US3819382A - Light-sensitive material having developers embedded therein - Google Patents

Light-sensitive material having developers embedded therein Download PDF

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US3819382A
US3819382A US00156047A US15604771A US3819382A US 3819382 A US3819382 A US 3819382A US 00156047 A US00156047 A US 00156047A US 15604771 A US15604771 A US 15604771A US 3819382 A US3819382 A US 3819382A
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silver
light
solution
sensitive
layer
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E Roos
K Ley
A Koenig
H Kampfer
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • 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
    • G03C1/49827—Reducing agents
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • 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
    • G03C8/06—Silver salt diffusion transfer

Definitions

  • the photographic processes for processing exposed, light-sensitive materials which contain embedded developer substances may be subdivided into two main groups, one group comprising those processes in which aqueous treatment baths are used, whereas the other group comprises processes in which the exposed photographic materials are processed at elevated temperature without the use of development baths.
  • the materials are developed simply by the action of an alkaline solution and are stabilized against further changes by light by means of stabilizer baths or by fixing and washing with water.
  • German Patent Specification, No. 880,045 The principle of heat copying processes has been described in German Patent Specification, No. 880,045 and involves developing the material by simply heating it after exposure.
  • German Patent Specification No. 1,300,014 also belongs to the heat copying type of process.
  • photographic recording materials which contain an oxidizing agent, a reducing agent and a minorquantity of a light-sensitive substance whose photolytic products initiate the redox reaction which is accompanied by production of color.
  • the oxidizing agents used in this process are organic silver salts and the reducing agents are aminophenols, hydroxylamines, pyrazolidones or phenols. Phenylene diamine and etherified naphthols e.g.
  • Compounds suitable for use as light-sensitive compounds are heavy metal salts which form traces of the free metal on exposure to light, especially light-sensitive silver salts such as silver halides which form silver by a photolytic reaction on exposure to light. These photolytic heavy metal nuclei initiate the redox reaction. 7
  • the materials used in the said process also have the above mentioned disadvantage of being relatively unstable in storage due to the sensitivity of the reducing agents to oxidation by atmospheric oxygen. To obtain sufficient stability in storage for practical requirements, it is, therefore, necessary to take additional steps to protect the reducing agents against the action of atmospheric oxygen. This is achieved mainly by the addition of antioxidants.
  • R R R R R and R hydrogen or alkyl groups having up to 9 carbon atoms, preferably methyl groups;
  • R and R or R and R may be joined together to complete a carbocyclic ring system having 5, 6 or 7 carbon atoms which can contain a double bond and/or which can be substituted by alkyl groups having up to 4 carbon atoms;
  • R may further stand for an alkoxy group having up to 6 carbon atoms or a tertiary amino group of the following formula:
  • R and R represent alkyl having up to 6 carbon atoms or are together the ring members required for completing a S-membered, 6-membered or 7- membered ring which may contain an oxygen atom or a nitrogen atom as ring member in addition to the nitrogen atom already present;
  • R and R hydrogen, alkyl or alkoxy having up to 6 carbon atoms, preferably methyl or tertiary alkyl groups, and, at least one of them represents a by droxyl group;
  • R and R hydrogen, alkyl or alkoxy having up to 9 carbon atoms, preferably methyl or tertiary alkyl groups, cycloalkyl such as cyclopentyl or cyclohexyl, aralkyl such as benzyl or phenyl ethyl, or aryl, especially a phenyl ring, or a group of the formula:
  • the photographic materials according to the invention which contain one or more of the foregoing developer substances are not in principle subject to any restrictions as regards their photographic application. They may be used wherever light-sensitive materials which contain developer substances are required. They may be used both for wet and for dry processing methods.
  • the optimum developer substances for any given photographic process can be selected by means of simple tests.
  • the materials according to the invention may contain both silver halides and organic silver salts, e.g. the silver salts of carboxyalkylthio derivatives or silver salts of carboxylic acids as described in British Patent Specification Nos. 1,11 1,492 and 1,110,046 or mixtures of these silver salts. These silver salts are sufficiently lightsensitive if precipitated in the presence of a protective colloid such as gelatin.
