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
  • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
  • C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
  • C07D241/52—Oxygen atoms

Definitions

• R which may be the same or different groups, represents a member selected from the group consisting of a hydrogen atom, an alkyl group having one to eight carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfogroup, an acylamino group, a sulfonamino group, a halogen atom and a carbocyclic aromatic residue formed by the condensation of two of said Rs bonded to adjacent carbon atoms.
• the present invention relates to color photography and more particularly to a method of preparing a photographic color image by a silver dyestuff bleaching process 2.
• Description of the Prior Art As is well known, the preparation of color photographic images by a silver dyestuff bleaching process is based on the principle that dyestuffs, especially azo dyestuffs, are destroyed by an appropriate treatment in the presence of metallic silver in the photographic layer.
• the emulsion layer is treated with a dyestuff bleaching bath in which there occurs a simultaneous decolorization of the dyestuff with an oxidation of the metal image at the points where silver is present, i.e., the metallic silver is converted into a silver compound which may be removed subsequently by fixation in a solution of hypo or dissolved in the dyestuff bleaching solution, such as a strong alkali iodide or an alkali thiocyanate solution.
• a dyestuff bleaching bath in which there occurs a simultaneous decolorization of the dyestuff with an oxidation of the metal image at the points where silver is present, i.e., the metallic silver is converted into a silver compound which may be removed subsequently by fixation in a solution of hypo or dissolved in the dyestuff bleaching solution, such as a strong alkali iodide or an alkali thiocyanate solution.
• the dyestuff bleaching baths employed in this process have relatively low pH values and consist of an aqueous solution of a hydrohalic acid, such as hydrochloric, hydrobromic acids, etc., sulfuric acid, sulfamic acid or acetic acid, containing an alkali halide, such as potassium chloride, sodium chloride, potassium iodide, etc., and at least one complex forming agent (with silver), such as thiourea, semicarbazide, etc.
• a hydrohalic acid such as hydrochloric, hydrobromic acids, etc., sulfuric acid, sulfamic acid or acetic acid
• alkali halide such as potassium chloride, sodium chloride, potassium iodide, etc.
• complex forming agent with silver
• the bleaching of the dyestuff should take place stoichiometrically depending on the silver present, in which process 4 atoms of silver are required to destroy one azo group.
• the gradation of the component color images are solely dependent on the gradations of the developed silver images. However, this is not the case.
• the gradations of the component color images are dependent on many other factors. For example, they are dependent on the nature of the dyestuffs, the colloid layer, the thickness of the layer, the silver distributed within the layer, the composition of the bleaching bath, and the duration of action of the bleaching bath.
• the duration of action of the bleaching bath is varied from a few minutes to several hours. It is known that the duration of the bleaching can be controlled by the addition of some compounds. Moreover, it is possible to completely bleach a dyestuff which is not bleached or bleached only insufficiently bythe addition of a compound to the dyestuff bleaching bath.
• Such a compound is usually called a bleaching catalyst" and as such a compound, there may be illustrated: 2-hydroxy-3-aminophenazine, 2,3,-dimethylaguinoxaline, anthraquinone sulfonic acid, pyrazine, etc.
• an object of the present invention is to provide a series of effective, novel bleaching catalysts.
• Another object of the present invention is to provide a method of preparing color photographic images by a silver dyestuff bleaching process using the novel bleaching catalysts of the present invention.
• phenazine-N-oxides used in the practice of the present invention may be represented by the following formula:
• R which may be the same or different group, represents a hydrogen atom, an alkyl group having one to eight carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, etc.; an aryl group such as phenyl, tolyl, xylyl, etc.; a hydroxy group; an alkoxy group having one to four carbon atoms such as methoxy, ethoxy, butoxy, etc.; a nitro group; a cyano group; a carboxy group; a sulfo group an acylamino group such as acetylamino, propionylamino, valerylamino, benzoylamino.
• toluoylamino etc.
• a sulfonamino group such as methylsulfonamino, ethylsulfonamino, phenylsulfonamino, etc.
• phenazineN-oxides may be prepared by one of the following two known methods:
• the phenazine-N-oxides used in this invention have profitable characteristics as compared with known bleaching catalysts. For example, since the compounds have a strong catalysts. For example, since the compounds have a strong catalytic action, an effective result can be obtained even when only a slight amount of the compound is used. Also, by utilizing the compounds of this invention, the duration required for the dye bleaching procedure can be shortened. Moreover, since the amount of acid contained in dye bleachingbath can be reduced, and also since the pH value of the dye bleaching bath can be increased by employing the compound of this invention, the photographic layers and the support of a photographic light-sensitive element during processing can be prevented from being injured. Furthermore, the bleaching catalyst of this invention causes no undesirable coloring of the gelatin or the support.
• the phenazine-N-oxides of this invention may be incorporated in at least one of the silver halide emulsion layers and the gelatin intermediate layer of a photographic light-sensitive element to be processed by a silver dyestuff bleaching method.
• SYNTHESIS EXAMPLE 2 SYNTHESIS EXAMPLE 3 Preparation of l-acetamidophenazine-5-oxide To a solution of 3 g. of acetamidophenazine in 100 m1. of acetic acid was added l5 ml. of 30 percent hydrogen peroxide.
• SYNTHESIS EXAMPLE 5 Preparation of 2-ethoxyphenazine-5-oxide (6) ethyl alcohol to give additional crystals. The crystals were recrystallized from ethyl alcohol to give 26 g. of compound (6), golden yellow needles, m.p. 154-l 55C
• SYNTHESIS EXAMPLE 6 Preparation of 8-chloro-lphenazinecarboxylic acid-S-oxide To a stirred suspension of 78.5 g. of p-nitrochlorobenzene and 31 g. of anthranilic acid in 300 ml. of toluene was added 1 15 g.
• the bleaching catalyst can be used in a processing bath. That is, the phenazine-N-oxide of this invention maybe added to a dyestuff bleaching bath or a bath prior to the dyestuff bleaching bath, such as a developing bath, a fixing bath, a stopping bath, a hardening bath, or an additional bath for the phenazine-N-oxide processing.
• the bleaching catalyst of this invention when 0.0005 0.100 g. of the bleaching catalyst of this invention is added to 1 liter of a usual dyestuff bleaching bath, containing hydrochloric acid, potassium bromide, and thiourea, surprisingly excellent results can be obtained.
• the optimum amount of the bleaching catalyst of this invention for use according to the invention can be readily determined by methods well known in the art.
• the phenazine-N-oxide of this invention can be used together with other different bleaching catalysts such as a quinoxaline, a phenazine, and the like.
• the organic soluble dyestuffs are substantially insoluble in water and suitable dyestuffs are solvent dyestuffs shown in Color Index; 2nd Ed., published by The Society of Dyers and Colourists.
• suitable dyestuffs are solvent dyestuffs shown in Color Index; 2nd Ed., published by The Society of Dyers and Colourists.
• AlZEN Spillon Blue E2BH Cl Solvent Blue 73
• AIZEN Spillon Yellow GRH Cl Solvent Yellow 6
• AZOSOL Brilliant Green BA Cl Solvent Green 2
• AZOSOL Fast Red BE Cl Solvent Red 8
• Ceres Blue GN CI Solvent Blue 63
• Ceres Red 58 Cl Solvent Red 27
• Ceres Yellow 3G Cl Solvent Yellow 16
• Ceres Yellow GRN CI Solvent Yellow 29
• Fat Orange R CI Solvent Yellow 14
• Lithfor Yellow AS Cl Solvent Yellow 30
• Oil Yellow GR Cl Solvent Yellow 29
• disperse dyestuffs shown in Color Index can be used.
• Celliton Discharge Blue 56 (Cl Disperse Blue 15)
• Diacelliton Fast Rubin 38 (Cl Disperse Red 5)
• Diacelliton Fast Yellow G (Cl Disperse Yellow 3)
• Kayalon Polyester Blue 3GR (CI Disperse Blue 98)
• Kayalon Polyester Yellow RF (Cl Disperse Yellow 7)
• Kayalon 4 Polyester Yellow YLF CI Disperse Yellow 42
• organic solvents for dissolving the aforesaid organic solvent soluble dyestuffs there may be illustrated the following.
• alcohols such as methanol, ethanol.
