US3443942A - Colored photographic direct positive images - Google Patents

Colored photographic direct positive images Download PDF

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US3443942A
US3443942A US470615A US3443942DA US3443942A US 3443942 A US3443942 A US 3443942A US 470615 A US470615 A US 470615A US 3443942D A US3443942D A US 3443942DA US 3443942 A US3443942 A US 3443942A
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carbon atoms
alkyl
phenyl
amino
compounds
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Walter Puschel
Karl-Wilhelm Schranz
Wolfgang Lassig
Paul Marx
Hans-Heinrich Credner
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D215/38—Nitrogen atoms
    • C07D215/42—Nitrogen atoms attached in position 4
    • 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
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • 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
    • C07D231/38—Nitrogen atoms
    • 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
    • C07D231/38—Nitrogen atoms
    • C07D231/42—Benzene-sulfonamido pyrazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/82—Nitrogen atoms
    • 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

Definitions

  • dihydrazones of a,5-dicarbonyl compounds are described in British patent specification No. 916.657 for the production of direct positive images. These dihydrazones are practically colorless and react at the light-struck areas during the colorforming development with the developer oxidation products to form likewise colorless products.
  • the silver image is bleached out by means ofan oxiding bath, they are transformed at the unexposed areas into a yellowish orange-colored substance. It is possible in this way to produce colored direct positive images, but these are, however, relatively weak in color. They are suitable for the production of color-correcting masks.
  • Amidrazones of a specific constitution are used in Belgian Patent 602,250 for the production of colored masking images.
  • the amidrazones are capable of coupling by oxidation with color couplers, so that a colored positive image is formed in the bleaching bath at the unexposed and undeveloped areas remaining after the color development.
  • the principle of the reaction used therein is described in an article by S. Hiinig and F. Miiller, Annalen 651 (1962), pages 73 et seq.
  • the present invention provides a very simple and inexpensive technique for the production of direct positive color-photographic images which is unexpectedly desirable and which the prior art did not consider possible.
  • Many compounds are suitable for the process of the present invention. Particular utility is exhibited by compounds of the following groups:
  • Aryl amines such as phenylamines or naphthylamines or derivatives thereof.
  • the a ryl amines include preferably those of the following formula:
  • R stands for a phenyl or a naphthyl group
  • R: and R" which may be like or different, represent hydrogen, alkyl having up to 20 carbpn atoms, aryl preferably phenyl or naphthyl; aralkyl, such as benzyl or phenylethyl or heterocyclic radicals such as pyridine or quinoline.
  • R and R" together can stand for the ring members necessary to complete a 5- or 6-membered heterocyclic ring, particularly a saturated ring, such as morpholine, piperidine, pyrrolidine, piperazine and the like.
  • R and/or R" together with the ortho-methine group of the benzene ringv of R can likewise form 5- or 6-membered heterocyclic rings. Included herein are, for example, rings of the tetrahydroquinoline type. t
  • the phenyl ring of R in the above general formula can be substituted in any suitable manner, it only being necessary to ensure that either one of the two ortho-positions or the para-position to the' amino group is unsubstituted or substituted with groups, for example sulfo groups which are capable of being split off under the processing conditions.
  • Halogen such as chlorine or bromine
  • alkyl or alkoxy radicals containing up to 20 carbon atoms carboxyl, carboxyl esters, preferably with aliphatic alcohols'containing up to ZO-car bon atoms, sulfo, sulfonamide, or carbonamide radicals
  • the amide groups it being possible for the amide groups to be substituted with alkyl radicals containing up to 20 carbon atoms, or acyl radicals, more especially those which are derived from aliphatic carboxylic acids containing up to 20 carbon atoms, and also nitro, nitrile, or amino groups.
  • the amino group can be substituted by alkyl radicals with up to 20 carbon atoms, acyl, more especially an acyl radical which is derived from aliphatic carboxylic acids containing up to 20 carbon atoms, or phenyl.
