US3871887A - Photothermographic composition, element and process - Google Patents

Photothermographic composition, element and process Download PDF

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US3871887A
US3871887A US430364A US43036474A US3871887A US 3871887 A US3871887 A US 3871887A US 430364 A US430364 A US 430364A US 43036474 A US43036474 A US 43036474A US 3871887 A US3871887 A US 3871887A
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photothermographic
iodide
silver
preparing
composition
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Cynthia G Jones
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US430364A priority Critical patent/US3871887A/en
Priority to CA215,566A priority patent/CA1039553A/en
Priority to DE2460547A priority patent/DE2460547C2/de
Priority to FR7442632A priority patent/FR2256434B1/fr
Priority to JP49149311A priority patent/JPS5217415B2/ja
Priority to CH1738574A priority patent/CH607092A5/xx
Priority to GB71/75A priority patent/GB1480653A/en
Priority to BE152102A priority patent/BE824051A/xx
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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
    • G03C1/49836—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 Improved sensitivity to certain wavelengths of light and improved contrast are provided by certain photothermographic compositions containing a sensitizing concentration of a non-silver iodide salt.
  • Such photothermographic compositions prepared by (A) preparingia dispersion of (a) an oxidation-reduction imageforming combination comprising (i) a silver salt oxidizing agent and (ii) an organic reducing agent, with (b) ex situ, synthetic polymer-peptized photosensitive silver halide, (c) a cyclic imide toner in (d) a nongelatin polymeric'binder, contain a sensitizing concentration of a non-silver iodide salt, such as lithium iodide.
  • the described non-silver iodide salt can be mixed with described photothermographic compositions at different stages of preparation of the compositions.
  • photothermographic materials It has been desirable to provide increased photosensitivity to certain wavelengths of light in photothermographic materials. This is defined and employed herein as the sensitivity to ranges of electromagnetic radiation to which the photothermographic materials are exposed imagewise to provide a latent image. It has also been desirable in some cases to provide increased contrast of the images produced with the described photothermographic materials.
  • the described photothermographic materials contain silver halide which is prepared employing a polymeric peptizer.
  • a typical polymeric peptizcr employed for this purpose is poly(- vinyl butyral).
  • the silver halide can then be mixed with other components of the photothermographic composition such as an oxidation-reduction image-forming combination comprising (1) a silver salt oxidizing agent, such as silver behenate, and (2) an organic reducing agent, such as a sulfonamidophenol reducing agent.
  • a photothermographic composition comprising an oxidation-reduction image-forming combination containing (1) a silver salt oxidizing agent, such as silver behenate, with (2) an organic reducing agent, such as a sulfonamidophenol reducing agent, with poly(vinyl acetal) peptized silver halide in a polymeric binder does not provide desired increased photosensitivity to the desired wavelength of light.
  • a silver salt oxidizing agent such as silver behenate
  • an organic reducing agent such as a sulfonamidophenol reducing agent
  • a photothermographic composition and element comprising a dispersion of (a) an oxidation-reduction image-forming combination comprising (i) a silver salt oxidizing ,agent, and (ii) anorganic reducing agent, with (b) ex situ, synthetic polymer peptized photosensitive silver halide, (c) a cyclic imide toner, and (d) a polymeric binder whereinthe non-silver iodide salt has the property of increasing the desired photosensitivity of the photothermographic composition.
  • the described non-silver iodide salt can be mixed with the described photothermographic compositions at different stages of preparation of the compositions depending on such factors as the wavelengths to be used for imagewise exposure and particular 10mporients of the photothermographic material.
  • the surprising increase in photosensitivity to certain wavelengths of light is illustrated by comparative examples and the results set out in the following tables.
  • non-silver iodide compounds can be employed according to the invention.
  • the non-silver iodide salt must have the property of increasing the photosensitivity of the described photothermographic materials to the desired wavelengths of light for imagewise exposure. Merely adding a silver iodide emulsion to the photothermographic materials does not provide the desired increase in photosensitivity. Accordingly, the term non-silver iodide compounds or salts as employed herein is intended to exclude silver iodide.
  • One test which can be employed to determine a suitable non-silver iodide salt is set out in following Example 1.
  • the iodide is considered to be acceptable.
  • the useful concentration of non-silver iodide salt in this test is about 0.01 mole to about 0.50 moles of the described non-silver iodide salt per mole of the photosensitive silver halide in the photothermographic material.
  • Acceptable non-silver iodide salts according to the invention are, for instance, lithium iodide, ammonium iodide, sodium iodide, potassium iodide and mixtures of these iodides.