• esters such as ethyl acetate, butyl acetate, and the like
• ethers such as diethyl ether, dioxane, tetrahydrofuran. and the like
• ketones such as acetone, methyl ethyl ketone, and the like
• amides such as a lactam, a dialkyl carbamide, and the like.
• high-boiling oily solvents can be used.
• alkylesters of phthalic acid such as dibutyl phthalate. dioctyl phthalate. and the like
• phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate. and the like
• alkyl amides such as N, N-dibutyl laurylamide, and the like.
• acetanilides such as butylacetanilide, and the like.
• a color photographic image can be obtained by a silver dyestuft' bleaching process.
• the photographic light-sensitive'film thus prepared was exposed through a gray optical step wedge, developed in a developer of a p-methylaminophenol-hydroquinone type, and fixed by a conventional method. Thereafter, the photographic film was processed in a dyestuff bleaching bath containing 60 g. of thiourea, g. of potassium bromide, 30 ml. of concen- 30 trated hydrochloric acid, and 5 mg. of the compound shown by aforesaid 'formula (15) (per liter) and then subjected to the usual silver bleaching and fixing to provide a positive wedge image. The highlight portions of the photograph were completely white and the gradation of the dye image was in good balance.
• EXAMPLE3 The multilayer photographic light-sensitive film as described" in example 2 was exposed through a gray optical step wedge and developed for 10 minutes in a developer of the following composition:
• the thus-prepared solution was added to 10 ml. of a 10 percent aqueous gelatin solution containing 2 ml. of a 10 percent aqueous solution of sodium alkylbenzene sulfonate and the resulting mixture was emulsified by means of a homoblender. Then, g. of the emulsion obtained was mixed with 100 g. of
• EXAMPLE 5 In 2.0 ml. of tricresyl phosphate was dissolved 0.2 g of Yelasol Red 3BKS (CI Solvent Red 91). The solution prepared was added to 10 ml. of a 10 percent gelatin solution containing 2 ml. of a 10 percent aqueous solution of sodium alkylbenzene sulfonate and the mixture was emulsified by means of a homoblender. The, 30 g. of the emulsion was mixed with 100 g. of a green-sensitive silver chlorobromide emulsion (7.4 percent silver halide and 7.3 percent gelatin) and after adding the usual additives, the resulting silver halide emulsion was applied to a white film base.
• Yelasol Red 3BKS CI Solvent Red 91
• the thus-prepared solution was added to 10 ml. ofa 10 percent aqueous gelatin solution containing 2 ml. of a 10 percent aqueous solution of sodium alkylbenzene sulfonate and the mixture was emulsified by means of a homoblender. Thereafter. 13 g. of the emulsion was mixed with 35 g. of a silver chlorobromide emulsion (7.4 percent silver halide and 7.3 percent gelatin) and the resulting mixture was applied to a glass plate.
• the photographic light-sensitive plate thus prepared was exposed through an optical step wedge and processed as in example I, wherein, however, the dyestuff bleaching processing was conducted for 10 minutes in the following bath:
• R which may be the same or different groups
• a hydrogen atom represents a member selected from the group consisting of a hydrogen atom, an alkyl group'having one to eight carbon atoms, an aryl group, a hydroxy group, an alkoxy group having one to four carbon atoms, a nitro group, a cyano group, .a carboxy group, a sulfo group, an acylamino group, a sulfonamino group, a halogen atom and a carbocyclic aromatic residue formed by the condensation of two of said Rs bonded to adjacent carbon atoms.

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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)
• Plural Heterocyclic Compounds (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=12849577

Family Applications (1)

Country Status (7)

Cited By (4)

• 1969
  • 1969-07-14 DE DE19691935705 patent/DE1935705A1/de active Pending
  • 1969-07-15 BE BE736092D patent/BE736092A/xx unknown
  • 1969-07-16 GB GB35904/69A patent/GB1277660A/en not_active Expired
  • 1969-07-16 FR FR6924225A patent/FR2013073A1/fr not_active Withdrawn
  • 1969-07-16 US US842378A patent/US3615494A/en not_active Expired - Lifetime
  • 1969-07-16 NL NL6910917A patent/NL6910917A/xx unknown
  • 1969-07-16 CH CH1088069A patent/CH512087A/de not_active IP Right Cessation

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