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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/60—Processes for obtaining vesicular images
• • 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
  • G03C1/64—Compositions containing iron compounds as photosensitive substances
• • 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
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/40—Chemically transforming developed images
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/144—Hydrogen peroxide treatment

Definitions

• This invention relates to a process for the production of photographic images by the imagewise decomposition of addition compounds of hydrogen peroxide with organic compounds, the image being made visible, either physically by developing the gas bubbles formed during decomposition, or chemically by using the oxygen formed during decomposition for a color-forming oxidation reaction.
• U.S. Pat. No. 3,615,491 discloses a process for the production of photo-graphic images consisting of a silver image and a vesicular image superimposed upon the silver image.
• a silver image is initially produced in the usual way in a hydrophilic layer although it has far weaker density than conventional black-white images produced in that way.
• the layer is then brought into contact with hydrogen peroxide, which decomposes to form oxygen gas bubbles at those places at which the silver is present imagewise in finely divided form.
• the oxygen formed during the image-wise decomposition of hydrogen peroxide can be made visible chemically, by using it for a colorforming oxidation reaction, rather than physically by bubble formation as described above.
• a light-sensitive layer is exposed imagewise to form nuclei from noble metals of the Groups lb or VIII of the Periodic Table in imagewise arrangement, after which this layer is treated with peroxidic compounds which decompose catalytically at the nuclei formed in an imagewise arrangement, in the presence of reaction components for a color-forming oxidation reaction.
• the chemical nature of the organic addition component is not critical.
• the only requirements which the organic compound has to satisfy are that the addition compound with hydrogen peroxide should be sufficiently stable and should only be split at temperatures of from to 150C, preferably from to C, under the conditions of the process, accompanied by the liberation of H 0
• Addition products of hydrogen peroxide with organic, preferably aliphatic, acid amides, for example with succinimide, asparagin or, in particular, urea are particularly favourable. It is also possible, however, to use addition products with aliphatic polyhydric alcohols, preferably containing from three to six carbon atoms, for example with erythritol, mannitol or pinacol.
• Addition products of hydrogen peroxide with organic amines or acid hydrazides for example addition products of H 0 with hexamethylene triamine, diacetyl hydrazine, succinic acid dihydrazine or malonic acid dihydrazide, can also be used.
• Photosensitive layers which, on exposure to light, from imagewise noble nuclei which catalytically accelerate the decomposition of hydrogen peroxids, are preferred for carrying out the process according to the invention. It is preferred to use silver halide emulsion layers with a relatively low silver halide content, of the kind described in German Offenlegungsschrift'No.
• the process is particular advantageous since it is possible to start from silver salt and, more particularly, silver halide emulsion layers which have a relatively high sensitivity compared with conventional materials for the production of vesicular images.
• the addition compounds of H 0 with organic compounds used in accordance with the invention can be used in a variety of different forms.
• the form in which they are used is governed primarily by the nature of the light-sensitive layer.
• the addition compound can be added to the light-sensitive layer itself during preparation, or alternatively it can be brought into contact with the light-sensitive layer, either before or after exposure.
• the addition product of H 0 is brought into contact with the exposed and developed layer. Contacting can be carried out either by applying a paste containing the addition compound, or directly by applying a separate layer to the light-sensitive layer, in which case a sufficient quantity of the peroxidecontaining addition compound must be present in this separate layer.
• the concentration of the peroxide-containing addition compound in thelight-sensitive layer or separate layers can be varied within wide limits.
• the density of the image formed and the intensifying effect upon the silver image obtained by exposure and photographic development, if any, are governed to a'certain extent by the concentration of the peroxide in the layer.
• Pastes containing the addition compound can be prepared according to the recipes normally used for producing processing pastes of this kind. For example, it is possible to use polyglycols, viscous or pasty organopolysiloxanes, waxes of widely differing chemical origin, fatty acids, amino fatty acids, fatty acid amides and fatty alcohols etc. To prepare the pastes, these sub stances are fused and the finely ground addition compound, for example the carbamide perhydrate, is added to the resulting melt. Naturally, the temperature should not be increased beyond the decomposition point of the addition compound.