  • Lithium iodide is especially useful when employing a sulfonamidophenol reducing agent with a silver salt oxidizing agent, such as silver behenate, and an ex situ, poly(vinyl butyral) peptized photosensitive silver bromide in a polymeric binder such as poly(vinyl butyral).
  • a range of concentration of the described non-silver iodide salt can be employed. The concentration must be sufficient to provide the desired increase in photosensitivity in the described photothermographic composition. Typically, a concentration of non-silver iodide salt is about 0.01 mole to about 0.50 mole of the described non-silver iodide salt per mole of photosensitive silver halide in the described photothermographic material. A concentration of non-silver iodide salt which is about 0.01 mole to about 0.05 mole of the iodide, typically lithium iodide, per mole of the described silver halide is usually preferable.
  • the method of preparing the described photothermographic composition and element comprising a dispersion of oxidation-reduction image-forming combination with ex situ, synthetic polymer peptized photosensitive silver halide, and a cyclic imide toner in a polymeric binder can vary depending on the particular photothermographic material, desired image, processing conditions and the like.
  • a typical method of preparing the dispersion involves thoroughly mixing the described components. These can be mixed employing any suitable apparatus such as a ball-mill or similar mixing means.
  • One method of preparing the described dispersion and means for preparing the dispersion are set out, for instance, in Belgian Pat. No. 774,436 issued Nov. 12,1971.
  • the photothermographic elements and compositions according to the invention comprise an oxidationreduction image-forming combination which contains a silver salt oxidizing agent.
  • the silver salt oxidizing agent can be a silver salt of an organic acid such as a fatty acid which is resistant to darkening upon illumination.
  • An especially useful class of silver salts of organic acids is represented by the water insoluble silver salts of long-chain fatty acids which are stable to light.
  • Compounds which are suitable silver salt oxidizing agents include, for instance, silver behenate, silver stearate, silver oleate, silver laurate, silver hydroxy stearate, silver caprate, silver myristate and silver palmitate with silver stearate and silver behenate being especially useful.
  • silver salts can be employed as the silver salt oxidizing agent which are not silver salts of longchain fatty acids.
  • Such silver salt oxidizing agents which are useful include, for example, silver benzoate, silver benzotriazole, silver terephthalate, silver phthalate and the like. In most instances, however, silver behenate is most useful.
  • a variety of organic reducing agents can be employed in the described oxidation-reduction image forming combination.
  • Sulfonamidophenol reducing agents are especially useful in the described oxidationreduction image-forming combination.
  • Sulfonamidophenol reducing agents in photothermographic materials are described in US. Application Ser. No. 272,832 of Evans and McLaen, filed July 18, 1972.
  • the sulfonamidophenol reducing agents useful according to the invention can be prepared employing known procedures in the art and include such compounds as described in Canadian Pat. No. 815,526 of Bard issued June 17, 1969.
  • a useful class of sulfonamidophenol reducing agents according to the invention is represented by the structure:
  • R and R are each selected from the group consisting of hydrogen; chlorine; bromine; iodine; alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl; aryl containing 6 to 12 carbon atoms such as phenyl and tolyl; arylsulfonyl containing 6 to 12 carbon atoms, such as phenylsulfonyl; amino; hydroxy; alkoxy containing 1 to 4 carbon atoms, such as methoxy and ethoxy; and atoms completing with R and R a naphthalene nucleus;
  • Z and Z are each selected from the group consisting of hydrogen; bromine; chlorine; alkyl containing 1 to 4 carbon atoms, as described; aryl containing 6 to 10 carbon atoms, such as phenyl and tolyl; arylsulfonyl containing 6 to 12 carbon atoms, as described; amino; hydroxy; alkoxy containing 1 to 4 carbon atoms, such as methoxy and ethoxy; and R SO NH- wherein R is alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl; aryl containing 6 to 10 carbon atoms, such as phenyl and tolyl and hetero ring substituents, such as thienyl, quinolinyl and thiazyl,
  • o o o Z is hydrogen, alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, chlorine and bromine when R and R are other than atoms completing containing l to 3 carbon atoms such as methyl, ethyl,
  • the amino group in some cases, provides an overly active reducing agent.
  • One especially useful class of sulfonamidophenol reducing agents are compounds of the formula:
  • R is phenyl, naphthyl, methylphenyl, thienyl, quinolinyl, thiazyl, or alkyl containing 1 to 4 carbon atoms,
  • R is hydrogen, R SO NH, alkoxy containing 1 to 4 carbon atoms, hydroxy, alkyl containing 1 to 4 carbon atoms, bromine or chlorine;
  • R is hydrogen, bromine, chlorine, alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, or alkoxy containing 1 to 4 carbon atoms, such as methoxy, ethoxy and propoxy.
