US3708304A - Use of divalent metal salt image amplifiers in photosensitive and thermosensitive elements - Google Patents

Use of divalent metal salt image amplifiers in photosensitive and thermosensitive elements Download PDF

Info

Publication number
US3708304A
US3708304A US00043173A US3708304DA US3708304A US 3708304 A US3708304 A US 3708304A US 00043173 A US00043173 A US 00043173A US 3708304D A US3708304D A US 3708304DA US 3708304 A US3708304 A US 3708304A
Authority
US
United States
Prior art keywords
photosensitive
image
thermosensitive
mole
metal salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00043173A
Other languages
English (en)
Inventor
G Hiller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Application granted granted Critical
Publication of US3708304A publication Critical patent/US3708304A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • Y10S430/156—Precursor compound
    • 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

  • a divalent metal salt such as zinc acetate, cadmium acetate or cupric acetate, in combination with an oxidation-reduction image-forming combination containing a heavy metal salt oxidizing agent, such as silver behenate, and a reducing agent, such as a bis-naphthol reducing agent, in a photosensitive and thermosensitive element suitable for dry processing with heat, provides increased image density with no adverse increase in background density.
  • a heavy metal salt oxidizing agent such as silver behenate
  • a reducing agent such as a bis-naphthol reducing agent
  • a combination of a bis-B- naphthol reducing agent and zinc acetate, cadmium acetate or cupric acetate in conjunction with a stable source of silver for physical development is useful in photosensitive elements for dry processing with heat.
  • the element can contain a sensitizing dye, an activator-toning agent and other addenda employed in elements for dry processing with heat.
  • a stable, developed image can be provided by heating the element after exposure.
  • the photosensitive component can be photographic silver halide or other suitable photosensitive metal salts.
  • Metallic salts such as stannous stearate
  • a thermographic, non-silver halide image-receptor sheet such as described in U.S. Pat. No. 3,460,946 of Puerckhaver et al. issued Aug. 12, 1969.
  • These image-receptor sheets contain a reducing agent, such as 2,6-ditertiary -butyl-pcresol, an oxidizing agent such as silver behenate and a toner, e.g., (2H )-phthalazinone; however, they are not photosensitive.
  • An intermediate photosensitive sheet containing, for example, 4-methoxy-l-naphthol is first given a reflex exposure while in contact with the original. The exposed photosensitive intermediate sheet is then heated while in contact with the image-receptor sheet.
  • the photosensitive element can contain a reducing agent, a light insensitive silver salt of an organic acid as an oxidizing agent and photographic silver halide, such as described in U.S. Pat. No. 3,152,904 of Sorensen and Shepard issued Oct. 13, 1964, and U.S. Pat. No. 3,457,075 of Morgan and Shely issued July 22, 1969. Elements of this type are also described, for example, in French Pat. No. 1,441,619 and Belgian Pat. No. 705,872.
  • the described improvements are provided in a photosensitive and thermosensitive element composition or process with an oxidation-reduction image-forming combination comprising (i) a heavy metal salt oxidizing agent with (ii) a reducing agent, a catalyst for said oxidation-reduction imageforming combination and a binder, by employing a divalent metal salt image amplifier, which is a zinc, cadmium or copper salt, with the described combination.
  • a divalent metal salt image amplifier which is a zinc, cadmium or copper salt
  • a number of divalent metal salts which are image amplifiers can be employed in the practice of the invention to cause an increase in maximum image density with more neutral'tone without undesirably increased background density.
  • a suitable image-amplifying compound is a divalent metal salt, e.g., a zinc salt such as zinc acetate.
  • Other suitable inorganic divalent metal salts which can be employed in the practice of the invention include acetate salts of cadmium and copper.
  • the described image-amplifying compounds are suitable in a range of concentration of about 0.005 to about 0.20 mole of divalent metal salt per mole of heavy metal salt oxidizing agent, e.g., per mole of silver salt oxidizing agent; however, they are especially suitable at a concentration of about 0.010 mole to about 0.10 mole of divalent metal salt per mole of silver salt oxidizing agent.
  • thermosensitive and thermosensitive elements which are suitable for dry processing with heat, can provide a developed image by physical development as described, for example, in U.S. Pat. No. 3,457,075 of Morgan et al. issued July 22, 1969.
  • Other elements of this type are described, for example, in U.S. Pat. No. 3,429,706 of Shepard et al. issued Feb. 25, 1969, and U.S. Pat. No. 3,152,904 of Sorensen et a1. issued Oct. 13, 1964.
  • the described element contains a photosensitive salt, especially a photosensitive silver salt. It is believed this is a catalyst for the described oxidation-reduction image-forming combination.
  • a typical concentration range of photosensitive silver salt is about 0.005 to about 0.50 mole of photosensitive silver salt per mole of heavy metal salt oxidizing agent, e.g., per mole of silver behenate.
  • Preferred photosensitive silver salts are photosensitive silver halides, e.g., silver chloride, silver bromide, silver bromoiodide, chlorobromoiodide, or mixtures thereof.
  • the photosensitive silver halide can be coarseor finegrain, very fine-grain emulsions being especially useful.
  • the emulsion containing the photosensitive silver hasilver.
  • lide can be prepared by any of the well-known procedures in the photographic art, such as single-jet emulsions, double-jet emulsions, such as Lippmann emulsions. ammoniacal emulsions, thiocyanate or thioether ripened emulsions, such as those described in U.S. Pat. No. 2,222,264 of Nietz et al. issued Nov. 14, 1940, U.S. Pat. No. 3,320,069 of lllingsworth issued May 15,1967, and U.S. Pat. No. 3,271,157 of McBride issued Sept. 6, 1966.