  • any silver halide emulsions may be used for producing the silver halide emulsion layers, such as silver chloride, silver bromide or silver chlorobromide emulsions, and they may also contain up to 10 mols percent of silver iodide. These emulsions may contain 0.05 to 0.5 mol of silver halide per litre.
  • the layers may contain the organic silver salts of carboxyalkylthio derivatives described in British Patent Specification No. 1,111,492 instead of silver halides or in admixture with silver halides.
  • the binder used for the photographic layers is preferably gelatin but this may be partly or completely replaced by other natural or synthetic binders.
  • Suitable natural binders are, e.g. alginic acid and its derivatives such as salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or its derivatives such as ethers or esters or carrageenates.
  • Suitable synthetic binders are, e.g. polyvinyl alcohol, partially saponified polyvinyl acetate or polyvinyl pyrrolidone andthe lilce.
  • the binder mixtures of gelatin and cellulose acetate described in German Auslegeschrift No. 2,000,926 may also be used, the gelatin solution for the layer being in that case mixed in the presence of phthalic acid in quantities of 10 to 50 percent by weight, based on the total amount of solids in the mixture, with cellulose acetate having an acetic acid content of between 30 and 50 percent by weight.
  • the emulsions may also be chemically sensitized, e.g. by adding compounds which contain sulfur, such as allyl isothiocyanate, allyl thiourea or sodium thiosulfate and the like, at the stage of chemical ripening. Reducing agents may also be used as chemical sensitizers, e.g. the tin compounds described in Belgian Patent No. 493,464 and 568,687,
  • polyamines such as diethylene triamine or formamidine sulfinic acid derivatives, e.g. according to Belgian Patent No. 547,323.
  • the emulsions may also be sensitized with polyalkylene oxide derivatives, e.g. with polyethylene oxide having a molecular weight of between 1000 and 20,000, with condensation products of alkylene oxides and the aliphatic alcohols, glycols or cyclic dehydration products of hexitols or with alkyl substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have a molecular weight of at least 700 and preferably more than 1000.
  • the emulsions may also be spectrally sensitized, e.g. with the usual polymethine dyes such as merocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes or oxonoles. Sensitizers of this type have been described in the work by F. M. Hamer The Cyanine Dyes and Related Compounds (1964).
  • The'emulsions may contain the usual stabilizers, e.g. homopolar or salt-type compounds of mercury which have aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • stabilizers e.g. homopolar or salt-type compounds of mercury which have aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • Azaindenes are also suitable for use as stabilizers, especially tetraor penta-azaindenes and especially those which are substituted with hydroxyl or amino groups.
  • Suitable stabilizers are e.g. heterocyclic mercapto compounds such as phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazoles or the substituted 4-aminobenzotriazoles described in British Patent No. 919,061.
  • the emulsions may be hardened for wet processing in the usual manner, for example with formaldehyde or halo-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters or dialdehydes.
  • formaldehyde or halo-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters or dialdehydes.
  • 1,174,159 or salts which form clearly defined hydrates such as sodium acetate, sodium citrate or sodium sulfate.
  • Compounds of the second type mentioned include glycols, polyethylene glycols, glycerol, sorbitol' or mono or oligo-saccharides. These substances are added to the casting solutions for the light-sensitive layer in such quantities that the dry layer contains about 0.1 to g/m of these substances.
  • the light-sensitive layer may be arranged on any layer support such as paper, synthetic resin, fabric or layer support must be stable at the usual temperatures employed.
  • the developer substances to be used according to the invention may be added to the emulsion layers which contain silver salts or to the intermediate layers in amounts of 50 to 1000 g, preferably to 700 g, per mol of silver salt.
  • photographic materials can be developed simply by the action of an alkaline solution after exposure to light and are, therefore, suitable both for use as negative rnaterial for the silver salt diffusion process and as copying material for processing in the two-bath process and for conventional processing by fixing and washing.