  • R, R and/or R can contain substituent groups which do not adversely affect the reducing properties of the described sulfonamidophenol reducing agents or the desired sensitometric properties of the photothermographic elements and materials of the invention. These substituent groups are the same as described for generic structure I.
  • sulfonamidophenol reducing agents which are useful in photothermographic elements and compositions of the invention are sulfonamidonaphthols ofthe formula:
  • the sulfonamidophenol group in the described sulfonamidonaphthols can be in the ortho, meta or para position.
  • the sulfonamidonaphthols are more active compounds within the sulfonamidophenol reducing agent class. Also, within this class, sulfonamidophenols which contain three sulfonamidophenol groups are more active. These sulfonamidophenols are employed for shorter developing times or with heavy metal salt oxidizing agents which are less active than silver behenate.
  • image discrimination provided by photothcrmographic materials containing the sulfonamidonaphthols and trifunctional sulfonamidophenols is less than that provided by other of the scribed sulfonamidophenols.
  • Combinations of sulfonamidophenol reducing agents can be employed in photothermographic materials and elements according to the inven tion.
  • Especially useful sulfonamidophenol reducing agents include benzenesulfonamidophenol reducing agents, such as 2,6-dichloro-4- benzenesulfonamidophenol and/or 4- benzenesulfonamidophenol.
  • organic reducing agents which can be employed alone or in combination with the described sulfonamidophenol reducing agents include substituted phenols and naphthols, for example, bis-B-naphthols, such as described in US. Pat. No. 3,672,904 of deMauriac, issued June 27, 1972.
  • Suitable bis-B-naphthols include, for instance, 2,2'-dihydroxy-l,1-binaphthyl; 6,- 6-dibromo-2,2-dihydroxy-1,1-binaphthyl; 6,6- dinitro-2,2'-dihydroxy-l,1'-binaphthyl and/or bis-(2- hydroxy-l-naphthol) methane.
  • a so-called activator-toning agent also known as-an accelerator-toning agent or toner, can be employed in the photothermographic materials according to the in-' vention to obtain a desired image.
  • the activator-toning agent is a cyclic imide and is typically useful in a range of concentration such as a concentration of about 0.10 mole to about 1.1 mole of activator-toning agent per mole of silver salt oxidizing agent in the photothermographic material.
  • Typical suitable activator-toning agents are described in Belgian pat. No. 766,590 issued June 15, 1971.
  • Typical activator-toning agents include, for example, 1 phthalimide, N-hydroxyphthalimide, N-hydroxy-l,8-naphthalimide, N-potassium phthalimide, N-mercury phthalimide, succinimide and/or N- hydroxysuccinimide. Combinations of so-called activator-toning agents can be employed if desired.
  • Other activato r-toning agents which can be employed include phthalazinone, 2-acetyl-phthalazinone and the like.
  • a photothermographic element can contain various non-gelatin compounds alone or in combination as vehicles, binding agents and in various layers.
  • Suitable materials can be hydrophobic or hydrophilic. They are transparent or translucent and include such synthetic polymeric substances as water soluble 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.
  • Effective polymers include water insoluble polymers of polyesters, polycarbonates, alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates, methacrylates and those which have crosslinking sites which facilitate hardening or curing as well as those having recurring sulfobetaine units as described in Canadian Pat. No. 774,054.
  • Especially useful high molecular weight materials and resins include poly(vinyl butyral), cellulose acetate butyrate, polymethyl methacrylate, poly(vinyl pyrrolidone), ethylcellulose, polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-styrene copolymers, vinyl chloride-vinyl acetate copolymers, copolymers of vinyl acetate, vinyl chloride and maleic acid and polyvinyl alcohol.
  • the described non-silver iodide salt can be mixed with the described photothermographic compositions at different stages of preparation of the composition.
  • the optimum stage of addition will depend on such factors as the wavelength to be used for imagewise exposure of the photothermographic composition, particular components of the photothermographic materials, desired image, particular activator-toning agent and the like.
  • one embodiment of the invention comprises a method of preparing a silver halide photothermographic composition or element comprising respectively A. preparing a dispersion of silver behenate in poly(- vinyl butyral),
  • Another embodiment of the invention comprises a method of preparing a silver halide, photothermographic composition or element comprising respec tively A. preparing poly( vinyl butyral) peptized photosensitive silver halide,
  • the photothermographic composition can be coated on a suitable support to provide a photothermographic element.
