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
  • 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
  • G03C1/49836—Additives
  • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
• • 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
  • Y10S430/166—Toner containing

Definitions

• ABSTRACT Photographic recording material with a light-sensitive layer comprising a substantially non-light-sensitive silver salt, a reducing agent, a toning agent and in admixture therewith a light-sensitive heavy metal compound and/or a polymethine sensitizing agent for the spectral sensitization of the non-light-sensitive silver compound, wherein the light-sensitive layer comprises a phthalazinone toning agent according to the follow- PLEEWE mug;
• the invention relates to a photographic material for the production of photographic copies in a dry manner, the photographic material comprising toning agents for the formation of black silver images.
• the invention also relates to a photographic heat-copying process, wherein the formation of the silver image is performed in the presence of toning agents that shift the image tone from yellow to black-brown and black.
• non-light-sensitive silver salts as oxidizing agents, e.g. silver saccharide or silver salts of long chain fatty acids.
• the amount of the reducing agent present in the light-sensitive material has to be restricted to a minimum to avoid any undesired darkening of the coating solution or of the layer, i.e., to avoid the reduction of the organic silver salts during the manufacture and storage of the material. Therefore, weak reducing agents of the type of the o-alkyl-substituted phenols as described, e.g. in the published German Patent Application No. 1,908,761 filed Feb. 18, 1969 by Minnesota Mining & manufacturing Co. are added.
• toning agents shifting the image tone to brown and black to the light-sensitive layers in order to obtain images having a sufficient optical density and a sufficient contrast in the finished copy.
• a compound is, e.g. 2H-phthalazinone( l)
• This toning agent when combined with various silver salts and reducing agents causes a darkening of the coating solution or of the materials obtained, so that it has but a limited utility.
• R represents 1. an aliphatic group including a cycloaliphatic group and such groups in substituted form, e.g. an alkyl group having a straight carbon chain or branched chain structure including a substituted alkyl group, e.g. an alkoxy-substituted alkyl group, an alkoxycarbonyl-substituted alkyl group e.g. a carbethoxymethyl group, preferably a C -C alkyl group, e.g.
• alkenyl group including a substituted alkenyl group e.g. an ally] group
• a cycloalkyl group including a substituted cycloalkyl group e. g. a cyclopentyl, cyclohexyl, or methylcyclohexyl group
• an aralkyl group including a substituted aralkyl group e.g. abenzyl group or phenethyl group
• a phenyl group e.g. a phenyl group, a naphthyl group, or a biphenyl group including these groups in substituted form, e.g. a halogen-substituted phenyl group, e.g. 4-chlorophenyl and 3,4-chlorophenyl, alkylsubstituted phenyl, e.g. a tolyl group, alkoxysubstituted phenyl, in which the alkyl group in the alkoxy group is, e.g. a C,-C,,, alkyl group, a carboxy-substitutcd phenyl group, an esterified carboxy-substituted .phenyl group,
• Suitable examples of such compounds are the follow- Melting point (O /N o H lTI-CONHCO WN N-CONH-Q w I IIICONHCHa y (5) 71-73 ⁇ III-COHN'(OI ⁇ 2)I7CIIJ WN 1 -i-o0NHotII5 yN o ll NCONHCl I I A ⁇ /CH2CH2 N-cNHor r om 1's 0 carom
• compounds corresponding to the above general formula and containing 2-phthalazinone nuclei, which in the 2-position are linked by a CO--NHX- -NH-CO- group can be used, X being a bivalent organic group, e.g.
• phthalazinone derivatives of the above general formula are prepared according to known methods, e.g. by reaction of phthalazinone with an isocyanate. The preparation of the compounds 1 and 2 is described hereinafter.
• Other phthalazinones that can be used according to the invent are pre arsgin.a ianalo ous y- Preparation of compound 1 A mixture of 146 g (1 mole) of phthalazinone and 138 g (1.1 mole) of phenylisocyanate in 1 lot dry benzene are boiled 4 hours with stirring. The resulting solution is then cooled and the precipitate formed is filtered with suction. The precipitate is then washed with dry diethyl ether.
• a photographic material having a layerthat contains a non-light-sensitive silver salt and usually small amounts of a light-sensitive heavy metal salt, more particularly a silver salt, as well as a reducing agent for the reduction of the silver salt at the exposed areas.
• vention is substantially non-light-sensitive as well as a reducing agent and usually a small amount of polymethine sensitizing agent for the spectral sensitization of the non-light-sensitive silver salt.
• the sensitizing agents are dissolved in organic solvents and added to the solutions ready for coating. They may also be added in solid form to the silver salt before the grinding or a short time before the application of the coating solution to the support.
