Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
  • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D257/04—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/82—Carbazoles; Hydrogenated carbazoles
  • C07D209/88—Carbazoles; Hydrogenated carbazoles 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 carbon atoms of the ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
  • C07D233/84—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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
  • C07D235/28—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
  • C07D239/32—One oxygen, sulfur or nitrogen atom
  • C07D239/38—One sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/56—One oxygen atom and one sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/58—Two sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/60—Three or more oxygen or sulfur atoms
• • 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
  • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
  • C07D241/40—Benzopyrazines
  • C07D241/44—Benzopyrazines 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 carbon atoms of the hetero ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
  • C07D249/12—Oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
  • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
  • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
  • C07D263/60—Naphthoxazoles; Hydrogenated naphthoxazoles
• • 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
  • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
• • 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
  • C07D277/70—Sulfur atoms
  • C07D277/74—Sulfur atoms substituted by carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
  • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
  • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
  • C07D285/135—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
  • G03C1/00—Photosensitive materials
  • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
  • G03C1/498—Photothermographic systems, e.g. dry silver
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development
• • 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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals

Definitions

• the invention relates to a process for the production of photographic images, in particular a copying process, wherein a supported layer which contains imagewisely distributed development nuclei for dissolved silver salts, in either visible or invisible form, is developed in the presence of an aqueous solution of silver salts soluble in water at pH values between 1 and 7.
• a light-sensitive silver halide emulsion layer is exposed to light through an original and then developed in an alkaline medium and fixed in the usual manner.
• supported layers which contain in imagewise distribution development nuclei for silver salts are developed into visible images at pH values between 1 and 7, if during the development they are in effective contact with an aqueous solution of silver salts having a solubility in water at a pH between 1 and 7 of at least 0.2 g./l. silver.
• the layer containing the development nuclei distributed according to the image will hereinafter be termed the imagewise nucleated layer.
• a very wide variety of imagewise nucleated layers can be used for the process according to the invention.
• the only condition to be fulfilled is that the said layer contains nuclei at which the soluble silver salts 'can be reduced.
• layers which contain a photographic silver image or an image of other finely divided metals for instance, of gold or of heavy metal sulfides, such as silver sulfide, nickel sulfide or the like.
• a silver halide emulsion layer which contains development nuclei in the form of latent image specks produced on exposure.
• Light-sensitive silver halide emulsion layers such as silver chloride, chlorobromide or bromide layers, which may have a silver iodide content of up to 30 mols percent, preferably up to about 10 mols percent, are for example suitable for this purpose.
• Conventional silver halide emulsion layers contain between 1l0 g. silver/m. in the form of silver halide.
• silver halide emulsion layers which have only a relatively small concentration of silver halide of about 0.01 to 1.5 g., preferably 0.1 to 1.0 g., silver per square meter.
• Layers of the kind can be produced in the usual manner, for example, by diluting silver halide gelatin emulsions of common concentration with a hydrophilic binding agent, for example, with alginic acid or its derivatives such as salts, in particular alkali metal salts, esters, in particular with aliphatic alcohols of up to 5 carbon atoms, or amides, or starch ethers, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethylcellulose or the like, or gelatin or other proteins such as casein, albumin or zein. It is also possible to precipitate the silver halide in a diluted low concentration.
• the preparation of such emulsions is described, for example, in
• the light-sensitive layers can be chemically or optically sensitized in the usual manner.
• any dyes suitable for silver halide e.g., any polymethine dyes such as carbocyanines, merocyanines, betaine cyanines and styryl dyes.
• the usual stabilizers may be added.
• heterocyclic mercapto compounds such as lphenylmercaptotetrazoles, 1-phenyl-3-mercapto-triazole-l, 2,4 or azaindenes as described in the article by Birr in Z. wiss, pnot, vol. 47 (1952), pp. 2-8.
• the process of the invention includes the essential steps of placing the imagewise nucleated layer, preferably an exposed silver halide emulsion layer containing an extremely low amount of silver halide, in contact with an aqueous solution of a soluble silver salt and developing at a pH between 1 and 7.