  • the phenyl ring of R in the above formula can furthermore be substituted by other phenyl or even naphthyl rings in simple manner, or contain these rings in anellated (fused) form.
  • the production of the amines is generally known per se.
  • the introduction of the radicals providing diffusion resistance into the Compounds I, X, XII and also of the pyrrolidinyl radical into the Compound XI can be performed by reacting the known unsubstituted amines with the corresponding alkyl phenyl halides in a manner which is generally known.
  • Compounds V and XIII are rendered fast to diffusion by acylation reactions.
  • Cornpound III is prepared by reacting the corresponding 1- acetaminophenol, in the form of the alkali phenolate with octadecyl bromide. The free amine is obtained by acid or alkali saponification.
  • R aryl, preferably a phenyl or naphthyl, which can be substituted with nitro, halogen, such as chlorine or bromine, alkyl preferably alkyl having up to 5 carbon atoms such as methyl or ethyl, hydroxy, alkoxy, having preferably up to 5 carbon atoms, such as methoxy or ethoxy, carboxyl, esterified carboxyl, having preferably up to 5 carbon atoms, amino, alkyl amino, the alkyl group of which having preferably up to 5 carbon atoms, phenyl amino, acylamino with preferably acyl groups, which are derived from aliphatic carboxylic acids, having up to 20 carbon atoms, such as acetyl or stearoyl, or benzyl amino, sulfonamide, sulfo, alkyl sulfon, sulfonyl, or esterified sulfo groups, in particular with aliphatic alcohol
  • alkyl having up to 20 carbon atoms such as methyl, ethyl, butyl or heptadecyl, olefinically unsaturated alkyl having up to 20 carbon atoms, such as allyl, cycloalkyl, such as cyclohexyl, aryl, preferably phenyl or naphthyl or aralkyl, such as benzyl or phenyl ethyl; the above radicals and preferably the rings of the benzene series can in turn be substituted with hydroxy halogen, such as chlorine or bromine, alkyl preferably alkyl having up to 5 carbon atoms, such as methyl or ethyl, alkoXy, having preferably up to 5 carbon atoms, such as methoxy or ethoxy, carboxyl, esterified carboXyl, having preferably up to 5 carbon atoms, amino, alkyl amino the alkyl group of which preferably
  • R carbamyl, N-alkylcarbamyl the alkyl groups of which have up to 20 carbon atoms, N-phenylcarbamyl, acyl preferably derived from aliphatic carboxyl acids having up to 20 carbon atoms or benzoyl, alkyl having up to 20 carbon atoms such as methyl, ethyl, butyl, heptadecyl, olefinically unsaturated alkyl having up to 20 carbon atoms such as allyl or undecenyl, cycloalkyl such as cyclohexyl, aryl preferably phenyl or naphthyl, or aralkyl such as benzyl or phenyl ethyl; the above substituents particularly the phenyl groups can in turn be substituted with substituents such as nitro, halogen such as chlorine or bromine, alkyl preferably having up to 5 carbon atoms such as methyl or ethyl,
  • R hydrogen, carbamyl, carboxyl, esterified carboxyl groups preferably esterified with aliphatic alcohols having up to 20 carbon atoms, alkyl having up to 20 carbon atoms such as methyl, ethyl, butyl or heptadecyl, olefinically unsaturated alkyl having up to 20 carbon atoms such as allyl or undecenyl, cycloalkyl such as cyclohexyl, aryl preferably phenyl or naphthyl, or aralkyl such as benzyl or phenyl ethyl; the above substituents particularly the phenyl groups can in turn be substituted with substituents such as nitro, halogen such as chlorine or bromine, alkyl preferably having up to 5 carbon atoms such as methyl or ethyl, hydroxy, alkoxy having preferably up to 5 carbon atoms such as methoxy or ethoxy, carboxyl
  • phenyl groups of the above substituents can further be substituted by phenyl or naphthyl groups or can contain phenyl or naphthyl groups in anellated form.
  • S-imino-M-pyrazolines are prepared according to common practice by reacting acyl acetonitriles with desired hydrazine derivative.
  • Compound XLVIII is, for example, prepared in the following manner:
  • S-imino-M-pyrazolines can be prepared in analogous manner.
  • R represents one of the following substituents:
  • carbamyl, carboxyl, esterified carboxyl groups preferably esterified with aliphatic alcohols having up to 20 carbon atoms, alkyl having up to 20 carbon atoms such as methyl, ethyl, butyl or heptadecyl, olefinically unsaturatel alkyl having up to 20 carbon atoms such as allyl or undecenyl, cycloalkyl such as cyclohexyl, aryl preferably phenyl or naphthyl, or aralkyl such as benzyl or phenyl ethyl; the above substituents particularly the phenyl groups can in turn be substituted with substituents such as nitro, halogen such as chlorine or bromine, alkyl preferably having up to carbon atoms such as methyl or ethyl, hydroxy, alkoxy having preferably up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, esterified