• the concentration of the sensitizing agent in the layer may vary within wide limitations. It depends on the desired effect and on the nature of the sensitizing agent used in combination with the silver salt. In general, concentrations of 0.1 to 2 g of sensitizing dye, preferably of 0.2 to 0.6 per mole of silver salt, appeared to be sufficientpln certain cases amounts of sensitizing agents beneath or beyond this range may be added.
• the toning agents of the invention are added preferably to the light-sensitive layer. However, they may be added partially to an adjacent layer.
• Varying amounts of the compounds used according to the invention can be added to the layers.
• the optimum amount depends on the desired effect and on the composition of the layer. It can easily be established by the average technician skilled in the art by making some tests. 1n general, additions of 0.5 to 6 mole, preferably of l to 4 mole of the phthalazinone derivative per mole of non-light-sensitive silver compound, preferably an organic silver salt, appeared to be sufficient.
• the phthalazinone derivatives used according to the invention can also be used in combination with known toning agents.
• concentration ofthe additional toning agents is preferably lower than that of the toning agents used according to the invention.
• Suitable additional toning agents are, e.g. the unsubstituted phthalazinone, phthalimide, and phthalimide derivatives.
• the toning agents of the invention can be used in combination with substances and compounds known for the heat transfer process and for the light-sensitive copying material.
• substances and compounds are, e.g. reducing agents, binders, silver salts, and other heavy metal salts, white pigments, and stabilizing agents.
• Such materials are generally known and they have been described e.g. in the published German Patent Application Nos. l,300,0l4 filed Apr. 23, 1964 by Minnesota Mining & Manufacturing Co., 1,547,878 filed June 6, 1967 by Fuji Co., 1,572,203 filed Apr. 23, 1965 by Minnesota Mining & Manufacturing Co. and 1,908,761 filed Feb. 18, 1969 by Minnesota Mining & Manufacturing Co.
• Organic reducing agents known for these processes comprise an active hydrogen atom linked to an oxygen, nitrogen or carbon atom, e.g. o-alkyl-substituted phenol derivatives, diand trihydroxyaryl-derivatives, aminophenol derivatives, aminonaphthol derivatives, pphenylenediamine derivatives, and hydroxylamine derivatives, alkoxy-naphthols and derivattives of acetoacetonitrile, pyrazolidin-3-one, pyrazolidin- 5-one, indanedione-l,3, ascorbic acid and hydroxychroman or hydrocumaran.
• Preferred examples are e.g. o-alkyl-substituted phenols, hydroquinone, aminophenol derivatives, and methoxy-naphthol derivatives.
• the layers can be sensitized optically by the addition of dyes.
• Suitable sensitizing agents are preferably compounds, which are used customarily for the optical sensitization of conventional silver halide emulsion layers, e.g. cyanine dyes, merocyanine, oxonols, or rhodacyanides, of varying types as described e.g. in The Cyanine Dyes and Related Compounds (1964) of F. M. Hamer.
• binders are the usual natural or synthetic film-forming polymers e.g. proteins, e.g. gelatin, cellulose derivatives, such as cellulose ethers, cellulose esters or carboxymethylcellulose, alginic acid and derivatives thereof, starch ether or gallactomannan.
• Preferred binders are the organic polymers such as copolymers of vinyl chloride and vinyl acetate, or of butadiene and styrene, polyethylene, polyamide, polyisobutylene, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, or wholly or partially saponified polyvinyl acetate, polyvinyl-idene chloride, polyvinylpyrrolidone, polystyrene, chlorinated rubber, polyvinyl butyral, polymers of acrylates or methacrylates, acrylamide, or copolymers of the derivatives of acrylic acid and methacrylic acid, cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, or mixtures thereof, such as cellulose acetobutyrate, etc.
• organic polymers such as copolymers of vinyl chloride and vinyl acetate, or of butadiene and styrene, polyethylene, polyamide, polyisobut
• the light-sensitive layer can be used in the form of a self-supporting layer though it is preferably applied to an appropriate support.
• the support has to be stable at processing temperatures between and 200 C.
• Suitable supports are, e.g. sheets or foils of paper, cellulose acetate, polyethylene terephthalate, fabric, metal foils, and glass.
• the paper may carry the usual auxiliary layers such as baryta coatings, polyethylene coatings, etc.
• silver compounds are substantially non-light-sensitive in the conditions of the process of the invention.
• Such silver compounds are, e.g. the silver salts of aliphatic carboxylic acids with a thioether group or silver salts of long chain fatty acids such as silver behenate, silver palmitate, silver stearate, etc., described in the UK. Pat. No. 1,111,492 filed Aug. 13, 1965 by Agfa AG.
• Light-sensitive heavy metal salts suited for the first process and forming metal nuclei upon exposure, which metal nuclei are capable of initiating the imageforming redox reaction, are e.g. inorganic or organic salts of silver, mercury, or gold.
• Heavy metals of group lb of the periodic table of the elements, more particularly silver salts and especially silver halides are preferred.