  • Surface-image silver halide emulsions can be used. If desired, mixtures of surfaceand internal-image silver halide emulsions can be used as described in U.S. Pat. No. 2,996,332 of Luckey et al. is-
  • Negative-type emulsions can be used.
  • the silver halide emulsion can be a regular-grain emulsion such as described in Klein and Moisar, Journal ofPhotographic Science, Volume 12, No. 5, Sept.- Oct. 1964), pages 24225 1.
  • the silver halide emulsions employed in the practice of the invention can be unwashed or washed to remove soluble salts.
  • the soluble salts can be removed by chill setting and leaching or the emulsion can be coagulation washed.
  • the silver halide employed in the practice of the invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • chemical sensitizers such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • Suitable procedures are described, for example, in U.S. Pat. No. 1,623,499 of Shepard issued Apr. 5, 1927; U.S. Pat. No. 2,399,083 of Waller et al. issued Apr. 23, 1946; U.S. Pat. No. 3,297,447 of McVeigh issued Jan. 10, 1967; and U.S. Pat. No. 3,297,446 of Dunn issued Jan. 10, 1967.
  • Photosensitive silver halide emulsions employed in the practice of the invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable antifoggants and stabilizers include, for example, thiazolium salts; azaindenes; mercury salts as described, for example, in U.S. Pat. No. 2,728,663 of Allen et al. issued Dec. 27, 1955; urazoles; sulfocatechols; oximes described, for example, in British Pat. No. 623,448; nitron; nitroindazoles; polyvalent metal salts described, for example, in U.S. Pat. No.
  • Suitable organic reducing agents which can be employed in the described combination include, for example, phenol and naphthol reducing agents.
  • the bisnaphthol which is preferred is a bis-B-naphthol of the formula:
  • R, and/or R are hydrogen, alkyl with one to three carbon atoms, alkoxy, e.g., alkoxy containing one to two carbon atoms, such as methoxy or ethoxy; halogen, nitro, amino or a diazonium halide salt, and n is 0 or 1.
  • Suitable bis-B-naphthols which can be employed in the practice of the invention include:
  • the described reducing agents are suitable in a range of concentration; however, they are especially suitable at a concentration from about 0.10 to about 2.0 moles, e.g., about 0.40 mole to about 0.75 mole, of reducing agent per mole of oxidizing agent, as described.
  • Suitable silver halide developing agents include, for example, polyhydroxybenzenes such as hydroquinone developing agents, e.g., hydroquinone, alkyl-substituted hydroquinones as exemplified by tertiary butylhydroquinone, methylhydroquinone, 2,5-dimethylhydroquinone and 2,6-dimethylhydroquinone; catechols and pyrogallol; halo-substituted hydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxy-substituted hydroquinones such as methoxyhydroquinone or ethoxyhydroquinone; methylhydroxynaphthalene; phenylenediamine developing agents; methylgallate; aminophenol developing agents, such as 2,4- diaminophenols and
  • a suitable activatortoning agent is a heterocyclic activator-toning agent containing at least one nitrogen atom and of the formula:
  • R is hydrogen, hydroxyl, or a metal ion such as potassium, sodium, lithium, silver, gold or mercury
  • Z represents atoms completing a heterocyclic nucleus, especially a 5- or 6-member heterocyclic nucleus.
  • the atoms completing the heterocyclic nucleus can be, for example,
  • an especially suitable activator-toning agent is a heterocyclic activatortoning agent containing at least one nitrogen atom which is preferably a cyclicimide of the formula:
  • R can be hydrogen, hydroxyl, or a metal ion such as potassium, sodium, lithium, silver, gold or mercury
  • Z represents carbon atoms of a series completing a cyclicimide nucleus, typically consisting of from five to six carbon atoms, e.g., a phthalimide or succinimide nucleus.
  • the atoms of the cyclicimide nucleus can contain various substituent groups, especially amino, alkyl, such as alkyl containing one to five carbon atoms, such as methyl, ethyl, propyl, butyl or pentyl or aryl, such as aryl containing six to 20 carbon atoms, such as phenyl, tolyl and xylyl.
  • activator-toning agents examples include:
  • the described activator-toning agents are suitable in a range of concentration depending on several factors such as the desired image, the particular oxidationre'duction image-forming combination, processing tem-' perature and the like. However, they are especially suitable at a concentration from about 0.10 mole to about 1.05 moles of activator-toning agent per mole of oxidizing agent, as described.
  • activator-toning agents can be employed in combination with other components of the described photosensitive and thermosensitive element in the practice of the invention.
  • Various compounds which have been designated as toners can be employed for this purpose.
  • a heterocyclic organic toning agent containing at least two hetero atoms in the heterocyclic ring of which at least one is a nitrogen atom is employed.
  • Suitable toners include, for example, phthalazinone, phthalic anhydride, 2-acetylphthalazinone and 2- phthalylphthalazinone.
  • Other suitable toners are described, for example, in U.S. Pat. No. 3,446,648 of Workman issued May 27, 1969.
  • a non-aqueous, polar, organic solvent such as a compound containing a ment suitable for dry processing with heat can provide improved maximum image densities, e.g., tetrahydrothiophene-1,1-dioxide, 4-hydroxybutanoic acid lactone and/or methylsulfinylmethane.
  • the described elements comprise a heavy metal salt oxidizing agent, especially a silver salt oxidizing agent, e.g., a silver salt of an organic acid.
  • a silver salt oxidizing agent e.g., a silver salt of an organic acid.
  • the silver salt of the organic acid should be resistant to darkening under illumination to prevent undesired deterioration of a developed image.
  • An especially suitable class of silver salts of organic acids is represented by the water-soluble silver salts of organic acids of long-chain fatty acids which are stable to light.
  • Compounds which are suitable silver salts include, for example, silver behenate, silver stearate, silver oleate, silver laurate, silver hydroxystearate, silver caprate, silver myristate and silver palmitate.