  • a further embodiment of the invention comprises preparing a photothermographic composition
  • preparing a photothermographic composition comprising (A) preparing a dispersion of (a) an oxidation-reduction image-forming combination comprising (i) a silver salt oxidizing agent, typically silver behenate, and (ii) a sulfonamidophenol reducing agent, with (b) ex situ, synthetic polymer peptized photosensitive silver halide, in (c) a poly(vinyl butyral).
  • a photothermographic ele-- It is desirable, in some cases, to employ an image stabilizer and/or image stabilizer precursor in the described photothermographic materials of the invention.
  • image stabilizers or stabilizer precursors are described, for example, in Belgian Pat. No. 768,071 issued July 30, 1971.
  • Typical stabilizer precursors include, for example, azole thioethers and blocked azoline thione stabilizer precursors as described in this Belgian patent'and described in US. Pat. No. 3,700,457 of Youngquist, issued Oct. 24, 1972. i
  • the described photothermographic compositions and elements according to the invention can contain various addenda to aid the compositions and elements such as development modifiers that function as additional speed-increasing compounds, hardeners, antistatic layers, plasticizers and lubricants, coating aids, brighteners, spectral sensitizing dyes, absorbing and filter dyes, also as described in the Product Licensing Index, Volume 92, Dec., 1971, publication 9232, pages lO7l l0. 1
  • Spectral sensitizing dyes can be used in the described photothermographic materials of the invention to confer additional sensitivity to the elements and compositions of the invention.
  • Useful sensitizing dyes are described, for example, in the Product Licensing Index, Volume 92, Dec., 1971, publication 9232, pages 107-1 10, paragraph XV and Belgian Pat. No. 772,371 issued Oct. 15, 1971.
  • a spectral sensitizing dye which provides a sensitivity to the red region of the spectrum is employed in the described photothermographic material according to the invention.
  • the photothermographic compositions and other compositions according to the invention can be coated on a suitable support by various coating procedures including dip coating, air knife coating, curtain coating or extrusion coating using hoppers such as described in US. Pat. No. 2,681,294 of Beguin issued June 15, 1954. If desired, two or more layers can be coated simultaneously such as described in US. Pat. No. 2,761,791 of Russell, issued Sept. 4, 1956 and British Pat. No. 837,095.
  • a range of concentration of various components of the photothermographic materials can be employed according to the invention.
  • a useful concentration of reducing agent is typically about 0.25 mole to about 4 moles of reducing agent, such as sulfonamidophenol reducing agent, per mole of photosensitive silver halide in the photothermographic material.
  • a useful concentration range of reducing agent is typically about 0.10 mole to about 20.0 moles of reducing agent per mole of silver salt oxidizing agent, such as silver behenate and/or silver stearate. If a combination of reducing agents is employed, the total concentration of reducing agent is typically within the described concentration range.
  • a typical concentration range of photosensitive silver halide is about 0.01 mole to about 20 moles of photosensitive silver halide per mole of silver salt oxidizing agent, for instance, per mole of silver behenate and/or silver stearate.
  • Preferred photosensitive silver halides are silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide of mixtures thereof.
  • the photosensitive silver halide can be coarse or fine-grain, very fine-grain photosensitive silver halide being especially useful.
  • the photosensitive silver halide can be chemically sensitized, can be protected against the production of fog and/or stabilized against the loss of sensitivity during keeping, as described in the Product Licensing Index reference mentioned previously.
  • synthetic polymer peptized photosensitive silver halide can be prepared with a range of synthetic polymer peptizers.
  • Useful synthetic polymer peptizers include, for example, those described in US. Pat. No. 3,713,833 of Lindholm et al., issued Jan. 30, 1973 and US. Pat. No. 3,706,565 of Ericson, issued Dec. 19, 1972, and vinyl pyridine polymers, e.g., polymers of 2-vinyl pyridine, 4-vinylpyridine and 2-methyl-5-vinylpyridine.
  • Poly(vinyl acetals), such as poly(vinyl butyral), are especially useful as peptizers in the described preparation of ex situ silver halide.
  • the procedure can be carried out in a non-aqueous medium under controlled reaction conditions.
  • an organic solvent such as acetone or methylisobutyl ketone, can be employed with the peptizer,such as po1y(vinyl butyral).
  • An example of a suitable preparation of photosensitive silver halide is as follows: Lithium bromide, silver trifluoroacetate and poly(vinyl butyral) are mixed in acetone under controlled conditions. The resulting, finegrain silver bromide can then be mixed with an oxidation-reduction image-forming combination, such as a sulfonamidophenol with silver behenate, to provide a photothermographic material.