  • the developer substances to be used according to the invention have been embedded in the photographic layer, they are differentiated from known developer substances such as hydroquinone, aminophenol or p-methylaminophenol etc. by their improved resistance to oxidation. Furthermore, the photographic materials produced with these developer substances have less fog.
  • the compounds to be used according to the invention and the photographic materials containing them are especially suitable for a heat copying process of the following type.
  • a photographic recording material for the production of copies by the dry process contains as oxidizing agent a silver salt which is substantially insensitive to light, a reducing agent and a light-sensitive heavy metal compound which on exposure forms metal nuclei by photolysis, thus initiating the redox reaction on heating, the reducing agent used being one or more of the compounds according to the invention represented by the general formula indicated, which compounds are capableof reducing the light-sensitive silver salt at temperatures of between 50C and C in the presence of the photolytically produced heavy metal nuclei.
  • Suitable oxidizing agents of the image-producing redox system are silver salts of organic acids which, under the conditions of the process, are either insensitive to light or sensitive to light only to a negligible extent, e.g. silver saccharide, silver 5-chlorosalicylic aldoxime, silver 5-nitrosalicylic aldoxime or, preferably, a silver salt of a long chained fatty acid having up to 30 carbon atoms, e.g. silver stearate, silver palmitate or silver behenate or the silver salts of aliphatic carboxylic acids containing a thioether group as described in US. Patent No. 3,330,663. Silver salts of the last mentioned kind are light-insensitive if prepared in the absence of protective colloids such as gelatin.
  • the light-insensitive silver salt serving as oxidizing agent generally is used in a molar ratio of between 1:1 and 1:10 with respect to the above-defined reducing agent.
  • Suitable light-sensitive heavy metal salts which when exposed to light form metal nuclei capable of initiating the image-producing redox reaction are e.g. inorganic or organic salts of silver, mercury or gold.
  • the heavy metals of the sub-group lb of the Periodic System of Elements are preferred, especially silver salts and among these again the silver halides.
  • the metal salt may be mixed with the components of the redox reaction in the form of its aqueous suspension. If it is to be suitable, it must not undergo any change in the dark but when the mixture is exposed to UV light, it should undergo discoloration within a few seconds. If both these conditions are fulfilled, the heavy metal salt is suitable for the redox system.
  • the light-sensitive heavy metal salt is used in comparatively small quantities of about 0.05 to 0.2 percent by weight, based on the weight of the oxidizing agent. This proportion of light-sensitive salt is sufficient in most cases but a higher or lower percentage may, of course, also be used.
  • the light-sensitive heavy metal salt e.g. silver halide
  • the light-sensitive heavy metal salt should be present in such small quantities that the photolytically produced heavy metal nuclei are capable of initiating the redox reaction, but at the same time the concentration of the silver halide is so low that the metal nuclei formed do not cause any discoloration of the copying material, or only to a negligible extent.
  • the silver halide may be added to the casting solution for the layer which contains the components of the redox reaction or it may be formed in situ in the casting solution, e.g. by precipitation of the silver halide in the mixture.
  • the silver ions for the precipitated silver halide may in that case be derived mainly from the silver salt which is not light-sensitive.
  • the silver salts which are not light-sensitive and which are present as oxidizing agents may be obtained in a known manner exactly like the silver halide by precipitation of silver salt solutions, e.g. by the precipitation of silver nitrate with the alkali metal salts ofthe organic acids preferably in the absence of protective colloids.
  • the free acid may, of course, be present during precipitation but, in order to obtain highly transparent layers, it is advantageous to have only a slight excess of free acid present or even to use stoichiometric quantities of the organic acid and the silver salt.
  • the surface of the light-insensitive silver salts may be treated with vapors of hydrohalic acids, e.g. hydrochloric acid, hydrobromic acid or hydriodic acid.
  • hydrohalic acids e.g. hydrochloric acid, hydrobromic acid or hydriodic acid.
  • the quantity of silver halide produced on the surface may be kept within the required limits by adjusting the concentration of the hydrogen halide in the vapor phase and the treatment time.
