US3635719A - Heat developable light-sensitive elements - Google Patents

Heat developable light-sensitive elements Download PDF

Info

Publication number
US3635719A
US3635719A US570768A US3635719DA US3635719A US 3635719 A US3635719 A US 3635719A US 570768 A US570768 A US 570768A US 3635719D A US3635719D A US 3635719DA US 3635719 A US3635719 A US 3635719A
Authority
US
United States
Prior art keywords
group
member selected
oxalate
light
sensitive element
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
US570768A
Other languages
English (en)
Inventor
Kinji Ohkubo
Junpei Noguchi
Takao Masuda
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.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
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 Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3635719A publication Critical patent/US3635719A/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

Definitions

  • the present invention relates to a light-sensitive element and more particularly to a heat developable light-sensitive element containing a light-sensitive silver salt and one which is capable of forming images by heating.
  • the most widely used photographic light-sensitive element uses silver halide. This is because photographic light-sensitive elements using a silver halideare generally excellent in the areas of sensitivity and gradation, as compared with electrophotographic light-sensitive elements and other light-sensitive elements.
  • a developing solution must be employed for developing the photographic element after exposure and in order to prevent the developed photographic images from being discolored or faded and the background thereof from being blackened under usual light, the developed photographic element must be further subjected to several processing steps. The latter additional processings are usually called stopping, fixing or stabilizing.
  • the image obtained from conventional heat developable light-sensitive elements using a silver halide salt become blackened due to the printing out of the silver halide when the element, after development, is placed as is in a light place, which makes the discrimination of the image dilficult. Therefore, it is necessary in such a system to process the developed photographic element with a stabilizing solution or a fixing solution to make the undeveloped silver halide particles light-insensitive or convert them into water-soluble materials, which are then removed by washing.
  • the present invention relates generally to the last of the aforementioned proposals, i.e., a photographic light-sensitive element having a mixture of a light-insensitive and oxidizing organic silver salt, a slight amount of a light-sensitive silver salt, and more particularly to a photographic light-sensitive element containing a mixture of a silver salt of benzotriazale and a slight amount of a silver halide.
  • an object of the present invention is to provide a novel light-sensitive composition.
  • Another object of the present invention is to provide a novel process for reproducing images.
  • Still another object of the present invention is to provide a highly sensitive light-sensitive element capable of forming images by a dry process or by only heating without using any solutions in the developing process.
  • a further object of the present invention is to provide a light-sensitive element capable of providing light-stable images by developing, and one which is aiso capable of being preserved substantially pennanently after development without the necessary of conducting fixing and other procedures.
  • the heat developable light-sensitive element of the present invention has a single-layer or multilayer containing a mixture of an organic silver salt which is light-insensitive and which can be reduced and a very slight amount of a light-sensitive silver salt, particularly a silver halide.
  • the light-sensitive element comprises a support bearing thereon at least one layer containing at least (a) a light-insensitive silver salt; (b) a material for providing light sensitivity, i.e., a silver halide, or an inorganic halide capable of producing a silver halide by reaction with the light-insensitive silver salt (a); (c) a compound capable of being decomposed into a basic material by heating and, if necessary, a compound capable of releasing water by heating; and (d) a reducing agent.
  • the light-sensitive element comprises a support bearing thereon at least one layer containing at least (a) a light-insem sitive silver salt; (b) a material for providing light sensitivity, i.e., a small amount of a silver halide or an inorganic halide capable of forming a silver halide by reaction with the light-insensitive silver salt (a); (c) a metal oxide or hydroxide capable of being converted into a basic material by heating; and (d) a reducing agent together with, if necessary, at least one compound capable of releasing water by heating and a catalyst for accelerating the oxidation of the reducing agent.
  • any of the above-mentioned light-sensitive elements of the present invention has color sensitivity and can provide stable images after exposure by a very simple dry process.