  • the following compounds exhibit particular utility:
  • N on-G-mrco-mrm -SOaH (LXI)
  • the above compounds are prepared in accordance with known manner by reacting vinylketones such as methylvinylketone, mesityl oxide or chalcone, or p-chloroethyleneketones with phenylhydrazine.
  • the cyclization can be accelerated by heating the reaction mixture, for example, in acetic acid.
  • Compound LVIII is prepared as follows:
  • l-phenyl-A -pyrazolines can be prepared in analogous manner, for example, as described in:
  • Amidrazones are compounds which contain the group mg v 16 No. 602,250 and German Auslegeschrift 1,146,751. Such compounds include those of the following formula:
  • Y represents a direct chemical bond, a vinylene group, an azomethine group or a phenylene group
  • X represents alkyl preferably of up to 18 carbon atoms such as methyl, ethyl, butyl, hexyl, palmityl or heptadecyl, olefinir cally unsaturated alkyl having up to 18 carbon atoms such as allyl; aryl such as a phenyl or a naphthyl; aralkyl such as benzyl or phenylethyl; or cycloalkyl such as cyclopentyl or cyclohexyl.
  • the above groups may in their turn be substituted, for example, with halogen such as chlorine or bromine; alkyl such as methyl or ethyl with advantageously up to 5 carbon atoms; hydroxy; alkoxy preferably having up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, carboxy ester preferably'with aliphatic alcohols having up to 18 carbon atoms, amino, acylamino preferably with acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms such as acetylamino or stearoylamino, alkylamino having preferably up to 18 carbon atoms, sulfo, aminosulfonyl, esterified sulfo groups or alkylsulfonyl having up to 18 carbon atoms;
  • halogen such as chlorine or bromine
  • alkyl such as methyl or ethyl with advantageously up to 5 carbon atoms
  • hydroxy alkoxy
  • R can represent hydrogen; alkyl with up to 20v carbon atoms such as methyl, ethyl, butyl or heptadecyl; olefinically unsaturated alkyl having preferably up to 18 carbon atoms such as allyl; cycloalkyl, such as cyclopentyl or cyclohexyl; aryl advantageously phenyl or naphthyl; or aralkyl such as benzyl or phenylethyl.
  • phenyl radicals in their turn, for example, with halogen such as chlorine or bromine; alkyl such as methyl or ethyl With advantageously up to 5 carbon atoms; hydroxy, alkoxy preferably having up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, carboxy ester preferably with aliphatic alcohols having up to 18 carbon atoms, amino, acyl'amino preferably with acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms such as acetylamino or stearoylamino, alkylamino having preferably up to 18 carbon atoms, sulfo, aminosulfonyl, esterified sulfo groups or alkylsulfonyl having up to 18 carbon atoms;
  • R can represent hydrogen; alkyl with up to 20 carbon atoms such as methyl, ethyl, butyl, stearyl or heptadecyl; olefinically unsaturated *alkyl of preferably up to 18 carbon atoms such as allyl; cycloalkyl such as cyclopentyl or cyclohexyl; aryl preferably phenyl or naphthyl; or aralkyl such as benzyl or phenylethyl.
  • halogen such as chlorine or bromine
  • alkyl such as methyl or ethyl with advantageously up to Scarbon atoms
  • hydroxy alkoxy preferably having up to5 car bon atoms such as methoxy or ethoxy, carboxyl, carboxy ester preferably with aliphatic alcohols having up to 18 carbon atoms
  • amino, acylamino preferably with acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms such as acetylamino or stearoylamino, alkylamino having preferably up to 18 carbon atoms, sulfo, aminosulfonyl, esterified sulfo groups or alkylsulfonyl having up to 18 carbon atoms
  • preferred substituents are those which have a diffusion-resistant or water-solubilizing action;
  • X and R and/ or X and R together can moreover repre sent the methylene or methine groups or hetero atoms such as O, S, Se or N, necessary for completing a 5- membered or 6-membered heterocyclic ring which may contain an anellated benzene ring;
  • the combination X H, and R can, for example, form the following heterocyclic rings: oxazole, benzoxazole, thiazole, benzthiazole, selenazole, benzselenazole, imidazole, benzimida- I zole, pyrrolidone, quinoline, piperidine or pyrimidine; 5 -N the combination X and R can represent piperidine, morpholine, pyrazole, pyrazoline, pyrrolidine or oxazolidine; 0
  • R represents hydrogen, acyl preferably acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms 10
  • R represents hydrogen, a sulfo group, aminosulfonyl
  • substituents which have a diffusion-resisting action substituents which have a diffusion-resisting action