  • oxidizing agents are, for example, silver benzoate, silver phthalazinone, silver benzotriazole, silver saccharin, silver 4'-n-octadecyloxydiphenyl-4-carboxylic acid, silver O-aminobenzoate, silver acetamidobenzoate, silver furoate, silver camphorate, silver P-phenylbenzoate, silver phenylacetate, silver salicylate, silver butyrate, silver terephthalate, silver phthalate, silver acetate and silver acid phthalate.
  • Oxidizing agents which are not silver salts can be employed, if desired, such as zinc oxide, gold stearate, mercuric behenate, auric behenate and the like, but silver salts are preferred.
  • a photosensitive and thermosensitive element, and emulsions described and used in the practice of the invention can contain various colloids alone or in combination as vehicles, binding agents and in various layers.
  • Suitable materials are typically hydrophobic, but hydrophilic materials can also be employed. They are transparent or translucent and include both naturally occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as watersoluble polyvinyl compounds like poly(vinyl pyrrolidone), acrylamide polymers and the like.
  • Other synthetic polymeric compounds which can be employed include dispersed vinyl compounds such as in latex form and particularly those which increase dimensional stability of photographic materials.
  • Suitable synthetic polymers include those described in U.S. Pat. No. 3,142,586 of Nottorf issued July 28, 1964; U.S. Pat. No. 3,193,386 of White issued July 6, 1955; U.S. Pat. No. 3,062,674 of Houck et al. issued Nov. 6, 1962; U.S. Pat. No. 3,220,844 of l-louck et al. issued Nov. 30, 1965; U.S. Pat. No. 3,287,289 of Ream et al. issued Nov. 22, 1966; and US. Pat. No. 3,411,911 of Dykstra issued Nov. 19, 1968.
  • Effective polymers include water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, and those which have cross-linking sites which facilitate hardening or curing, as well as those having recurring sulfobetaine units as described in Canadian Pat. No. 774,054.
  • Preferred high-molecularweight materials and resins include polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate,
  • a flexible support is employed, especially a paper support which can be partially-acetylated or coated with baryta and/or an alphaolefin polymer, particularly a polymer of an alphaolefin containing two to 10- carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like.
  • the photosensitive and thermosensitive and other hardenable layers of an element used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed-function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
  • various organic or inorganic hardeners such as aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy
  • the photosensitive and thermosensitive elements used in the practice of the invention can contain antistatic or conducting layers.
  • Such layers can comprise soluble salts such as chlorides, nitrates and the like, evaporated metal layers, ionic polymers such as those described in U.S. Pat. No. 2,861,056 of Minsk issued Nov. 18, 1958, and U.S. Pat. No. 3,206,312 of Sterman et al. issued Sept. 14,1965, or insoluble inorganic salts such as those described in U.S. Pat. No. 3,438,451 of Trevoy issued Feb. 18, 1969.
  • the photosensitive and thermosensitive elements can also contain antihalation materials and antihalation dyes.
  • the photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain plasticizers and lubricants.
  • plasticizers and lubricants include, for example, polyalcohols such as glycerin and diols described, for example, in U.S. Pat. No. 2,960,404 of Milton -et al. issued Nov. 1, 1966; fatty acids or esters such as those described in U.S. Pat. No. 2,558,765 of Robijns issued Mar. 11, 1952; U.S. Pat. No. 3,l2l,060 of Duane issued Feb. 11, 1964; and silicone resins such as those described in British Pat. No. 955,061.
  • the photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain surfactants such as saponin; anionic compounds such as alkyl aryl sulfonates described, for example, in U.S. Pat. No. 2,600,831 of Baldsiefen issued June 17, 1962; amphoteric compounds such as those described in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964; and adducts of glycidol and an alkyl phenol such as those described in British Pat. No. 1,022,878.
  • surfactants such as saponin
  • anionic compounds such as alkyl aryl sulfonates described, for example, in U.S. Pat. No. 2,600,831 of Baldsiefen issued June 17, 1962
  • amphoteric compounds such as those described in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964
  • the photosensitive and thermosensitive elements employed in the practice of the invention can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads described, for example, in U.S. Pat. No. 2,922,101 of Jelley et, al. issued July 11, 1961, and us. Pat. No. 2,701,245 of Lynn issued Feb. 1, 1955.
  • matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads described, for example, in U.S. Pat. No. 2,922,101 of Jelley et, al. issued July 11, 1961, and us. Pat. No. 2,701,245 of Lynn issued Feb. 1, 1955.
  • the photosensitive and thermosensitive elements employed in the practice of the invention can contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
  • Brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
  • Water-soluble brightening agents can be used such as those described in German Patent No. 972,067 and U.S. Pat. No. 2,933,390 of McFall et al. issued April 19, 1960, or dispersions of brighteners can be used such as those described in German Pat. No. 1,150,274, U.S. Pat. No. 3,406,070 of Oetiker et al. issued Oct. 15, 1968, and French Pat. No. 1,530,244.
  • the various layers including the photosensitive and thermosensitive layers of an element employed in the practice of the invention can contain light-absorbing materials, filter dyes, antihalation dyes and absorbing dyes such as those described in U.S. Pat. No. 3,253,921 of Sawdey issued May 31, 1966; U.S. Pat. No. 2,274,782 ofGaspar issued Mar. 3, 1942; U.S. Pat. No. 2,527,583 of Silberstein et al. issued Oct. 31 1950; and U.S. Pat. No. 2,956,879 of VanCampen issued Oct. 18, 1960.
  • the dyes can be mordanted, for example, asdescribed in U.S. Pat. No. 3,282,699 of Jones et al. issued Nov. 1, 1966.