• the pastes can be applied to the exposed light-sensitive layer or to a separate layer support, for example of paper or a cellulose ester.
• the layer is then brought into intimate contact with the light-sensitive layer containing the decomposition nuclei for H 0 and heated beyond the decomposition temperature of the addition compound. It is also possible, however, to arrange the layer with the addition compound at a certain distance, for example up to a few millimetres, from the exposed layer containing the decomposition nuclei, and subsequently to heat the two layers.
• a permeable support such as a fleece or felt of glass or of a polymer for example a celluloseester e.g. celluloseacetate
• the layer in these embodiments it is advantageous to increase the amount of the peroxide compound in the layer. in most cases a concentration of at least 5 g of active hydrogen peroxide per square meter in the layer leads to satisfactory results.
• the layer may, however, contain far higher concentrations, for example up to 50 g per square meter. A higher amount and thicker layer is in particular desirable if the layer is to be used several times.
• the process according to the invention comprises the steps of exposing the light-sensitive layer and, optionally, a further process step for producing the decomposition nuclei for the hydrogen peroxide, for example in the form of a photographic development for forming silver nuclei. This is followed by heating in the presence of the peroxide addition compound, as a result of which hydrogen peroxide is liberated.
• the hydrogen peroxide is decomposed on the catalytically active decomposition nuclei.
• the image is made visible as mentioned above, either physically by bubble formation, or chemically by the presence of reaction components for a color-forming oxidation reaction. Fuller details in this respect can be found in the aforementioned Patent Specifications.
• the present invention obviates the disadvantages attending known processes using dissolved or gaseous hydrogen peroxide.
• the small quantities of hydrogen peroxide required for photographic processes of this kind which have to be present briefly in high concentrations are formed in a uniform and highly reproducible manner during decomposition of the peroxide addition compound. As a result, highly uniform photographic images of high coverage are obtained.
• the decomposition temperature of the peroxidecontaining addition compounds can be varied within certain limits by the addition of certain compounds which influence the stability of the addition compounds.
• additives such as these include small quantities of acid-reacting substances such as oxalic acid, citric acid, salicylic acid, tannin, boric acid, sodium bisulfate or acid sodium phosphate.
• the stability of the addition compounds can be improved by the addition of substances such as these.
• the layers according to the invention contain the light-sensitive substances, preferably in dispersion in a binder.
• suitable binders include silica gel, polyvinyl acetate, partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, cellulose esters such as cellulose acetate or cellulose butyrate, carboxymethyl cellulose or natural binders, especially proteins such as gelatin.
• the visible image can also be produced chemically by carrying out heating of the exposed layer with the addition compound in the presence of reaction components for a color-forming oxidation reaction. Suitable processes are described in the aforementioned U.S. Pat. No. 3,674,490, issued July 4, 1972.
• the peroxide-initiated dye formation also takes place more quickly when the layer has been subjected to a brief treatment with water vapour after exposure.
• Reaction components of the kind which give extremely deep-colored compounds during oxidation with the catalytically activated peroxide compound are of course preferred for the oxidative dye-forming reaction.
• reaction components can be organic compounds which themselves yield the image dye during oxidation, for example amino-, hydroxyor aminohydroxy compounds of isocyclic or heterocyclic aromatic compounds.
• the amino-, hydroxyor aminohydroxy compounds can also be substituted, for example by halogen, alkyl, aryl, alkoxy, sulfonic acid, nitro, keto, carboxylic acid or carbonamide groups.
• the following are mentioned by way of example: 2,5-dichloro-p-phenylene diamine, guaiacol, 4-methoxy-l-naphthol, l-hydroxy-Z-amino- 4-benzene sulfonic acid, 1-amin0-2-hydroxy-4-benzene sulfonic acid, 3-amino-5-sulfo-salicyclic acid, 1,6,7- trihydroxy naphthalene-3-sulfonic acid, benzidine-2,2'- disulfonic acid, benzidine-3,3'-disulfonic acid, 1,8- dihydroxy naphthalene-3,6-disulfonic acid and 4- nitropyro-catechol. 1
• mixtures of several of these compounds actually show much stronger dye formation than the individual components during oxidation.
• a mixture of o-phenylene diamine and pyrocatechol promotes greater dye formation.
• Even components which, in their own, do not give any dyes during oxidation for example tetrabromo-hydroquinone or tetrabromo-pyrocatechol, can intensify dye formation when added to other hydroxy-, aminoor aminohydroxy compounds.