  • (11) S OH; R and R together can represent the acyl radical of an aliphatic saturated or unsaturated 1,2- or 1,3-dicarboxylic acid or an aromatic o-dicarboxylic acid, in particular an o-dicarboxylic acid of benzene, so that the compound containing them has a S-membered or 6- 12 membered heterocychc ring, for example, the malerc imide ring, the succinimide ring, glutarimide ring or phthalimide ring.
  • N Suitable compounds include the following: S
  • aqueous solutions of potassium bichromate, or potassium ferricyanide Suitable baths are, for instance, a 20% by weight solution of potassium ferricyanide or a 10% by weight aqueous solution of potassium bichromate.
  • the required pH can be adjusted by adding the necessary amount of aqueous solution of acids or alkali metal hydroxides or carbonates.
  • (C) Fixing bath Any desired photographic fixing baths can be used.
  • the fixing agent must not have reducing properties.
  • Preferred are aqueous solutions of salts of .thiosulfate, e.g., sodium thiosulfate, potassium thiosulfate or ammonium thiosulfate.
  • the fixing agents can be used as about 20% by Weight aqueous solutions.
  • drying can be performed by means of conventional dryers for photographic materials at slightly raised temperatures.
  • the silver halide emulsions are produced in accordance with common practice.
  • the preparation involves three separate steps: 1) precipitation of the silver halide and physical ripening in the presence of gelatin, (2) freeing the resulting emulsion of excess water-soluble salt usually by washing and (3) after-ripening or chemical ripening to obtain the desired speed or sensitivity.
  • amidrazones or the reaction components which react with the oxidation products of amidrazones can be added at any desired stage to the light-sensitive silver halide emulsion layer.
  • reactants are understood in the following both the amidr-azones and compounds which react with the oxidation products of amidrazones to form a dye.
  • the arnidrazones are advantageously incorporated in the finished emulsion after the chemical ripening. It is convenient to add the reactants of the present invention from solutions in appropriate solvents. The solvent should, of course, be completely free from any deleterious eifect on the silver halide emulsion. Water or lower aliphatic alcohols or admixtures thereof have proven satisfactory as solvents for the majority of the :amidrazones of the invention.
  • the reactants are first dissolved in an oily organic material, and this combination is dispersed in a finely divided state throughout the emulsion.
  • concentration of the amidrazones in the emulsion can vary widely from about 1-120 preferably 2-50 g. per mol of silver halide, their specific concentration varying according to the type of light-sensitive emulsion and according to the effects desired. Preferred are concentrations of between 5 and 20 g. per mol of silver halide. The most suitable concentration for any given emulsion will be apparent upon making the test customarily used in the art.
  • the compounds which react with the oxidation products of amidrazones are added in amounts of 1'120 g. preferably 15-70 g. per mol of silver halide.
  • silver halides for the light-sensitive emulsions, it is possible to employ silver chloride or silver bromide, possibly with a few mol percent of silver iodide, or mixtures of these halides.
  • hydnophilic colloids are suitable as binders, such as, advantageously, gelatin, although this can be wholly or partially replaced by other film-forming materials, such as carboxymethyl cellulose, polyvinyl alcohol, alginic acid or derivatives thereof such as salts, esters or amides, polyvinyl pyrrolidone and the like.
  • the emulsions can also be optically sensitized with the ordinary sensitizing dyes, cyanines or merocyanines.
  • the emulsions can be stabilized with any of the known stabi- 23 lizers such as mercury compounds, triazoles, azaindenes, such as disclosed by Birr in Z.wiss.phot., vol. 47 (1952) pages 2-28.
  • the emulsions may be hardened by any suitable hardener, such as formaldehyde and halogen substituted aliphatic acids such as mucobromic acid.
  • suitable hardener such as formaldehyde and halogen substituted aliphatic acids such as mucobromic acid.
  • the process according to the present invention is suitable for the production of mono-color and also multicolor direct positive images.
  • the process can further be applied for the production of masking images for the color-correction of conventional multicolor images.
  • the multicolor images can be produced in conventional manner.
  • photographic multi-layer materials which contain in the usual manner light-sensitive layers which are sensitive to the three primary colors of the visible spectrum.