  • the light-insensitive silver salts of the organic acids may, of course, also be treated with a solution containing halogen ions, such as chloride ions, bromide ions or iodide ions.
  • halogen ions such as chloride ions, bromide ions or iodide ions.
  • These halogen ions may be obtained from the hydrohalic acids themselves or from their salts, in particular their ammonium, alkali metal, or alkaline earth metal salts.
  • the reaction of the light-insensitive silver salts with the compounds which give off halogen ions is preferably carried out with the silver salts in the form ofa suspension in a volatile, non-aqueous liquid, although also the dry salts may be reacted, for example with hydrogen halide vapors.
  • hydrohalic acids and their salts e.g. the alkali metal salts, ammonium salts and alkaline earth metal salts already mentioned above and other metal salts, e.g. zinc salts and mercury salts
  • the light-sensitive silver halides ionisable organic halogen compounds e.g. triphenylmethyl chloride, triphenylmethyl bromide, 2- bromo-2-methyl propane, 2-bromo-butyric acid, 2- bromoethanol or benzophenone dichloride.
  • the materials according to this embodiment of the invention are preferably prepared by formation of the light-sensitive silver halides from the'light-insensitive silver salts of the organic acids. This enhances the capacity of the silver halides to produce photolytic silver nuclei which are especially effective in initiating the redox reaction.
  • useful materials can also be obtained by preparing the silver halides separately and subsequently mixing them with the light-insensitive silver salts, the photolytic heavy metal nuclei formed from such mixtures are generally not so active.
  • the binders used are preferably organic polymers such as copolymers of vinyl chloride and vinyl acetate or of butadiene and styrene, polyethylene, polyamides, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl pyrrolidone, polystyrene, chlorinated rubber, polyvinyl butyral, polymers of acrylic acid or methacrylic acid esters or copolymers of the derivatives of acrylic acid and methacrylic acid, cellulose derivatives such as nitro cellulose, cellulose acetates, cellulose propionates or mixtures thereof such as cellulose acetobutyrates.
  • organic polymers such as copolymers of vinyl chloride and vinyl acetate or of butadiene and styrene, polyethylene, polyamides, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl pyrrolidone, polystyrene
  • the light-sensitive layer may be used as a selfsupporting layer but it-is preferably applied to a suitable layer support.
  • the layer support must be stable at the processing temperatures of between 60C and 200C.
  • Suitable supports are e.g. sheets or foils of paper, cellulose acetate, polyethylene terephthalate, textile fabrics, metal foils or glass. Where paper supports are used, the paper may contain the usual suxiliary layers such as baryta layers and/or polyethylene layers.
  • the concentration of the reducing agent and of the oxidizing agent in the layer may vary within wide limits.
  • Proportions by weight of 4:1 to about 1:1 between the components of the redox reaction and the binder have generally been found sufficient.
  • the thickness of the light-sensitive layer may also be adapted to the requirements of the given reproduction process. Layer thicknesses of between 5 and microns are generally sufficient for the usual requirements.
  • the layer supports have the usual thicknesses of between about 0.1 and 0.8 mm.
  • the lightsensitive layers may be spectrally sensitized by the addition of dyes.
  • the usual white pigments such as silicon dioxide and toners such as phthalazone, phthalazone derivatives and phthalimide may be added to the light-sensitive layers.
  • the photographic materials according to the invention are processed in a known manner.
  • Image-wise exposure is carried out with the usual light sources used in photographic work, e.g. mercury lamps, iodine quartz lamps or simple incandescent lamps.
  • the type of light source used depends on the spectral sensitivity of the heavy metal salt. In the preferred method using silver halides, the usual incandescent lamps are sufficient.
  • the exposure time is a few seconds.
  • the exposed material is then uniformly heated to a temperature of between about 60C and 160C.
  • the time and temperature required for the heat treatment depends on the nature of the redox system. Periods of between 3 and 80 seconds are generally sufficient. A dark brown to black image is formed which is ready for immediate use.
  • An equimolar mixture of silver behenate and behenic acid is prepared by precipitating silver nitrate with a solution of sodium behenate and behenic acid in alcohol and water. The precipitate is carefully washed and dried.