  • the photosensitive and thermosensitive layers used in the practice of the invention can be coated by various coating procedures including dip coating, airknife coating, curtain coating or extrusion coating using hoppers such as described in U.S. Pat. No. 2,681,294 of Beguin issued June 15, 1954. If desired, two or more layers can be coated simultaneously such as by the procedures described in 'U.S. Pat. No. 2,761,791 of Russell issued Sept. 4, 1956, and British Pat. No. 837,095.
  • thephotosensitive silver halide can be prepared in situ, in the photosensitive and thermosensitive coatings of an element employed in the practice of the invention.
  • a method is described, for example, in U.S.Pat. No. 3,457,075 of Morgan et al. issued July 22, 1969.
  • a dilute solution of a halogen acid such as hydrochloric acid can be applied to the surface of a thin coating containing an organic silver salt, such as silver behenate, on a suitable substrate followed by removal of the solvent, if desired.
  • Silver halide is thus formed in situ throughout the surface of the coating of the organic silver salt.
  • the photosensitive silver halide can be prepared on the oxidizing agent, such as silver behenate or silver stearate or other organic silver salt, prior to application of the silver halide on the support employed. This is also described in U.S. Pat. No. 3,457,075 of Morgan et al. issued July 22, 1969.
  • a halogen acid such as hydrochloric acid or hydrobromic acid can be mixed with an organic silver salt in a suitable reaction medium.
  • a halide salt more soluble than the organic silver salt can be added to a suspension of the organic silver salt to form the silver halide.
  • a suitable reaction medium includes water or other solutions which do not interfere with the reaction.
  • Stability to print-out from light exposure is increased by employing highly purified materials; for example, freedom from halides and sulfides increases stability to light exposure.
  • highly purified silver behenate can, for example, reduce propensity to printout in background areas of an element prepared according to the invention.
  • a range of azole thioethers and/or blocked azole thiones can be employed in the practice of the invention to improve post-processing stability, e.g., to reduce post-processing print-out due to room-light exposure and to reduce background stain.
  • a suitable stabilizer precursor is a heterocyclic stabilizer precursor which is an azole compound of the formula:
  • Z represents atoms completing a or 6- member heterocyclic nucleus, such as thiazole, thiadiazole, thiazoline and tetrazole;
  • R is alkyl containing l to carbon atoms, e.g., methyl, ethyl, propyl, butyl and pentyl,
  • R is wherein R is alkyl containing one to five carbon atoms, such as methyl, ethyl, propyl, butyl and pentyl, carboxy, cyano, aryl containing six to 12 carbon atoms, substituted aryl such as nitrophenyl, methoxyphenyl, ethoxyphenyl or heterocyclic such as furoyl; R is hydrogen, alkyl containing one to five carbon atoms, substituted alkyl such as oxoalkyl, carboxy and carboxyalkyl; R is hydrogen, alkyl containing one to five carbon atoms such as methyl, ethyl, propyl, butyl, tert.-.
  • alkyl such as hydroxymethyl, carboxy and carboxyalkyl, aryl, substituted aryl, e.g., nitrophenyl, methoxyphenyl, benzoyl; n is 0 or 2.
  • Alkyl as employed herein includes alkyl containing substituent groups which do not adversely affect the desired stabilizing activity of the described compounds.
  • the alkyl group can be, for example, carboxyalkyl or dicarboxyalkyl.
  • thiazole thioether S-acetyl- 4-methyl-2-(3-oxobutylthio )thiazole ofthe formula:
  • R is as described previously; R is alkyl containing one to five carbon atoms, aryl containing 6 to l2 carbon atoms, or furoyl; n is 0 or 2.
  • thiadiazole thioether 4-furoyl-3-methylthio-1 ,2,4-thiadiazole-5-thione of the formula:
  • thiadiazole thioether stabilizer precursors which can be employed in the practice of the invention include:
  • Still another suitable azole thioether stabilizer precursor which can be employed in the desired combination includes, for example, tetrazole thioethers of the formula:
  • R is phenyl, substituted phenyl such as 2,6-dit-butyl-phenyl, alkyl or wherein R is as described previously;
  • R can be alkyl, especially alkyl containing one to three carbon atoms, such as methyl, ethyl and propyl, and aryl, such as phenyl; n is or 2.
  • tetrazole thioether 2,6- ditert.-butyl-4-( l-phenyl--tetrazolyl)thiophenyl of the formula: n V
  • R R and R and n are as described previously.
  • An especially suitable blocked azole thione is 5- acetyl-4-methyl-3-(3-oxobutyl)thiazoline-Z-thione of the formula: v
  • Suitable blocked thiazoline thione stabilizer precursors which can be employed in the practice of the invention include:
  • the described stabilizer precursors are suitable in a range of concentration; however, they are especially suitable at a concentration from about 0.002 to about 0.10 mole of stabilizer precursorper mole of oxidizing agent, e.g., silver behenate, according to the invention, in an element as described.
  • oxidizing agent e.g., silver behenate
  • the desired concentration will'depend on several factors, such as the particular image-forming combination and other components of the element, desired image, processing temperature and the like.
  • a simple test may be used to determine whether or not a compound or material is functioning as an image stabilizer as described. If the compound, after incorporation in the invention as described, prevents the build-up of background density or minimum density above 0.l0 without undue stain, as in following Example 2, in comparison to a coating, as in following Example l, where the stabilizer precursor has been omitted, then the compound is considered to be a suitable stabilizer.
  • the azole thioethers and blocked azole thiones can be prepared by the Michael addition of 0:,B-unsaturated ketones such as methyl vinyl ketone to 4- thiazoline-Z-thione.
  • either azole thioethers or blocked azole thiones can be prepared almost exclusively of one another as described in J. Heterocyclic Chem., 6, 397-401 (1969) of Humphlett.
  • the thermal reversibility of some of the azole thioethers formed via the Michael addition to 4-thiazoline-2-thiones is reported in Canadian J. Chem., 44, 2315-2321 (1966) of Allen et al.