  • the silver halide employed in the practice of the invention can he unwashed or washed to remove soluble salts.
  • the soluble salts can be removed by chill-setting and decantation or an emulsion containing the silver halide can be coagulation washed.
  • Poly((vinyl acetal) peptized photosensitive silver halide is useful and is described, for example, in Belgian Pat. No. 774,436 issued Nov. 12, 1971.
  • the photosensitive silver halide is prepared according to this method by mixing a source of silver ions with a source of halide ions in the presence of a poly(vinyl acetal) such as poly(vinyl butyral).
  • This polymer peptized photosensitive silver halide is especially useful when the photothermographic material contains a polymeric binder which is the same as the polymer employed to peptize the silver halide.
  • the polymeric binder can be poly(vinyl butyral) which can also be employed to peptize the photosensitive silver halide.
  • An especially useful embodiment of the invention is in a photothermographic composition
  • a photothermographic composition comprising the combination of (a) an oxidation-reduction imageforming combination comprising (i) silver behenate and/or silver stearate with (ii) a sulfonamidophenol reducing agent, as described, with (b) poly(vinyl butyral) peptized silver halide in (c) a poly(vinyl butyral) binder, the improvement comprising (d) about 0.01 mole to about 0.5 mole, such as about 0.01 mole to about 0.15 mole, of lithium iodide per mole of the silver halide.
  • an especially useful activator-toning agent is succinimide.
  • the resulting latent image can be developed merely by uniformly overall heating the element to moderately elevated temperatures. This merely involves overall heating the described photothermographic element from about C. to about 250C. such as for about 0.5 second to about 60 seconds. By increasing or decreasing the length of time of heating, a
  • a developed image is typically produced within several seconds, such as about 0.5 second to about 60 seconds.
  • a processing temperature of about C. to about C. is especially useful.
  • While visible light can be employed to produce the latent image, other sources of electromagnetic radiation can be employed.
  • the described photothermographic elements of the invention are useful for high intensity imagewise exposure.
  • a laser can be employed to produce an image in the described photothermographic material.
  • the heating means can be a simple hot plate, iron, roller or the like.
  • Processing is usually carried out under ambient conditions of pressure and humidity. Conditions outside normal atmospheric pressure and humidity can be employed if desired.
  • one or more components of the photothermographic element described can be in one or more layers of the element.
  • EXAMPLE 1 This is a comparative example.
  • a silver behenate dispersion is prepared by ballmilling the following components for 100 hours:
  • a photothermographic composition is prepared by combining 100 ml of the above-described dispersion with the following addenda in the order indicated:
  • composition is then held 4 hours at room temperature, i.e., about 20C.
  • composition is coated at 6.9 ml/ft on unsubbed poly(ethylene terephthalate) film support.
  • the element is also overcoated with the following composition at 2.3 ml/ft. 1
  • the dried element is exposed sensitometrically to light for lO'- seconds with a Mark VII exposing device marketed by Edgerton, Germeshausen and Grier, Inc. and then overall heated for 5 seconds at l32C.
  • the sensitometric results are given in Table 1.
  • EXAMPLE 2 This example is like Example 1 except that 4 ml of an acetone solution containing 2.28% by weight anhydrous lithium iodide is added to the described composition prior to coating. The element is sensitometrically exposed and processed by overall heating the exposed element for 5 seconds at 132C. as described in Example l. The sensitometric results appear in Table I.
  • EXAMPLE 7 The procedure described in Example 2 is repeated with the exception that 0.05 mole of lithium iodide is employed per mole of the described photosensitive silver bromide in the photothermographic composition. Results similar to those of Example 2 are observed.
  • EXAMPLE 8 The procedure described in Example 2 is repeated with the exception that 0.25 mole of lithium iodide is employed per mole of the described photosensitive silver bromide in the photothermographic composition. Results similar to those of Example 2 are observed.
  • Example 15 the element most sensitive to red light, i.e., light to which the elements have been spectrally sensitized, is Example 15. This element was prepared Table Ill SPECTRALLY SENSITIZED COATINGS Clear lue Red Order Rel. Rel. Rel. of Ex.
  • 0A Other addenda, e.g. polyvinylbutyral, developer, 2,4-dihydroxyhcnzophenone,
  • silicone AF-70 silicone AF-70, respectively
  • D Silver behenate, polyvinylbutyral dispersion
  • Tp Phthalazinone toner
  • l Lithium iodide
  • E Washed polyvinylbutyral-silvcr bromide emulsion
  • Dy Spectral sensitizing dye
  • b a synthetic polymer-peptized photosensitive sil-' ver halide
  • sensitizing concentration is about 0.01 mole to about 0.50 mole of' said iodide salt per mole of said photosensitive silver halide.