  • the suspension used for preparation of the layer is prepared by treating the mixture described below in a ball mill for 12 hours:
  • the above mixture is applied to a conventional paper support at a concentration of 100 g/sq.m and dried at room temperature.
  • the light-sensitive layer is exposed through a transparent original.
  • the source of light used is a 750 Watt UV lamp at a distance of 5 cm.
  • the exposure time is 2 seconds and the distance from the source of light 5 cm.
  • the material is then heated to a temperature of 80C for 5 seconds.
  • a black-brown negative image of the original is obtained.
  • the suspension for the bottom layer is ground in a ball mill for about 16 hours and then applied on baryta paper and dried.
  • the silver application is 0.3 to 0.4 g/m
  • the top layer is cast on thedry bottom layer.
  • the amount of reducing agent applied is 0.5 to 1.5 g/m
  • the following reducing agents may be added to the top layer:
  • the reducing agents may also be added to the suspension for the bottom layer instead of that for the top layer, and ground with this suspension in a ball mill for about one-half hour, e.g.:
  • the light-sensitive material is exposed with tungsten lamps for 3 to 30 seconds depending on the intensity of the lamps and the required gradation, and developed by heat.
  • the development time varies from 3 to 80 seconds according to the height of the temperature within the range of 60C to 160C and the apparatus used.
  • the apparatus used for development may be heatable presses, drying drums, rollers or the apparatus described in Belgium Patent No. 628,174 or in French Patents Nos. 1,512,332; l,416,752 or 1,419,101 or the usual commercial apparatus.
  • the layer surface of the material may be kept in contact with a polyester foil during the heat development.
  • the images obtained-on development are brown or brownish black to neutral black images on a white to yellow ground, depending on the developer substance used and the processing conditions.
  • the pH of the emulsion is adjusted to 5.1 with sulfuric acid.
  • the emulsion is applied on a baryta paper in a known manner and dried.
  • the rear surface of the coated paper is placed in contact for 0.5 to 60 seconds with a metal or synthetic resin surface heated to 90 to 200C or with a liquid heat transfer agent.
  • the apparatus used for development may be conventional heat development apparatus or heatable presses, drying drums, rollers or the apparatus described in Belgian Patent No. 628,174 or the image-wise exposed negative may be exposed to infra-red radiation for about 10 to 180 seconds.
  • the well-covered silver image has little sensitivity to light. It may be stabilized by fixing and washing in water or by bathing it in an alcoholic solution of 2,5-dimercaptol ,3 ,4-thiadiazole or l-phenyl-S- mercaptotetrazole.
  • a paper is coated with a solution of:
  • Example 5 The following substances are added to 1 kg of an unwashed silver chlorobromide gelatin emulsion which contains per kg 0.18 mol of silver halide (20 mols AgBr):
  • This emulsion is added with stirring to a solution of 3 litres of a 3 percent solution of a cellulose acetate (acetate group content 40 percent by weight) in acetone/- water (1:4) and 1 litre of a 10 percent solution of phthalic acid in methanol and 60 g of Compound 38 or 60 g of Compound 43, and the emulsion is then applied to a baryta paper. Silver application 1.2 g/m The material is exposed and processed as described in Example 3 and a brown image is obtained.
  • the exposed material may also be developed for 1 minute in 10 percent sodium hydroxide solution and fixed and washed in the usual manner. A black, wellcovered image is obtained.
  • Example 6 2 m1 of a 40 percent aqueous citric acid solution are added to 1 litre of a 10 percent aqueous gelatin solution, and the solution is heated to 40C. 22 g of 2-noctylthio-5-carboxymethylthio-1,3,4-thiadiazole dissolved in the equimolar quantity of sodium hydroxide solution are then added and the solution is precipitated with 100 ml of a 10 percent silver nitrate solution with vigorous stirring, and 1 litre of a 10 percent solution of phthalic acid in methanol is added with stirring.
  • This emulsion is added with stirring to a solution of 2 litres of a 3 percent solution of a cellulose acetate (acetate group content 40 percent by weight) in acetone/water (4:1) and 200 ml of a 10 percent solution of phthalic acid in methanol and 50 g of Compound 38 or 50 g of Compound 25, and the emulsion is then applied to a layer support as in Example 3.
  • Silver application 0.6 g/m
  • 10.2 g of 3-carboxymethylthio-l,2,4- triazole may be used instead of 22 g of 2-n-octylthio-5- carboxymethylthio-l ,3,4-thiadiazole.
  • the material is processed as described in Example 3 and a brownish black image is obtained.
  • the exposed material may also be developed for 1 minute in a 10 percent sodium carbonate solution and fixed and washed in the usual manner. A black image is obtained.