  • Spectral-sensitizing dyes can be used conveniently to confer additional sensitivity to the light-sensitive silver halide employed in the practice of the invention.
  • additional spectral sensitization can be obtained by treating the silver halide with asolution of a sensitizing dye in an organic solvent, or the dye can be added in the form of a dispersion as described in British Pat. No. 1,154,781.
  • the dye can beadded tothe emulsion either as a final step or at some earlier stage.
  • Sensitizing dyes useful in sensitizing silver halide emulsions are described, for example, in U.S. Pat. No.
  • Spectral sensitizers which can be used, include the cyanines, merocyanines, complex (trinuclear or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines such as enamine, hemicyanines, oxonols and hemioxonols.
  • Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
  • Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl, and enamine groups that can be fused to carbocyclic or heterocyclic-ring systems wither unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano or alkoxy groups.
  • the dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or'polymethine chain.
  • the merocyanine dyes can contain the basic nuclei described, as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones and malononitrile.
  • acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamine groups or heterocyclic nuclei. Combinations of these dyes can be used, if desired.
  • supersensitizing addenda which do not absorb visible light may be included such as, for instance, ascorbic acid derivatives, azaindenes, cadmium salts and organic sulfonic acid as described in U.S. Pat. No. 2,933,390 of McFall et al. issued Apr. 19, 1960, and U.S. Pat. No. 2,937,089 of Jones et al. issued May 17, 1960.
  • the sensitizing dyes and other addenda used in the practice of the invention can be added from water solutions or suitable organic solvent solutions can be used.
  • the compounds can be added using various procedures including, for example, those described in U.S. Pat. No. 2,912,343 of Collins et al. issued Nov. 10, 1959; U.S. Pat. No. 3,342,605 of McCrossen et al. issued Sept. 19, 1967; U.S. Pat. No. 2,996,287 of Audran issued Aug. 15, 1961; and U.S. Pat. No. 3,425,835 ofJohnson et al. issued Feb. 4, 1969.
  • a range of concentration of dye can be employed in the practice of the invention.
  • the desired concentration will be influenced by the desired spectral sensitivity, other components in the system, the desired image, processing conditions and the like.
  • a concentration of the described sensitizing dye is about 0.05 to about 1 milligram per square foot of the described photographic and thermosensitive element, usually about 0.1 milligram per square foot of dye being employed.
  • One embodiment of the invention is a photosensitive and thermosensitive element comprising a support, an oxidation-reduction image-forming combination comprising (i) a heavy metal salt oxidizing agent, such as a silver salt oxidizing agent, with (ii) a reducing agent, such as a bis-naphthol reducing agent, a catalyst for the described oxidation-reduction image-forming combination, e.g., photosensitive silver halide, a binder and a divalent metal salt image amplifier, e.g., zinc acetate, copper acetate or cadmium acetate.
  • the photosensitive element as described can comprise:
  • a sensitizing dye and i. a divalent metal salt image amplifier such as zinc acetate or cadmium acetate.
  • an oxidation-reduction image-forming combination comprising (i) a heavy metal salt oxidizing agent, e.g., a silver salt oxidizing agent, with (ii) a reducing agent, e.g., a bis-naphthol reducing agent,
  • a catalyst for the described oxidation-reduction image-forming combination e.g., photosensitive silver halide
  • the photosensitive and thermosensitive composition can comprise:
  • reducing agent such as 2,2-dihydroxy-l,l'-binaphthyl
  • heavy metal salt oxidizing agent such as silver behenate oxidizing agent
  • a visible image on the photosensitive and thermosensitive element can'be produced within a few seconds, e.g., about 0.5 to about 60 seconds, after exposure by heating the element to moderately elevated temperatures, e.g., about to about 250 C.
  • another embodiment of the invention IS: in a method of developing a latent image in an exposed photosensitive and thermosensitive element comprising a support, an oxidation-reduction image-forming combination comprising (i) a heavy metal salt oxidizing agent with (ii) a reducing agent, a catalyst for the described oxidation-reduction image-forming combination, a binder and a divalent metal salt image amplifier which is a zinc, copper or cadmium salt, comprising heating said element to about 80 C. to about 250 C.
  • a temperature range of about C. to about C is usually suitable for developing and stabilizing a desired image. By increasing or decreasing the length of time of heating, a higher or lower temperature within the described range can be employed.
  • a developed image is typically produced within a few seconds, such as about 0.5 second to about 60 seconds.
  • the photographic process can comprise, for example, exposing to actinic radiation a photosensitive and thermosensitive element comprising a support,
  • an oxidation-reduction image-forming combination comprising: Y
  • a divalent metal salt such as zinc acetate
  • an image-stabilizer precursor such as 5-acetyl-4- methyl-2-(3-oxobutylthio)thiazole and g. a sensitizing dye, and heating the described element from about 80 C. to about 250 C. for about 0.5 to about 60 seconds.
  • Processing is usually carried out under ambient conditions of temperature, pressure and humidity. Temperatures, pressures and humidity outside normal atmospheric conditions can be employed if desired; however, normal atmospheric conditions are preferred.
  • an element can be prepared wherein the described silver halide can be in one layer and other components in other layers.
  • an element according to the invention can comprise a support, a layer containing photographic silver halide and a layer comprising a so-called thermosensitive processing composition comprising:
  • a heavy metal salt oxidizing agent e.g., a silver salt oxidizing agent such as a silver salt of an organic acid
  • a reducing agent as described, such as a bisnaphthol reducing agent