• the light-sensitive heavy metal salt that is best for the redox system used can be found by making some simple tests.
• the metal salt in the form of an aqueous suspension can be mixed with the components of the redox reaction: no change at all must occur in the dark. When this mixture is exposed to ultraviolet radiation, it should change colour rather quickly. If a particular heavy metal salt behaves in this way, it is suited for the redox system.
• the light-sensitive heavy metal salt e.g. the silver halide should be used in such small amounts that the photolytically formed heavy metal nuclei can initiate the redox reaction.
• concentration of the silver halide should, however, be so low that the metal nuclei formed do not colour the copying material or do so in a neglegible way only.
• Some of the silver salts that are non-light-sensitive by nature and can be used according to the invention show a certain inherent sensitivity, however low it may be, when precipitated in the presence of a protective colloid such as proteins, e.g. gelatin, as is generally done for the preparation of conventional gelatin silver halide emulsions.
• a protective colloid such as proteins, e.g. gelatin, as is generally done for the preparation of conventional gelatin silver halide emulsions.
• the precipitation of the silver salts for the manufacture of the material according to the invention should thus be performed in such a way that the silver salts formed are non-light-sensitive.
• the silver salts are non-light-sensitive when they'are formed by precipitation in the absence of a protective colloid.
• the dried silver salts are then incorporated in the solutions or dispersions of the desired binding agent.
• concentration of the silver salt in the binder solutions or dispersions may vary within wide limits depending on the desired silver content of the photographic layers. In general, amounts of 0.] to 0.01 mole of silver salt per kg of coating solution, will do. Preferably amounts of 0.02 to 0.04 mole of silver salt are used per kg of solution or dispersion. The same applies to the silver content of the finished photographic layer.
• the concentration therof also varies within wide limits depending on the desired effect and the intended use.
• the coating ratio will be of 0.1 to l g of silver in the form of the silver salt per sq.m., preferably of 0.3 to 0.6 g per sq.m. It is obvious that also mixtures of different non-light-sensitive silver compounds can be used in the material used according to the invention.
• non-lightsensitive heavy metal compounds can be added to the material, preferably to the layer containing the nonlight-sensitive silver salt.
• a lowering of the fog an increase of the density, or a shift of the image tone to desired colour tones, e.g. to neutral black, can be attained.
• Suitable heavy metal compounds are, e.g. salts or compounds of mercury, cadmium, lead, uranium, gold, platinum, palladium, or rhodium.
• the heavy metal compounds can be added already during the precipitation of the silver salt.
• solutions of the heavy metal salts and of the silver salts are added to the precipitation component in question according to the double jet method and precipitated at the same time.
• these heavy metal salts can, however, be added also in solid or dissolved form to the coating solutions for the photographic layer, which already contain the silver salt.
• the heavy metal salts can also be mixed with the dried silver salts by grinding or they can be added prior to the coating of the coating solution for the photographic layer. Obviously, combinations of different heavy metal salts can be used likewise. The added amount of the heavy metal salts or heavy metal compounds may vary within wide limits.
• concentration depends upon the nature of the heavy metal salt and the silver salt'as well as on the desired effect. The optimum amount can be established easily by the average technician skilled in the art by making some tests. In the case of simultaneous precipitation, the heavy metal salts show a higher activity. In order to obtain the desired effect concentrations of 0.001 to 10 mole percent or preferably of 0.01 to 5 mole percent will do mostly.
• concentrations of 0.001 to 0.2, preferably of 0.005 to 0.07 mole of heavy metal salt, e.g. mercury(Il)-acetate per mole of silver salt suffice.
• These layers may comprise white pigments such as zinc oxide, silica, or titanium dioxide as filling agents for the improvement of the whiteness of the image background and for influencing the stickiness of the layers.
• white pigments such as zinc oxide, silica, or titanium dioxide
• Further terpene resins and organic acids can be added to the layers for improving the keeping properties.
• Such layers have been described in the US. Pat. Nos. 3,074,809 of Richard Owen, issued Jan. 22, 1963, and 3,107,174 of Thomas G. Wartman, issued Oct. 15, 1963.
• the light sources known in the reproduction technique can be used, e.g. halogen lamps, iodine-quartz lamps, and incandescent lamps.
• the type of light source used depends on the spectral sensitivity of the heavy metal salt or sensitizing dye used. The exposure lasts a few seconds.