• the soluble silver salt can be provided by placing the imagewise nucleated layer into contact with a layer containing the soluble silver salt from which the silver salt is dissolved in the presence of water or by treating the imagewise nucleated layer directly with an aqueous solution of the silver salt.
• the soluble silver salt-containing layer can be applied either underneath or above the imagewise nucleated layer on the same support or on a separate support. The last mentioned arrangement is preferred since in that case it is possible to obtain a negative silver image in the silver halide layer and, after final processing, a direct positive silver image in the layer containing the soluble silver salts.
• the usual photographic types of gelatin can be used as binders for these layers.
• the gelatin may, however, be partly or completely replaced by other proteins, such as casein, albumin, zein, or by alginic acid or its derivatives such as salts, esters in particular with aliphatc alcohols of up to 5 C-atoms, or amides, or starch ethers, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose or the like.
• the application of silver in these layers is about 0.1 to 2.5 g./m. preferably 0.5 to 1.5 g./m. in the form of the soluble silver salt.
• the soluble silver salt is partly dissolved and diffusesinto the imagewise nucleated layer.
• the silver salt which has diffused over is reduced so that in that region a concentration gradient is established which considerably accelerates the dissolution of the silver salts in the layer which contains the silver salts.
• the silver salt image can subsequently be made visible by uniform exposure and development or by chemical reduction.
• silver salt layers of particular composition can be applied so that a silver image is immediately formed in the said layer.
• development nuclei of the kind described hereinbefore are uniformly added to the layer containing the soluble silver salts. With these uniformly nucleated layers an immediately visible silver image is formed in that layer upon development. That silver image is negative with respect to that formed in the imagewise nucleated layer.
• concentration of the nuclei is critical. If the concentration is too high, the soluble silver salts of the layer will be reduced before they have a chance to diffuse into the imagewise nucleated layer. If the concentration of the nuclei is insufficient, the result is an unsatisfactory formation of silver.
• the optimum concentration depends somewhat on the kind of the imagewise nucleated layer, the type of acid soluble silver salts and in particular the binder used for both layers. In general, a concentration of development nuclei corresponding to a silver nuclei concentration of about 1 to 150 mg. per m? of the layer containing the soluble silver salt is sufiicient.
• the layer containing the soluble silver salt is not removable in warm water.
• the silver salt layer is overcoated by the imagewise nucleated layer, for example, a silver halide layer which contains a binding agent that can be washed off with warm water, for example, unhardened gelatin or carboxymethyl cellulose. After exposure and imagewise formation of development nuclei in the upper layer, the material is developed and the imagewise nucleated layer is subsequently washed off in warm water, while the layer which contained the soluble silver salts and which after processing contains a silver image remains adhered on the support.
• the imagewise nucleated layer for example, a silver halide layer which contains a binding agent that can be washed off with warm water, for example, unhardened gelatin or carboxymethyl cellulose.
• the imagewise nucleated layer may either be initially treated with the solution and then in the developing bath or alternatively it may be initially treated with the developer solution and then with the silver salt solution.
• the silver is then deposited at the development nuclei, for example, the latent image specks formed by exposure, in the silver halide emulsion layer.
• An excellent silver image is formed with outstanding reproduction of the grey tone-values. How the process is carried out in detail will depend primarily upon the arrangement of the developer which may either be present in the imagewise nucleated layer or alternatively may be used in the form of an aqueous solution.
• the imagewise nucleated layer may be simply treated with water and then with an aqueous solution of the silver salts, or directly with an aqueous solution of the silver salts.
• the aqueous solution of the silver salts which have a pH between 1 and 7 should contain at least 0.2 g./l. silver in the form of the soluble silver salt. There is no upper limit of the concentration, so that saturated solutions of the silver salts can be used. Preferred are solutions which contain between 0.7 and about 4 g./l. silver in the form of the soluble silver salt.
• Pastes of this kind are obtained by adding a thickener as known per se to the aforementioned solutions, as known per se, such as derivatives of alginic acid, for instance sodium alginate, or alginic acid esters, polyvinyl alcohol or carboxyalkyl cellulose, for instance carboxymethyl cellulose.