  • said iodide salt is a compound selected from the group consisting of lithium iodide, potassium iodide, sodium iodide and ammonium iodide and combinations of these iodide compounds.
  • a method as in claim 1 of preparing a photothermographic composition also comprising, after said mixing, holding the resulting composition for about seconds to about 48 hours at about C. to about 30C. before any subsequent step.
  • a cyclic imide toner comprising succinimide, c. a poly(vinyl butyral) peptized silver halide in d. a poly(vinyl butyral) binder, and, after preparing said dispersion:
  • a method of preparing a photothermographic composition comprising:
  • an oxidation-reduction image-forming combination comprising:
  • a cyclic imide toner comprising succinimide, c. poly(vinyl butyral) peptized silver bromide in d. a poly(vinyl butyral) binder, and, after preparing said dispersion, B. mixing with said dispersion about 0.01 mole to about 0.05, mole of lithium iodide per mole of said silver bromide, and then C. holding the resulting photothermographic composition for about minutes to about 4 hours at about 20C. to about 30C. before any subsequent step. 8.
  • a method of preparing a silver halide photothermographic composition comprising respectively A. preparing a dispersion of silver behenate in poly(- vinyl butyral), B. mixing with the resulting silver behenate dispersion about 0.01 to about 0.05 mole of lithium iodide per mole of silver halide in the photothermographic composition, C. mixing with the resulting composition an ex situ, poly(vinyl butyral) peptized photosensitive silver halide, and
  • D a poly(vinyl butyral) binder
  • E mixing succinimide, a sulfonamidophenol reducing agent and a spectral sensitizing dye with the resulting composition.
  • a method of preparing a silver halide photothermographic composition comprising respectively A. preparing poly( vinyl butyral) peptized photosensitive silver halide, B. mixing with said silver halide about 0.01 to about 0.05 mole of lithium iodide per mole of said silver halide,
  • an oxidation-reduction image-forming combination comprising: i. a silver salt oxidizing agent and ii. an organic reducing agent with:
  • a cyclic imide toner in d. a non-gelatin polymeric binder the improvement comprising, after preparing said dispersion B. mixing with said dispersion a sensitizing concentration of a non-silver iodide salt, said iodide salt having the property of increasing the photosensitivity of said photothermographic composition,
  • said iodide salt is a compound selected from the group consisting of lithium iodide, potassium iodide, sodium iodide, ammonium iodide and combinations of these iodide compounds.
  • a method of preparing a photothermographic element comprising:
  • an oxidation-reduction image-forming combination comprising: i. silver behenate and ii. 4-benzenesulfonamidophenol and 2,4-dihydroxybenzophenone, and
  • a method of preparing a photothermographic element comprising respectively A. preparing a dispersion of silver behenate in poly(- vinyl butyral),
  • a method of preparing a photothermographic element comprising respectively A. preparing poly(vinyl butyral) peptized photosensitive silver halide,
  • an oxidation-reduction image-forming combination comprising:
  • a photothermographic composition as in claim 16 wherein said iodide salt is a compound selected from the group consisting of lithium iodide, potassium iodide, sodium iodide, ammonium iodide and combinations of these iodide compounds.