  • the multicolor images preferablyconsist of the subtractive colors yellow, cyan and magenta.
  • EXAMPLE '1 A silver bromide emulsion containing, per 100 ml., 1.0 g. of amine I and 1.0 g. of amidrazone 2 is applied to a suitable support, exposed to light and developed for minutes at 20 C. in the following developer:
  • Example 1 If the above photographic material described in Example 1 but which contains 1 g. of amine II is processed in a black and White developer of the methylamino phenol type, e.g., the developer A4 a blue positive image is likewise obtained.
  • EXAMPLE 3 In corresponding manner, a blue positive image is obtained if the photographic material of Example 1 is processed with an amino phenol developer, for example, the developer A3, a blue direct positive image is obtained.
  • EXAMPLE 4 A silver bromide emulsion containing, per 100 ml., 1 g. of Compound XXIX and 1.0 g. of amidrazone 2 is applied to a suitable support, exposed to light and developed for 5 minutes at 20 C. in the following developer:
  • magenta image is also obtained if the photographic material is developed with an amino phenol developer, for example, the developer A3.
  • EXAMPLE 6 A silver bromide emulsion containing, per ml. 1.0 g. of Compound XLI and 1.0 g. of amidrazone 2 is applied to a suitable support, exposed to light and developed for 5 minutes at 20 C. in the following developer:
  • EXAMPLE 8 A silver bromide emulsion containing per 100 ml. 1.0 g. of Compound LVIII and 1.0 g. of amidrazone 2 is applied to a suitable support, exposed to light and developed for 5 minutes at 20 C. in the following developer:
  • a photographic material having a silver halide emulsion layer containing a color coupler and an amidrazone compound that reacts with the oxidation products of a photographic developer during development without forming color but forms color during the bleaching step of photographic processing by reaction with the color coupler under the oxidizing conditions of the bleaching
  • the improvement according to which the color coupler is replaced by a difierent colorless compound which is an aryl amine, a thiazole, a S-amino-M-pyrazoline or a l-phenyl-A -pyrazoline that will not give rise to color during color development but will produce color by reaction with the amidrazone compound during the bleaching.
  • R stands for phenyl or a naphthyl
  • R' together with the o-carbon atom of the benzene 26' ring of R, represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring;
  • R" together with the o-carbon atom of the benzene ring of R represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring;
  • R represents an aryl group
  • R stands for hydroxyl, alkyl of up to 20 carbon atoms
  • olefinically unsaturated alkyl having up to 20 carbon atoms, cycloalkyl, aryl or aralkyl;
  • R represents hydrogen or an organo sulfon grouping
  • R stands for carbamyl, N-alkyl carbamyl, N-phenyl carbamyl, acyl, alkyl having up to 20 carbon atoms, olefinically unsaturated alkyl having up to 20 carbon atoms, cycloalkyl, aryl or aralkyl;
  • R and R separately represent hydrogen, carbamyl, carboxyl, esterified carboxyl, alkyl having up to 20 carbon atoms, olefinically unsaturated alkyl having up to 20 carbon atoms, cycloalkyl, aryl or aralkyl.
  • R stands for a phenyl or a naphthyl
  • R and R" separately represent hydrogen, alkyl having up to 20 carbon atoms, aryl, aralkyl or heterocyclic radicals; or
  • R and R" together represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring;
  • R together with the o-carbon atom of the benzene ring of R represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring;
  • R together with the o-carbon atom of the benzene ring of .R represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring;
  • R represents an aryl group
  • R stands for hydroxyl, alkyl of up to 20 carbon atoms, olefinically unsaturated alkyl having up to 20 carbon atoms, cycloalkyl, aryl or aralkyl;
  • 3,443,942 27 28 R represents hydrogen or an organo sulfon grouping
  • References Cited R stands for carbamyl, N-alkyl carbamyl, N-phenyl UNITED STATES PATENTS esterified carboxyl, alkyl having u to 20 carbon carbamyl, acyl, alkyl having up to 20 carbon atoms, 3,293,032 12/1966 Jaeken at 96 53 olefinically unsaturated alkyl having up to 20 carbon atoms cycloalkyl, aryl or aralkyl; and 5 NORMAN G. TORCHIN, Pumary Exammer.
  • R and RF separately represent hydrogen, carboxyl, A. T. SUROPICA, Assistant Examiner. esterified carboxyl, alkyl having up to 20 carbon atoms, olefinically unsaturated alkyl having up to 20 US. Cl. X.R. carbon atoms, cycloalkyl, aryl or aralkyl. 10 969, 21