  • Example 7 The following substances are added to 1 kg of a silver chloride gelatin emulsion which contains, per kg of emulsion, 0.2 mol of silver halide which has a silver iodide content of less than 0.1 mols percent:
  • the emulsion is applied to baryta paper in a known manner and dried. Silver application 1.3 g/m The exposed material is developed in a 10 percent aqueous sodium carbonate solution for one minute and fixed and washed in the usual manner. A well-covered black image is obtained.
  • Example 8 The exposed material described in Example 7 may also be brought into contact with the image-receiving layer described hereinafter in a commercial apparatus conventionally used for the silver salt diffusion process, and developed in the following activator solution:
  • Image-receiving material A black image with good whites is obtained.
  • Image-receiving material A black image with good whites is obtained.
  • a layer of baryta is applied from the follwing solution to a layer support of paoer g/m): 6 ml of a 50% aqueous suspension of barium sulfate,
  • the baryta layer is dried and then coated with an image-receiving layer from the following casting solution:
  • a light-sensitive photographic material comprising a silver chloride gelatin emulsion layer on a support, which emulsion layer contains per kg of casting solution 0.2 mol of silver halide with less than 0.1 mol percent of silver iodide (silver application 1.3 g/m and Compound 38 or Compound 43 g/kg of emulsion) is exposed image-wise and developed in the following 7 activator solution in an ordinary'commercial two bath apparatus:
  • the developed material is treated with the following stabilizer solution:
  • a light-sensitive photographic sheet material con taining a silver salt composition which comprises a light-insensitive silver salt, a catalytic amount of silver wherein n is 0 or 1;
  • R R R R R and R are hydrogen or alkyl groups having up to 9 carbon atoms, but
  • R and R may be joined together to complete a carbocyclic ring system having 5, 6 or 7 carbon atoms, and
  • R may further represent an alkoxy group having up to 6 carbon atoms or a tertiary amino group of the formula:
  • R and R represent alkyl having up to 6 carbon atoms or are together the ring members required for completing a 5-, 6- or 7-membered ring;
  • R R are hydrogen, alkyl or alkoxy having up to 6 carbon atoms, and at least one of them represents a hydroxyl group
  • R R are hydrogen, alkyl or alkoxy having up to 9 carbon atoms, cycloalkyl, aralkyl, aryl or a group of the formula:
  • a light-sensitive photographic sheet material containing 21 silver salt composition which comprises silver behenate reducible in the proximity of a catalytic amount of silver nuclei by weak reducing agents, and containing a reducing agent that causes development of a visible image by reducing the silver salt composition when processed with heat, wherein the improvement comprises the reducing agent has the following formula:
  • R11 R R11 R; 0 Rs wherein n is 0 or 1;
  • R and R or R and R may be joined together to complete a carbocyclic ring system having 5, 6 or 7 carbon atoms, and
  • R may further represent an alkoxy group having up to 6 carbon atoms or a tertiary amino group of the formula:
  • R R R R R and R are hydrogen or alkyl groups for completing a 5-, 6- or 7-membered ring; h i up t 9 carb at ms, but R R are hydrogen, alkyl or alkoxy having up to 6 5 R3 d R or R d R may b j i d t th t carbon atoms, and at least one of them represents complete a b li i system havi g 5, 6 or a hydroxyl g P; I 7 carbon atoms, and 11 12 are hydrogen, alkyl or alkoxy havmg up to 9 R may further represent an alkoxy group having up carbon atoms, cycloalkyl, aralkyl, aryl or a group to 6 Carbon atoms or a tertiary amino group of the of the formula: 0 formula.
  • a light-sensitive photographic sheet material containing a silver salt composition which comprises a light-insensitive silver salt of a fatty acid, a catalytic amount of silver nuclei, and containing a reducing agent that causes development of a visible image by reducing the silver salt composition when processed with a hydroxyl p; heat, wherein the improvement comprises the reducing 11 12 are hydrogeni alkyl or alkoxy havmg up to 9 agent h th f ll i f l carbon atoms, cycloalkyl, aralkyl, aryl or a group of the formula:
  • R and R represent alkyl having up to 6 carbon atoms or are together the ring members required for completing a 5-, 6- or 7-membered ring;
  • R R are hydrogen, alkyl or alkoxy having up to 6 carbon atoms, and at least one of them represents C n R; R! 7 R1 R4 R1: R5 wherein 0 R. 5 R and R" have the meanings indicated above.
  • 9 i k i 1 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 9, 3 Dat d June 25, 197' Inventor(s) Anita von Konig et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