  • thermosensitive processing composition comprising:
  • a polyvinyl butyral binder is employed with the processing composition.
  • the bis-B-naphtho] reducing agent and/or the zinc acetate in a polyvinyl butyral or cellulose acetate binder and to coat the resulting composition as an anti-abrasion overcoat on the element as described previously.
  • the heating means can be a simple hot plate, iron or the like.
  • EXAMPLE 1 This is a comparative example.
  • a photosensitive element is prepared as follows:
  • a coating composition is prepared by mixing the following components:
  • Example 1 The procedure set out in Example 1 is repeated with the exception that 2.5 ml. of a methanol solution containing 1.0 percent by weight of zinc acetate is added to the final dispersion just prior to making the coating.
  • the final element is exposed and processed as in Example 1; the resulting image is jet-black, has a maximum density of 1.24 and a minimum density of 0.04.
  • a photosensitive and thermosensitive element comprising a support having thereon an oxidationreduction image-forming combination comprising (i) a heavy metal salt oxidizing agent with (ii) a reducing agent, a photosensitive silver salt catalyst for said oxidation-reduction image-forming combination and a binder; the improvement comprising a divalent metal salt image amplifier which is a zinc, copper or cadmium salt.
  • a photosensitive and thermosensitive element comprising a support having thereon a. an oxidation-reduction image-forming combination comprising (i) a silver salt oxidizing agent and (ii) a bis-beta-napthol reducing agent,
  • a catalyst for said oxidation-reduction imageforming combination comprising photosensitive silver halide
  • a divalent metal salt image amplifier which comprises zinc acetate and d. a binder.
  • a photosensitive and thermosensitive element as in claim 2 also comprising an activator-toning agent.
  • a photosensitive and thermosensitive element as in claim 2 also comprising an activator-toning agent which is phthalimide.
  • a photosensitive and thermosensitive element as in claim 2 also comprising a stabilizer precursor which is an azole thioether or a blocked azole thione.
  • a photosensitive and thermosensitive element as in claim 2 also comprising a stabilizer precursor which is 5 -acetyl-4-methyl-2-( 3-oxobuty1thio )thiazole.
  • a photosensitive and thermosensitive element comprising a support having thereon a. an oxidation-reduction image-forming combination comprising (i) an oxidizing agent comprising silver behenate and (ii) a reducing agent which is 2,2'-dihydroxy-1,1'-binaphthyl,
  • a photosensitive and thermosensitive element as in claim 2 also comprising a sensitizing dye.
  • a photosensitive and thermosensitive element as in claim 2 comprising a support having thereon a. about 0.10 mole to about 2.0 moles of said reducing agent per mole of said catalyst,
  • a photosensitive and thermosensitive composition comprising:
  • an oxidation-reduction image-forming combination comprising (i) a heavy metal salt oxidizing agent with (ii) a reducing agent,
  • a photosensitive silver salt catalyst for said oxidation-reduction image-forming combination and c. a divalent metal salt image amplifier which is a zinc, copper or cadmium salt.
  • a photosensitive and thermosensitive composition comprising:
  • an oxidation-reduction image-forming combination comprising (i) a silver salt oxidizing agent with (ii) a bis-beta-naphthol reducing agent,
  • a catalyst for said oxidation-reduction imageforming combination comprising photosensitive silver halide and c. a divalent metal salt image amplifier which com-' prises zinc acetate.
  • a photosensitive and thermosensitive composition as in claim 11 also comprising an activator-toning agent.
  • a photosensitive and thermosensitive composition as in claim 11 also comprising an activator-toning agent which is phthalimide.
  • a photosensitive and thermosensitive composition as in claim 11 also comprising a stabilizer precursor which is an azole thioether or a blocked azole thione.
  • a photosensitive and thermosensitive composition comprising:
  • an oxidation-reduction image-forming combination comprising (i) an oxidizing agent comprising silver behenate and (ii) a reducing agent which is 2,2'-dihydroxy-l,l'-binaphthyl,
  • an image-stabilizer precursor comprising S-acetyl- 4-methyl-2--(3-oxobutylthio)thiazole and g. a sensitizing dye.
  • a photosensitive and thermosensitive composition as in claim 11 also comprising a sensitizing dye.
  • a photosensitive and thermosensitive composition as in claim 11 comprising:
  • a method of developing an image in an exposed photosensitive and thermosensitive element comprising a support having thereon an oxidation-reduction image-forming combination comprising (i) a heavy metal salt oxidizing agent with (ii) a reducing agent, a
  • photosensitive silver salt catalyst for said oxidationreduction image-forming combination a binder and a divalent metal salt image amplifier which is a zinc, copper or cadmium salt, comprising heating said element to about C to about 250 C.
  • a method of developing and stabilizing an image in an exposed photosensitive and thermosensitive element comprising a support
  • an oxidation-reduction image-forming combination comprising (i) a silver salt oxidizing agent and (ii) a bis-beta-naphthol reducing agent,
  • a catalyst for said oxidation-reduction imageforming combination comprising photosensitive silver halide
  • a method of developing and stabilizing an image in an exposed photosensitive and thermosensitive element comprises a support, having thereon a. an oxidation-reduction image-forming combination comprising (i) an oxidizing agent comprising silver behenate and (ii) a reducing agent comprising 2,2'-dihydroxy-l ,l '-binaphthyl,
  • an image-stabilizer precursor comprising S-acetyl- 4-methyl-2-(3-oxobutylthio)thiazole and g. a sensitizing dye, comprising heating said element to about 80 C. to about 250 C.
  • a method as in claim 20 comprising heating said element for about 0.5 to about 60 seconds.
  • thermosensitive processing composition comprising:
  • thermosensitive processing composition comprising:
  • thermosensitive processing composition as in claim 22 comprising polyvinyl butyral binder.