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US470615A 1964-07-24 1965-07-08 Colored photographic direct positive images Expired - Lifetime US3443942A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEA46672A DE1213241B (de) 1964-07-24 1964-07-24 Verfahren zur Herstellung von photographischen direktpositiven Farbstoffbildern
DEA49001A DE1259700B (de) 1964-07-24 1965-04-22 Verfahren zur Herstellung von photographischen direktpositiven Farbstoffbildern
DEA49535A DE1259701B (de) 1964-07-24 1965-06-21 Verfahren zur Herstellung von photographischen direktpositiven Farbstoffbildern
DEA49534A DE1257570B (de) 1964-07-24 1965-06-21 Verfahren zur Herstellung von photographischen direktpositiven Farbstoffbildern

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US470615A Expired - Lifetime US3443942A (en) 1964-07-24 1965-07-08 Colored photographic direct positive images

Country Status (7)

Country Link
US (1) US3443942A (de)
BE (1) BE667369A (de)
CH (1) CH456343A (de)
DE (4) DE1213241B (de)
FR (1) FR1592055A (de)
GB (1) GB1123782A (de)
NL (1) NL6509590A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5695914A (en) * 1995-09-15 1997-12-09 Eastman Kodak Company Process of forming a dye image
US6033833A (en) * 1997-08-06 2000-03-07 Eastman Kodak Company Fogging solution for a reversal process

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293032A (en) * 1961-08-02 1966-12-20 Gevaert Photo Prod Nv Process for the preparation of colour images

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293032A (en) * 1961-08-02 1966-12-20 Gevaert Photo Prod Nv Process for the preparation of colour images

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5695914A (en) * 1995-09-15 1997-12-09 Eastman Kodak Company Process of forming a dye image
US6033833A (en) * 1997-08-06 2000-03-07 Eastman Kodak Company Fogging solution for a reversal process

Also Published As

Publication number Publication date
DE1259701B (de) 1968-01-25
FR1592055A (de) 1970-05-11
NL6509590A (de) 1966-01-25
BE667369A (de) 1966-01-26
DE1257570B (de) 1967-12-28
DE1259700B (de) 1968-01-25
DE1213241B (de) 1966-03-24
CH456343A (de) 1968-07-15
GB1123782A (en) 1968-08-14

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