• Suitable developers for the process according to the present invention include all developers capable of reducing the soluble silver salts under the processing conditions at acid or neutral pH-values.
• the following developers may be used: developers of the 3-pyrazolidone series, preferably 1-phenyl-3-pyrazolidone or its derivatives as well as 3-aminopyrazolines, for example, 1-paminophenyl-3-aminopyrazoline or its derivatives as described, for example, in British patent specification 768,- 071; 4-aminopyrazolones or its derivatives as described, for example, in British patent specification 768,071, for example, 1-phenyl-3-carbonamido-4-amino-5-pyrazolone and l-phenyl-3-methyl-4-amino-S-pyrazolone; hydroxytetronic acid or its derivatives such as ascorbic acid or similar products or salts of reducing heavy metals such as ferrous salts, for example ferrous citrate.
• the first-mentioned developers are particularly suitable.
• the following developers of the 3-pyrazolidone series exhibit particular utility: l-phenyl-3-pyrazolidone; 1-mtoluyl-3-pyrazolidone; l-p-toluyl-3-pyrazolidone; l-phenyl- 4-methylpyrazolidone; 1-phenyl-5-methyl-3-pyrazolidone; 1,4-dimethyl-3-pyrazolidone; 4-methyl-3-pyrazolidone; 4, 4-dimethyl-3-pyrazolidone; 1-phenyl-2-acetyl-3-pyraz0lidone; 1-phenyl 4,4-dimethyl-3-pyrazolidone; l-(4-bromophenyl) -3 -pyrazolidone.
• the aforementioned developers may be used in combination with one another or with other known developers.
• the developers may be used in the form of aqueous solutions of pH 1 to 7 or alternatively they may be added to the imagewise nucleated layer in which case they are used in quantities of preferably 0.01 to 2.5 g. per square meter.
• Aqueous solutions suitable for development preferably contain between 0.1 and 50 g., particularly 0.5 to 20 g., of developer per liter.
• the acids to be used must not form a silver salt which is less soluble than the we acid-soluble silver salts used. Consequently, hydrohalic' acids, for example, cannot be used.
• suitable acids are inorganic acids such as sulfuric acid and nitric acid and organic acids in particular aliphatic carboxylic acids having up to 6 carbon atoms such as acetic acid, citric acid, adipic acid and thelike, and acids the silver salts of which are used in the process according to the invention.
• the acids can also be added either to the imagewise nucleated layer, for instance the silver halide emulsion layer or to the layer which contains the acid soluble silver salt or to the developer. In cases where acidcontaining emulsion layers are used, the acids are added in quantities of between 0.001 and 10 g., preferably between 0.1 and 3 g. per square meter depending on the wherein:
• n 1 or 2.
• R alkyl, preferably with up to 3 carbon atoms, aralkyl such as benzyl or phenylethyl, aryl such as phenyl or naphthyl, or heterocyclic rings such as diazolyl, oxazolyl, triazolyl, oxadia zolyl, thiadiazolyl, tetrazolyl, azaindenyl, preferably tetraor penta-azaindenyl, benzthiazolyl, naphthiazolyl, benzooxazolyl, naphthoxazolyl, pyridyl, quinolyl, pyrimidinyl, quinoxalinyl, quinazolinyl, which radicals may in turn be substituted, for example, by alkyl, alkenyl, preferably with up to 6 carbon atoms, aryl such as phenyl or naphthyl, hydroxyl, alkoxy, aroxy such as phenoxy
• Aliphatic carboxylic acids the aliphatic chain or which is substituted with an organic thioether grouping, include the following:
• substitution products in which these compounds have 75 remaining compounds may be prepared from the corresponding mercaptans and organic halogen compounds or halogen carboxylic acids in alkaline solution by processes similar to those described in Houben-Weyl, vol. 9, PP. 103-113.
• the compounds can be isolated in the form of free acids or as alkali metal salts.