Landscapes

  • 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)
  • Heat Sensitive Colour Forming Recording (AREA)
US00043173A 1970-06-03 1970-06-03 Use of divalent metal salt image amplifiers in photosensitive and thermosensitive elements Expired - Lifetime US3708304A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US4317370A 1970-06-03 1970-06-03

Publications (1)

Publication Number Publication Date
US3708304A true US3708304A (en) 1973-01-02

Family

ID=21925863

Family Applications (1)

Application Number Title Priority Date Filing Date
US00043173A Expired - Lifetime US3708304A (en) 1970-06-03 1970-06-03 Use of divalent metal salt image amplifiers in photosensitive and thermosensitive elements

Country Status (6)

Country Link
US (1) US3708304A (de)
BE (1) BE768073A (de)
BR (1) BR7103419D0 (de)
CA (1) CA984207A (de)
DE (1) DE2127110A1 (de)
FR (1) FR2095790A5 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839041A (en) * 1970-06-03 1974-10-01 Eastman Kodak Co Stabilizer precursors in photothermographic elements and compositions
US4144062A (en) * 1976-07-08 1979-03-13 Eastman Kodak Company Organotellurium (II) and (IV) compounds in heat-developable photographic materials and process
US4207112A (en) * 1974-01-29 1980-06-10 Fuji Photo Film Co., Ltd. Heat developable light-sensitive materials
EP0054414A1 (de) * 1980-12-12 1982-06-23 EASTMAN KODAK COMPANY (a New Jersey corporation) Fotografisches Material, das eine Vorläuferverbindung eines Silberhalogenidstabilisators enthält
US4668612A (en) * 1984-09-04 1987-05-26 Fuji Photo Film Co., Ltd. Heat-developable color photosensitive material
US4670374A (en) * 1984-10-01 1987-06-02 Minnesota Mining And Manufacturing Company Photothermographic accelerators for leuco diazine, oxazine, and thiazine dyes
US5916487A (en) * 1996-07-03 1999-06-29 Saint Gobain Vitrage Process for obtaining a photochromic compound and products obtained
US20050095540A1 (en) * 2003-11-03 2005-05-05 Eastman Kodak Company Thermally developable imaging materials with barrier layer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3094619A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Ultra-violet radiation-desensitizable thermographic copy-sheet and method
US3322557A (en) * 1964-05-11 1967-05-30 Ncr Co Thermo-copy system
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
US3460946A (en) * 1966-02-03 1969-08-12 Minnesota Mining & Mfg Image receptor sheets containing organic silver salts and metal ion image
GB1161777A (en) * 1966-02-21 1969-08-20 Fuji Photo Film Co Ltd Thermally Developable Light-sensitive Elements
US3523795A (en) * 1964-12-25 1970-08-11 Fuji Photo Film Co Ltd Heat developable photographic copying materials

