupler and having three different sensitivity regions was exposed by a sensitometer and subjected to the following processing steps.
• compositions of the processing solutions were as follows:
• a sliver halide multilayer color photographic material selected from the group consisting of a color reversal film, a color negative film and a color paper
• the improvement which consists essentially of treating said material with a developing solution consisting essentially of an aqueous solution of at least one developer and a development inhibiting compound represented by the formula:
• R and R are each selected from the group consisting of hydrogen, alkyl and wherein R, is selected from the group consisting of hydrogen, amino and 5.
• said silver halide multilayer color photographic material is color reversal film and wherein said developer is at least one member selected from the group consisting of hydroquinone, l-phenyl-3- pyrazolidone and N-methyl-p-aminophcnol.
• said silver halide multilayer color photographic material is color negative film or color paper and wherein said developer is at least one p-phenylene-diamine derivative.
• said p-phcnylene-diamine derivative is at least one member selected from the group consisting of N,N-diethyl-p-phenylenediamine sulfite, N,N- diethyl-3-methyl-p-phenylenediamine hydrochloride, 4 amino-3-methyl-N-ethyl-N-methanesulfonamideethylaniline methyl-N-ethyl-N-methanesulfonamideethylaniline sulfate, 4- amino-3-methyl-N-ethyl-N-hydroxyethylaniline sulfate or N ethyl-N-hydroxyethyl-p-phenylenediamine sulfate.
• R and R are each selected from the group consisting of hydrogen, alkyl and wherein R is selected from the group consisting of hydrogen. amino and NH-C-R4' wherein R represents an alkyl group.
• said development inhibiting compound is a member selected from the group consisting of 3-mercapto-4-phenyl-,2,4-triazole, 3-mercapto-5- methyl-4-phenyl-l ,2,4-triazole, 5-ethyl-3-mercapto-4-phenyl- 1,2,4-triazole, 3-mercapto-5-pentyl-4-phenyll ,2,4-triazolc, 4,5-diphenyl-3-mercaptol ,2,4-triazole, 3-mercapto4-phcnyl-5-undecyll ,2,4-triazole, 4,5-diethyl-3-mercaptol ,2,4- triazole, 4-ethyl-3'mercapto-5-pentyl-1,2,4-triazole, 4-ethyl- 3-mercapto-5-phenyl-l ,2,4-triazole, 5-p-aminophenyl-4 ethyl-3-
• concentration of said development-inhibiting compound in said aqueous solution varies from about l l0" mole per liter to about lXlO mole per liter.
• aldehyde is selected from the group consisting of formaldehyde, glyoxal, succinaldehyde, and glutaraldehyde.
• aqueous solution further contains a salt, a buffering agent and a fog inhibitor.
• said salt is sodium sulfate
• said buffering agent is selected from the group consisting of borax, acetic acid, sodium acetate, sodium hydroxide, sodium carbonate, sulfuric acid and boric acid and wherein said fog inhibitor is an alkali metal halide.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Cited By (7)

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• 1969
  • 1969-07-11 DE DE1935310A patent/DE1935310C3/de not_active Expired
  • 1969-07-15 GB GB35637/69A patent/GB1248514A/en not_active Expired
  • 1969-07-15 US US842011A patent/US3615522A/en not_active Expired - Lifetime

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