  • an oxidation-reduction image-forming combination comprising:
  • a poly(vinyl butyral) binder for said composition the improvement comprising:

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US430364A 1974-01-02 1974-01-02 Photothermographic composition, element and process Expired - Lifetime US3871887A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US430364A US3871887A (en) 1974-01-02 1974-01-02 Photothermographic composition, element and process
CA215,566A CA1039553A (en) 1974-01-02 1974-12-10 Photothermographic compositions, element and process
DE2460547A DE2460547C2 (de) 1974-01-02 1974-12-20 Verfahren zur Herstellung einer photothermographischen Beschichtungsmasse sowie photothermographisches Aufzeichnungsmaterial
FR7442632A FR2256434B1 (ja) 1974-01-02 1974-12-24
JP49149311A JPS5217415B2 (ja) 1974-01-02 1974-12-28
CH1738574A CH607092A5 (ja) 1974-01-02 1974-12-30
GB71/75A GB1480653A (en) 1974-01-02 1975-01-02 Sensitive photothermographic material
BE152102A BE824051A (fr) 1974-01-02 1975-01-02 Composition, produit et procede photothermographiques

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US430364A US3871887A (en) 1974-01-02 1974-01-02 Photothermographic composition, element and process

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US (1) US3871887A (ja)
JP (1) JPS5217415B2 (ja)
BE (1) BE824051A (ja)
CA (1) CA1039553A (ja)
CH (1) CH607092A5 (ja)
DE (1) DE2460547C2 (ja)
FR (1) FR2256434B1 (ja)
GB (1) GB1480653A (ja)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4283477A (en) * 1978-11-02 1981-08-11 Eastman Kodak Company Photothermographic material and process
US4476220A (en) * 1982-07-29 1984-10-09 Minnesota Mining And Manufacturing Company Spectrally sensitized photothermographic materials and preparation thereof
EP0247473A2 (de) * 1986-05-30 1987-12-02 Agfa-Gevaert AG Durch Wärmebehandlung entwickelbares farbfotografisches Aufzeichnungsmaterial
US4725534A (en) * 1981-05-13 1988-02-16 Oriental Photo Industrial Co., Ltd. Process for producing a heat-developable photosensitive material
US4732560A (en) * 1981-12-21 1988-03-22 Gte Products Corporation Humidity protected radiation-responsive switch
US4743534A (en) * 1983-11-30 1988-05-10 Minnesota Mining And Manufacturing Company Preformed silver halides for photothermographic system
US4751176A (en) * 1983-11-30 1988-06-14 Minnesota Mining And Manufacturing Company Preformed silver halides for photothermographic system
US5478718A (en) * 1995-01-18 1995-12-26 Agfa-Gevaert, N.V. Preparation of silver halide tabular emulsions in the presence of non-aqueous polar aprotic solvents and/or protic solvents having a dissociation constant smaller than that of water
US5541051A (en) * 1995-01-18 1996-07-30 Agfa-Gevaert, N.V. Preparation of silver halide tabular emulsions in the presence of polar aprotic solvents and/or alcohols
US5578415A (en) * 1988-09-12 1996-11-26 Asahi Kasei Kogyo Kabushiki Kaisha Optical recording materials, method for preparing the same and optical cards having the same
EP0809141A1 (en) * 1996-05-22 1997-11-26 Eastman Kodak Company Photothermographic and thermographic films containing low levels of formate to prevent fog
US5843632A (en) * 1997-06-27 1998-12-01 Eastman Kodak Company Photothermographic composition of enhanced photosensitivity and a process for its preparation
US5858637A (en) * 1997-06-27 1999-01-12 Eastman Kodak Company Process of preparing a photothermographic composition of enhanced photosensitivity
US6040130A (en) * 1997-02-10 2000-03-21 Eastman Kodak Company Photothermographic and thermographic films containing low levels of unsaturated fatty acid to prevent fog
US6274297B1 (en) * 1997-12-12 2001-08-14 Agfa-Gevaert Photothermographic recording material with in-situ and ex-situ photosensitive silver halide and a substantially light-insensitive organic salt
US6607872B1 (en) * 1996-06-13 2003-08-19 Agfa-Gevaert Photothermographic recording material
EP1582919A1 (en) 2004-03-23 2005-10-05 Fuji Photo Film Co. Ltd. Silver halide photosensitive material and photothermographic material
EP1635216A1 (en) 2004-09-14 2006-03-15 Fuji Photo Film Co., Ltd. Photothermographic material
US20060065075A1 (en) * 2004-09-29 2006-03-30 Eastman Kodak Company Silver nanoparticles made in solvent

Citations (3)

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Publication number Priority date Publication date Assignee Title
US3178292A (en) * 1962-10-25 1965-04-13 Eastman Kodak Co Direct-print photographic silver halide emulsions
US3531288A (en) * 1966-03-11 1970-09-29 Eastman Kodak Co Direct positive silver halide emulsions containing excess iodide
US3647455A (en) * 1969-10-13 1972-03-07 Du Pont Direct positive emulsions containing iodide ions and a sensitizing dye