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3094619A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Ultra-violet radiation-desensitizable thermographic copy-sheet and method
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
US3322557A (en) * 1964-05-11 1967-05-30 Ncr Co Thermo-copy system
US3523795A (en) * 1964-12-25 1970-08-11 Fuji Photo Film Co Ltd Heat developable photographic copying materials
US3460946A (en) * 1966-02-03 1969-08-12 Minnesota Mining & Mfg Image receptor sheets containing organic silver salts and metal ion image
GB1161777A (en) * 1966-02-21 1969-08-20 Fuji Photo Film Co Ltd Thermally Developable Light-sensitive Elements

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, Vol. 68, 1968, pg. 64585, reference at 64592f, Light developable printing out photosensitive material. *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839041A (en) * 1970-06-03 1974-10-01 Eastman Kodak Co Stabilizer precursors in photothermographic elements and compositions
US4207112A (en) * 1974-01-29 1980-06-10 Fuji Photo Film Co., Ltd. Heat developable light-sensitive materials
US4144062A (en) * 1976-07-08 1979-03-13 Eastman Kodak Company Organotellurium (II) and (IV) compounds in heat-developable photographic materials and process
US4152155A (en) * 1976-07-08 1979-05-01 Eastman Kodak Company Organotellurium (II) and (IV) compounds in heat-developable imaging materials and process with physically developable nuclei
EP0054414A1 (de) * 1980-12-12 1982-06-23 EASTMAN KODAK COMPANY (a New Jersey corporation) Fotografisches Material, das eine Vorläuferverbindung eines Silberhalogenidstabilisators enthält
US4668612A (en) * 1984-09-04 1987-05-26 Fuji Photo Film Co., Ltd. Heat-developable color photosensitive material
US4670374A (en) * 1984-10-01 1987-06-02 Minnesota Mining And Manufacturing Company Photothermographic accelerators for leuco diazine, oxazine, and thiazine dyes
US5916487A (en) * 1996-07-03 1999-06-29 Saint Gobain Vitrage Process for obtaining a photochromic compound and products obtained
US20050095540A1 (en) * 2003-11-03 2005-05-05 Eastman Kodak Company Thermally developable imaging materials with barrier layer
WO2005045519A1 (en) * 2003-11-03 2005-05-19 Eastman Kodak Company Thermally developable imaging materials with barrier layer
US6991894B2 (en) * 2003-11-03 2006-01-31 Eastman Kodak Company Thermally developable imaging materials with barrier layer

Also Published As

Publication number Publication date
CA984207A (en) 1976-02-24
FR2095790A5 (de) 1972-02-11
DE2127110A1 (de) 1971-12-09
BR7103419D0 (pt) 1973-04-12
BE768073A (fr) 1971-11-03

Similar Documents

Publication Publication Date Title
US3839041A (en) Stabilizer precursors in photothermographic elements and compositions
US3846136A (en) Certain activator-toners in photosensitive and thermosensitive elements,compositions and processes
US3667959A (en) Photosensitive and thermosensitive element,compositions and process
US4022617A (en) Photothermographic element, composition and process for producing a color image from leuco dye
US3700458A (en) Chemical process
US3761270A (en) Photographic element composition and process
US3672904A (en) Photothermographic elements containing bis-beta-naphthols
US3782949A (en) Photographic element comprising a hydroxy substituted aliphatic carboxylic acid aryl hydrazide
CA1078656A (en) Use of 2,6-dihalo-4-substituted sulfonamidophenol reducing agents in thermographic and photothermographic compositions
US3785830A (en) Photothermographic element,composition and process
US3667958A (en) Photosensitive and thermosensitive elements,compositions and processes
US3761279A (en) Photothermographic element
US3666477A (en) Element,composition and process
EP0840906A2 (de) Verfahren zur herstellung eines photothermographischen aufzeichnungsmaterials
US3877940A (en) Photothermographic element, composition and process
US3700457A (en) Use of development inhibitor releasing compounds in photothermographic elements
US3730727A (en) Photographic element comprising an aliphatic carboxylic acid aryl hydrazide and ascorbic acid
US3871887A (en) Photothermographic composition, element and process
US3751252A (en) Photothermographic element and process
US3751249A (en) Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent
US4258129A (en) Thermally developable light sensitive material using trivalent and tetravalent cerium compounds
US3679422A (en) Photothermic composition containing onium halide sensitizer and the use thereof
US3997346A (en) Method for stabilizing the image of a thermally developable photosensitive material
US3708304A (en) Use of divalent metal salt image amplifiers in photosensitive and thermosensitive elements
US4211839A (en) Method of producing light-sensitive composition for use in thermally developable light-sensitive elements and elements so produced