• the development of the light-sensitive copying materials containing a silver salt is performed at temperatures between and 200 C.
• the heating can be carried out, e.g. by conducting the exposed light-sensitive layer over heated plates or rollers or by exposing the layer to ultraviolet radiation.
• the lightsensitive material containing a silver salt can be heatdeveloped in contact with a foil, e.g. a polyester foil.
• the optimum temperature and heating period depend, of course, on the composition of the light-sensitive material containing the silver salt. They can be established by some simple tests.
• silver behenate-behenic acid (molar proportion lzl) toning agent in the amount given in the table hereinafter mercury( ll )-acetatc celluloseacetobutyrate copolymer of vinyl chloride and vinyl acetate (weight proportion 60:40)
• the coating solution was applied to a paper support and dried. 0.5 to 0.6 g of silver in the form of the silver compound was present per sq.m.
• the light-sensitive material was exposed through a transparent original by means of tungsten lamps for 3 160 C) and on the equipment used the development time varied from 3 to 80 sec.
• the development equipment includes heatable presses, drying drums, rollers, the contrivances described in the Belgian Pat. No. 628,174 filed Feb. 8, 1963 by Agfa AG or the French Pat. Nos. 1,419,101 filed Dec. 4, 1964; 1,416,752 filed Dec. 2, 1964; and 1,512,332 filed Sept. 18, 1964 all by Agfa AG as well as commercial devices.
• Covering layer having the following composition:
• test strips of the material containing the toning agent to be tested were examined in the following way.
• the unexposed strips were developed for 20 sec. at increasing temperature with rising intervals of 5 C. Subsequently, the temperature was established, at which the unexposed material showed a development to a fog value of 0.150.2. The higher this temperature, the
• the coating solution for the light-sensitive layer was ground for 16 h in a ball-mill prior to the coating.
• the light-sensitive layer comprised 0.7 to 0.9 g of silver in the form of the silver salt per sq.m.
• the dried light-sensitive layer was coated with the covering layer.
• the concentration of the reducing agent in the covering layer varied from 0.5 to 1.5 g per sq.m.
• the exposed material was then heat-developed as described in example 1 so that a black image was obtained.
• An equimolar mixture of silver behenate and behenic acid was prepared by precipitation of silver nitrate with a solution of sodium behenate and behenic acid in alcohol and water. The precipitate was washed carefully and dried.
• the suspension for the layer was prepared by grinding the following ingredients for 12 h in a ball-mill:
• the suspension was applied to a common paper support at a ratio of 100 g per sq.m and dried at room temperature. Processing:
• the light-sensitive layer was exposed through a transparent original by means of an ultraviolet lamp of 750 watt placed at a distance of 5 cm. The exposure time was 2 sec. Subsequently, the layer was heated for 5 sec. to 120 C. A black negative image was obtained from the original.
• a photographic recording material having a lightsensitive layer comprising a substantially non-lightsensitive silver salt, a reducing agent, a toning agent and in admixture therewith a light-sensitive heavy metal compound and/or a polymethine sensitizing agent for the spectral sensitization of the non-lightsensitive silver compound, the improvement wherein the light-sensitive layer comprises a phthalazinone toning agent according to the following general formula:
• Photographic recording material according to claim 1, wherein the light-sensitive layer contains 0.05 to 0.02 percent by weight of light-sensitive heavy metal compound calculated on the weight of non-lightsensitive silver salt.
• Photographic recording material according to claim 1, wherein the phthalazinone toning agent is present in a molar proportion of at least 0.5 calculated on the non-light-sensitive silver salt.
• Photographic recording material comprises as the sole silver compound therein a non-light-sensitive silver salt, a reducing agent, and a polymethine sensitizing agent for the spectral sensitization of the non-lightsensitive silver salt.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Photoreceptors In Electrophotography (AREA)

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Cited By (28)

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Citations (6)

• 1972
  • 1972-04-27 DE DE2220597A patent/DE2220597C3/de not_active Expired
  • 1972-12-29 US US00319604A patent/US3844797A/en not_active Expired - Lifetime
• 1973
  • 1973-04-03 CA CA167,817A patent/CA1026611A/en not_active Expired
  • 1973-04-03 FR FR7312385A patent/FR2181868B1/fr not_active Expired
  • 1973-04-08 IT IT86226/73A patent/IT990469B/it active
  • 1973-04-09 GB GB1695073A patent/GB1420815A/en not_active Expired
  • 1973-04-13 CH CH521673A patent/CH575607A5/xx not_active IP Right Cessation
  • 1973-04-19 BE BE1004983A patent/BE798440A/xx unknown
  • 1973-04-25 JP JP4717573A patent/JPS5618938B2/ja not_active Expired

Patent Citations (6)

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