• Oxidizable organic compounds which only give the image dye in a subsequent reaction with other compounds, are also suitable for the process according to the invention.
• lsocyclic and heterocyclic hydrazines can also be oxidatively coupled with suitable components to form dyes (cf. for example H. HUNIG et al., Angew. Chem. 74 1958 215; S. HUNIG, Chimia (1961), 133 and Angew. Chem. 74 (1962) 818).
• the color-forming photographic developer substances are catalytically oxidized by the peroxide compounds on the catalyst distributed imagewise. Their oxidation products can then react with photographic color couplers known per se, whiqh are also present, to form dyes.
• Any color couplers can be used for this purpose, for example those of the phenol or naphthol series as blue-green couplers, those of the indazole series as purple couplers, and those auf the benzoyl acetanilide series as yellow couplers.
• EXAMPLE 1 A photographic material with a silver bromide emulsion layer on a cellulose acetate support which contains 3.5 mol of silver iodide, based on the silver halide, whose silver covering amounts to 0.2 g of silver per sq. metre, is exposed to form an image. This is followed by development in a developer of the following composition:
• a negative image of the original is obtained; it is only of low density and cannot be copied by conventional methods.
• percarbamide (1:1 addition product of H 0 with urea) 85.0 g of polyethylene glycol (molecular weight 8000). This is followed by heating for seconds at 90C as a result of which the peroxide compound decomposes on the image silver and a vesicular image is formed.
• the pastes are prepared by fusing the polyglycols at temperatures below the decomposition point of the peroxide compound, adding the very finely powdered organic peroxide and grinding to form a homogeneous suspension. For application to the film, this suspension is fused at the lowest possible temperature.
• polyethylene glycol instead of the aforementioned polyethylene glycol,it is also possible to use one with a different molecular weight. Polyethylene glycols with a molecular weight of from 6000 to 12.000 have proved to be the most suitable. To lower the melting point, it is also possible to use mixtures of polyethylene glycols with one another or with other compounds, for example mixtures with alcohols, in particular lower aliphatic alcohols, polyglycol ethers or alkyl polyglycol ethers, fatty alcohols, or methylene glycols. In this instance, the polyethylene glycol can also be replaced by the aforementioned substances. To improve the spreading properties of the pastes, it can occasionally be of advantage to use mixtures of filmforming agents or to add wetting agents to the pastes.
• EXAMPLE 2 Perparation of the light-sensitive material: 20 g of green ammonium ferricitrate are dissolved in 80 cc of water 6 g of ammonium ferrioxalate are dissolved in 60 cc of water 5 g of K Fe(CN) are dissolved in 50 cc of water 1 g of citric acid is dissolved in 10 cc of water 12 g of gelatin are dissolved in 200 cc of water.
• the dried layer is exposed behind a grey step wedge in a conventional Sensitometer (exposure time 10 seconds with a 100 Watt lamp). The layer is then exposed for about 1 minute to an atmosphere of water vapour at about C. It is then rinsed with water for 10 minutes, after which it can be exposed to daylight. A virtually invisible blue image of the original is obtained from this treatment.
• Example 1 The image is coated with a peroxide paste as described in Example 1, followed by further processing as described in that Example.
• EXAMPLE 3 A substantially fog-free silver bromide iodide gelatin emulsion layer (4.5 mol of silver) is cast on to a polyethylene terephthalate substrate. Layer thickness about 10 a. After image-wise exposure (0.5 seconds with X- rays between fluorescence-intensifying films), the layer is initially treated for 5 minutes at 20C in the following developer:
• the layer is then treated for 2 minutes with a bath of the following composition:
• EXAMPLE 4 A mixture of ml of a highly sensitive AgBremulsion and 500 ml of a 10 by weight aqueous solu tion of the cyan color coupler CO-NH-CIBHU I S H are cast to form an approcimately 10 thick layer. Silver covering approximately 0.5 g of AgNO per square metre. An approximately 5 1. thick gelatin protective layer is then cast over this layer.
• couplers of the indazole or pyrazolone series can be used as magenta couplers, and those of the ben zoylacetanilide series as yellow couplers.
• the hydrogen peroxide forming compound is an addition compound of hydrogen peroxide with an aliphatic acid amide, aliphatic polyhydric alcohol, aliphatic amine or acylsubstituted hydrazine.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (3)

• 1970
  • 1970-11-17 DE DE19702056359 patent/DE2056359A1/de active Pending
• 1971
  • 1971-11-12 GB GB5259271A patent/GB1354158A/en not_active Expired
  • 1971-11-12 CA CA127,471A patent/CA968210A/en not_active Expired
  • 1971-11-15 US US00198947A patent/US3765890A/en not_active Expired - Lifetime
  • 1971-11-15 IT IT54084/71A patent/IT944926B/it active
  • 1971-11-16 BE BE775327A patent/BE775327A/nl unknown
  • 1971-11-17 FR FR7141201A patent/FR2114821A5/fr not_active Expired
  • 1971-11-17 CH CH1672371A patent/CH566577A5/xx not_active IP Right Cessation

Patent Citations (3)

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