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  • General Physics & Mathematics (AREA)
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  • Inorganic Chemistry (AREA)
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US00156047A 1970-06-26 1971-06-23 Light-sensitive material having developers embedded therein Expired - Lifetime US3819382A (en)

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US05/482,228 US3951664A (en) 1970-06-26 1974-06-24 Light-sensitive material having developers embedded therein

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DE19702031748 DE2031748A1 (de) 1970-06-26 1970-06-26 Lichtempfindliches Material mit eingelagertem Entwickler

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US05/482,228 Division US3951664A (en) 1970-06-26 1974-06-24 Light-sensitive material having developers embedded therein

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US3819382A true US3819382A (en) 1974-06-25

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US (1) US3819382A (enrdf_load_stackoverflow)
JP (1) JPS5539817B1 (enrdf_load_stackoverflow)
BE (1) BE768374A (enrdf_load_stackoverflow)
CA (1) CA985556A (enrdf_load_stackoverflow)
CH (1) CH566573A5 (enrdf_load_stackoverflow)
DE (1) DE2031748A1 (enrdf_load_stackoverflow)
FR (1) FR2099957A5 (enrdf_load_stackoverflow)
GB (1) GB1338427A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960908A (en) * 1973-01-22 1976-06-01 Fuji Photo Film Co., Ltd. Process for preparing organosilver carboxylates
US3980482A (en) * 1974-06-05 1976-09-14 Minnesota Mining And Manufacturing Company Sensitizing a thermographic silver halide photographic material with monomeric amide
US3996397A (en) * 1973-04-04 1976-12-07 Agfa-Gevaert N.V. Thermographic recording process
US4082901A (en) * 1973-04-04 1978-04-04 Agfa-Gevaert N.V. Thermographic material
USRE30107E (en) * 1973-01-13 1979-10-02 Agfa-Gevaert N.V. Thermographic recording process
US5409798A (en) * 1991-08-30 1995-04-25 Canon Kabushiki Kaisha Plate blank, process for producing printing plate from plate blank, and printing method and apparatus using plate
US5599648A (en) * 1990-08-03 1997-02-04 Canon Kabushiki Kaisha Surface reforming method, process for production of printing plate, printing plate and printing process

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149993A (en) * 1962-01-18 1964-09-22 Nashua Corp Heat developable paper
US3166433A (en) * 1962-08-01 1965-01-19 Nashua Corp Heat sensitive copy and recording sheet
US3167444A (en) * 1962-11-19 1965-01-26 Nashua Corp Heat responsive marking sheets
US3185585A (en) * 1962-11-19 1965-05-25 Nashua Corp Heat responsive marking sheets
US3330663A (en) * 1964-08-14 1967-07-11 Agfa Gevaert Ag Silver salts of sulfur-containing aliphatic carboxylic acids as lightsensitive compounds
US3457075A (en) * 1964-04-27 1969-07-22 Minnesota Mining & Mfg Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide
US3463655A (en) * 1966-04-09 1969-08-26 Fuji Photo Film Co Ltd Pressure-sensitive copying paper

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149993A (en) * 1962-01-18 1964-09-22 Nashua Corp Heat developable paper
US3166433A (en) * 1962-08-01 1965-01-19 Nashua Corp Heat sensitive copy and recording sheet
US3167444A (en) * 1962-11-19 1965-01-26 Nashua Corp Heat responsive marking sheets
US3185585A (en) * 1962-11-19 1965-05-25 Nashua Corp Heat responsive marking sheets
US3457075A (en) * 1964-04-27 1969-07-22 Minnesota Mining & Mfg Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide
US3330663A (en) * 1964-08-14 1967-07-11 Agfa Gevaert Ag Silver salts of sulfur-containing aliphatic carboxylic acids as lightsensitive compounds
US3463655A (en) * 1966-04-09 1969-08-26 Fuji Photo Film Co Ltd Pressure-sensitive copying paper

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE30107E (en) * 1973-01-13 1979-10-02 Agfa-Gevaert N.V. Thermographic recording process
US3960908A (en) * 1973-01-22 1976-06-01 Fuji Photo Film Co., Ltd. Process for preparing organosilver carboxylates
US3996397A (en) * 1973-04-04 1976-12-07 Agfa-Gevaert N.V. Thermographic recording process
US4082901A (en) * 1973-04-04 1978-04-04 Agfa-Gevaert N.V. Thermographic material
US3980482A (en) * 1974-06-05 1976-09-14 Minnesota Mining And Manufacturing Company Sensitizing a thermographic silver halide photographic material with monomeric amide
US5599648A (en) * 1990-08-03 1997-02-04 Canon Kabushiki Kaisha Surface reforming method, process for production of printing plate, printing plate and printing process
US5409798A (en) * 1991-08-30 1995-04-25 Canon Kabushiki Kaisha Plate blank, process for producing printing plate from plate blank, and printing method and apparatus using plate

Also Published As

Publication number Publication date
CH566573A5 (enrdf_load_stackoverflow) 1975-09-15
JPS5539817B1 (enrdf_load_stackoverflow) 1980-10-14
BE768374A (nl) 1971-12-13
DE2031748A1 (de) 1971-12-30
FR2099957A5 (enrdf_load_stackoverflow) 1972-03-17
CA985556A (en) 1976-03-16
GB1338427A (en) 1973-11-21

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