• the compounds can be purified by recrystallization from or by solution and reprecipitation from water or alcohol.
• the process according to the invention is characterized by the excellent quality of the images obtained. This is partly due to the fact that the silver is deposited in a particularly fine form which yields excellent grey tones.
• a silver halide emulsion layer of low silver content is prepared as follows:
• a conventional silver bromide gelatin emulsion is diluted with an aqueous gelatin solution.
• a layer of the above emulsion is applied onto a paper support and dried.
• the final layer had a silver concentra tion of 0.1 g. Ag per m. in the form of silver bromide.
• Layer-containing soluble silver salt 33 g. of carboxymethylthiomalic acid (compound 9) are added in the form of a 10% aqueous solution to 1 liter of a 6% aqueous gelatin solution.
• the solution is acidified with ml. of a aqueous sulfuric acid, and the silver salt is then precipitated at 40 C. by the addition of 18.6 g. of silver nitrate in the form of a 10% aqueous solution.
• an aqueous colloidal solution of silver is added, so that the final material contains 0.05 g. of silver nuclei per square meter.
• a paper support is coated in the usual manner with the above mixture to which has been added 5 cc. of a aqueous saponin solution and 5 cc. of a formaldehyde solution.
• the completed, swelled layer has a thickness of about 10
• the silver content is about 0.5 g./m. in the form of the silver salt.
• the thioglycolic acid derivatives may be added in the solid form to the hinder or in the form of a 5 to 10% aqueous solution, if necessary with the addition of the quantity of alkali required for dissolving the acids, e.g. aqueous sodium hydroxide.
• the silver halide emulsion layer which has been exposed to form a latent image is passed through a 0.5% aqueous solution of 1-phenylpyrazolidone-(3) and then brought into intimate contact with the dry layer containing the soluble silver salts.
• a silver image is formed at the exposed areas by the reduction of the silver salt that has diffused over at the development nuclei of the latent image.
• the soluble silver salt layer an excellent silver image is formed, which is negative in relation to the silver image in the emulsion layer.
• a silver halide layer of low silver content is prepared as follows:
• the resulting emulsion is cast onto a paper support in the usual manner.
• the final layer contains per m?, 0.1 g. of silver in the form of silver chloride.
• the emulsion is applied in known manner onto a paper support so that the final layer contains about 0.8 g. of silver per In. in the form of silver phosphate.
• the exposed silver halide emulsion layer is moistened with water and brought into close contact with the dry silver phosphate containing layer. After a few seconds, the two layers are separated from each other. In the silver halide emulsion layer is obtained an excellent silver image, and in the layer that contained the silver phosphate a negative image which has excellent contrast and outstanding grey tones.
• An ordinary silver bromide gelatin emulsion having a silver iodide content of about 5% and containing 0.15 mol silver halide per liter is diluted in the ratio of 1:6 with a 2.5% aqueous solution of carboxymethylcellulose.
• This emulsion is applied over the layer of silver salt described above so that the silver halide content in the emulsion layer is about 0.3 g. silver per m.
• the thioglycollic acid derivative may be added to the binding agent either in the solid form or in the form of a 5-10% aqueous solution, if necessary with addition of the quantity of alkali, e.g., sodium hydroxide, necessary to bring them into solution.
• alkali e.g., sodium hydroxide
• a silver halide, emulsion layer is produced as follows:
• Example 1 Processing is carried out as in Example 1 with the soluble silver salt-containing layer of Example 1-.
• EXAMPLE 5 Processing A photographic material consisting of a gelatin layer bearing a negative silver image on a transparent support of cellulose triacetate is passed through a 0.5% aqueous solution of l-phenylpyrazolidone-(3) and brought into close contact with the soluble silver salt-containing layer described in Example 1. After a few seconds, the two lay ers are separated. A silver image which is negative with respect to the silver image of the above photographic material is obtained in the silver salt-containing layer and is stabilized in the usual manner by fixing and washing with water. The negative original is cleaned by fixing and washing with water.