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Publication number Priority date Publication date Assignee Title
DE1048778B (ja) * 1956-03-13
DE1797380C3 (de) * 1967-10-23 1974-07-11 Horst 8000 Muenchen Theilemann Verfahren zur Herstellung einer photographischen SiI berhalogenidemulsion und Vorrichtung zur Ausübung dieses Verfahrens
US3679422A (en) * 1970-06-03 1972-07-25 Eastman Kodak Co Photothermic composition containing onium halide sensitizer and the use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3178292A (en) * 1962-10-25 1965-04-13 Eastman Kodak Co Direct-print photographic silver halide emulsions
US3531288A (en) * 1966-03-11 1970-09-29 Eastman Kodak Co Direct positive silver halide emulsions containing excess iodide
US3647455A (en) * 1969-10-13 1972-03-07 Du Pont Direct positive emulsions containing iodide ions and a sensitizing dye

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4283477A (en) * 1978-11-02 1981-08-11 Eastman Kodak Company Photothermographic material and process
US4725534A (en) * 1981-05-13 1988-02-16 Oriental Photo Industrial Co., Ltd. Process for producing a heat-developable photosensitive material
US4732560A (en) * 1981-12-21 1988-03-22 Gte Products Corporation Humidity protected radiation-responsive switch
US4476220A (en) * 1982-07-29 1984-10-09 Minnesota Mining And Manufacturing Company Spectrally sensitized photothermographic materials and preparation thereof
US4751176A (en) * 1983-11-30 1988-06-14 Minnesota Mining And Manufacturing Company Preformed silver halides for photothermographic system
US4743534A (en) * 1983-11-30 1988-05-10 Minnesota Mining And Manufacturing Company Preformed silver halides for photothermographic system
EP0247473A3 (de) * 1986-05-30 1990-03-21 Agfa-Gevaert AG Durch Wärmebehandlung entwickelbares farbfotografisches Aufzeichnungsmaterial
EP0247473A2 (de) * 1986-05-30 1987-12-02 Agfa-Gevaert AG Durch Wärmebehandlung entwickelbares farbfotografisches Aufzeichnungsmaterial
US5578415A (en) * 1988-09-12 1996-11-26 Asahi Kasei Kogyo Kabushiki Kaisha Optical recording materials, method for preparing the same and optical cards having the same
US5478718A (en) * 1995-01-18 1995-12-26 Agfa-Gevaert, N.V. Preparation of silver halide tabular emulsions in the presence of non-aqueous polar aprotic solvents and/or protic solvents having a dissociation constant smaller than that of water
US5541051A (en) * 1995-01-18 1996-07-30 Agfa-Gevaert, N.V. Preparation of silver halide tabular emulsions in the presence of polar aprotic solvents and/or alcohols
EP0809141A1 (en) * 1996-05-22 1997-11-26 Eastman Kodak Company Photothermographic and thermographic films containing low levels of formate to prevent fog
US6037115A (en) * 1996-05-22 2000-03-14 Eastman Kodak Company Photothermographic and thermographic films containing low levels of formate to prevent fog
US6607872B1 (en) * 1996-06-13 2003-08-19 Agfa-Gevaert Photothermographic recording material
US6040130A (en) * 1997-02-10 2000-03-21 Eastman Kodak Company Photothermographic and thermographic films containing low levels of unsaturated fatty acid to prevent fog
US5843632A (en) * 1997-06-27 1998-12-01 Eastman Kodak Company Photothermographic composition of enhanced photosensitivity and a process for its preparation
US5858637A (en) * 1997-06-27 1999-01-12 Eastman Kodak Company Process of preparing a photothermographic composition of enhanced photosensitivity
US6274297B1 (en) * 1997-12-12 2001-08-14 Agfa-Gevaert Photothermographic recording material with in-situ and ex-situ photosensitive silver halide and a substantially light-insensitive organic salt
EP1582919A1 (en) 2004-03-23 2005-10-05 Fuji Photo Film Co. Ltd. Silver halide photosensitive material and photothermographic material
EP1635216A1 (en) 2004-09-14 2006-03-15 Fuji Photo Film Co., Ltd. Photothermographic material
US20060065075A1 (en) * 2004-09-29 2006-03-30 Eastman Kodak Company Silver nanoparticles made in solvent
WO2006039453A2 (en) * 2004-09-29 2006-04-13 Eastman Kodak Company Silver nanoparticles made in non-aqueous solvent
WO2006039453A3 (en) * 2004-09-29 2007-07-12 Eastman Kodak Co Silver nanoparticles made in non-aqueous solvent
US7329301B2 (en) 2004-09-29 2008-02-12 Eastman Kodak Company Silver nanoparticles made in solvent

Also Published As

Publication number Publication date
JPS50102326A (ja) 1975-08-13
BE824051A (fr) 1975-07-02
JPS5217415B2 (ja) 1977-05-16
CH607092A5 (ja) 1978-11-30
FR2256434B1 (ja) 1976-10-22
CA1039553A (en) 1978-10-03
DE2460547A1 (de) 1975-07-03
GB1480653A (en) 1977-07-20
DE2460547C2 (de) 1985-03-07
FR2256434A1 (ja) 1975-07-25

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