• EXAMPLE 6 An imagewise exposed silver bromide gelatin emulsion layer on a support with a silver coating of 0.1 g./m. in the form of silver bromide and a l-phenyl-3-pyrazolidone content of 1 g./m. is bathed for 40 seconds in a solution of 67.5 g. of carboxymethylthiomalic acid (compound 9) and 32.5 g. of silver nitrate in 1 liter of water, which had been adjusted to pH 1 with sulfuric acid, and then fixed and rinsed with water in the usual way.
• compound 9 carboxymethylthiomalic acid
• the final silver image essentially consists of silver from the silver salt of carboxymethyl thiomalic acid.
• EXAMPLE 7 An imagewise exposed silver chloride gelatin emulsion layer on a paper support, with a silver coating of 0.1 g./ m? in the form of silver chloride and a l-phenyl-3-pyrazolidone content of 0.7 g./m. is coated with a paste of the following composition which is removed in a fixing bath after a contact time of 20 seconds. The material thus treated is then rinsed with water.
• the paste has the following composition:
• the polyvinyl alcohol solution is stirred with the mixture of carboxymethylthiomalic acid and the silver nitrate.
• the pH of the paste is adjusted to 1 by adding sulfuric acid.
• Cellulose derivatives such as methyl cellulose can be used instead of polyvinyl alcohol.
• EXAMPLE 8 An imagewise exposed silver bromide gelatin emulsion layer on a paper support having the composition indicated in Example 1, is bathed for 60 seconds in the following solution and then fixed and rinsed with water in the usual way:
• EXAMPLE 9 An imagewise exposed silver bromide gelatin emulsion layer on a paper support with a silver content of 2.5 g./m. in the form of silver bromide is bathed in the soluble silver salt solution described in Example 8, developed for 60 seconds in an aqueous solution of 5 g./l. of 1- phenyl-3-pyrazolidone, and then fixed and rinsed with water in the usual way. An excellent continuous tone image is obtained.
• This procedure is more advantageous than that in which the paper is bathed first in the developer solution and then in the silver salt solution.
• the silver salt is selected from the group consisting of a salt of phosphoric acid and a salt of an aliphatic carboxylic acid, the aliphatic chain of which is substituted with an organo thioether grouping and having a solubility in water at a pH between 1 and 7 of at least 0.2 g./l. silver in the form of salt.
• the silver salt is selected from the group consisting of a salt of phosphoric acid and a salt of an aliphatic carboxylic acid, the aliphatic chain of which is substituted with an organo thioether grouping and having a solubility in water at a pH between 1 and 7 of at least 0.2 g./l. silver in the form of salt.
• the improvement according to which the silver salt is selected from the group consisting of a salt of phosphoric acid and a salt of an aliphatic carboxylic acid, the aliphatic chain of which is substituted with an organo thioether grouping and having a solubility in water at a pH between 1 and 7 of at least 0.2 g./l. silver in the form of salt.
• a dispersion in a water-permeable binder of a water-soluble silver salt of phosphoric acid or an organo thioether-substituted aliphatic carboxylic acid the said silver salt has a solubility in water at a pH of between 1 and 7 at least 0.2 g./l. silver in the form of the silver salt, said dispersion also containing development nuclei for the salt, both the salt and the nuclei being uniformly dispersed in the binder.
• the dispersion is a thin layer on a support
• the development nuclei are in a concentration corresponding to from about 1 to about milligrams of silver per square meter of the layer
• the salt is in a concentration of from about 0.1 to about 2.5 grams per square meter of the layer.

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• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)

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• 1965
  • 1965-05-19 DE DE1472757A patent/DE1472757C3/de not_active Expired
  • 1965-08-06 DE DE1472773A patent/DE1472773C3/de not_active Expired
• 1966
  • 1966-05-17 CH CH717566A patent/CH463273A/de unknown
  • 1966-05-19 GB GB22288/66A patent/GB1125646A/en not_active Expired
  • 1966-05-20 NL NL6606960A patent/NL6606960A/xx unknown
  • 1966-12-13 US US601319A patent/US3554750A/en not_active Expired - Lifetime

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