  • the printout of silver halide scarcely proceeds, and moreover, if the thus developed light-sensitive element is processed with water or other suitable solvent, the progress of printout can be completely prevented and, hence, permanent images can be obtained.
  • the support used in this invention may be any physically and chemically stable flexible sheet such as metal foils, synthetic resin films (generally cellulose diacetate films, cellulose triacetate films, polyethylene terephthalate films, or polycarbonate films) and papers; but among the suitable papers, a paper having a good water-absorbing power is most suitable for use in the present invention.
  • synthetic resin films generally cellulose diacetate films, cellulose triacetate films, polyethylene terephthalate films, or polycarbonate films
  • papers but among the suitable papers, a paper having a good water-absorbing power is most suitable for use in the present invention.
  • silver salts of organic compounds having imino groups such as a silver salt of benzotriazole, a halogen substitute thereof or a nitro substitute thereof, carbazolyl silver, the silver salt of saccharin and the like.
  • the silver salt of the halogensubstituted or nitro-substituted benzotriazole is lightinsensitive but the heat development thereof is difficult; that is, such a silver salt is not effectively reduced by heating.
  • Carbazolyl silver is also difficult to develop by heating.
  • the silver salt of saccharin (o-sulfobenzoic acid imide) may be developed by heating but the contrast between the image and the background is low; that is, the fonnation of heat fog is increased.
  • the unsubstituted silver salt of benzotriazale it can be developed by heating and the contrast between the image and background is high.
  • the silver salt of benzotriazole the element can be fixed by bathing with water, and if the temperature of the heat development is high, the density of the background is not increased even if the thus heatrdeveloped light-sensitive element is allowed to stand in usual light for a long period of time. Accordingly, the silver salt of benzotriazole is the most suitable light-insensitive salt for the light-sensitive element of the present invention.
  • Thesilver salt of benzotriazole may be prepared by dissolving, for example, 59.5 g. of 1,2,3-benmtriazole into 2 liters of methanol and adding into the resulting solution an aqueous solution of silver nitrate (85 g./200 ml.) with stirring at normal temperature. The thus-formed precipitate is washed with water by decantation times, recovered by filtration, washed with water three times and then dried.
  • the size of the crystal of the silver salt can be controlled.
  • the inorganic halide capable of forming silver halide by reaction with the light-insensitive silver salt used in this invention is a water-soluble or organic solvent-soluble compound shown by the general formula hrilX, wherein M represents hydrogen, ammonium or a metal, such as strontium, cadmium, zinc, tin, chromium, sodium, barium, iron, cesium, lanthanum, copper, calcium, nickel, magnesium, potassium, aluminum, antimony, gold, cobalt, mercury, lead, and beryllium; X represents a halogen atom, such as chlorine, bromine, and iodine; and n is the valency of M.
  • the iodide is particularly preferable in the present invention since the silver salt formed by the reaction with the iodide has a property of being difficult to printout.
  • the light-insensitive organic silver salt containing a small amount of a silver halide or the above-mentioned organic halide may be, after being dispersed in the below-described binder solution, subjected to a sulfur sensitization, a reduction sensitization, or a noble metal sensitization as in the case of conducting the preparation of conventional photographic emulsions to increase the light sensitivity.
  • the compound to be used in this invention which can be decomposed by heating into a basic material, can be an oxalate of an aliphatic amine such as dicyciohexylamine, an oxalate of an aromatic amine such as benzylamine, and an oxalate of a cyclic amine such as piperidine and morpholine.
  • These salts of amines may be prepared by adding an aqueous or alcohol solution of an amine into an excessive amount of an aqueous or alcohol solution of oxalic acid and then filtering, washing and drying the thus-formed precipitate.
  • These compounds may be used alone or as a mixture thereof.
  • the oxalates have excellent photographic properties as compared with the salts of other organic acids and the oxalates may be prepared easily.
  • the decomposition temperature of these salts by heating is about 120 C. for the oxalate of dicyclohexylamine, about 125 C. for the oxalate of benzylamine, about 105 C. for the oxalate of piperidine, and about 135 C. for the oxalate of morpholine.
  • the metal oxide or hydroxide employed in the present invention to provide basicity by heating is the oxide or hydroxide of a metal belonging to groups 2 or 3 of the periodic table; for example, zinc oxide, aluminum oxide, magnesium oxide, zinc hydroxide, aluminum hydroxide, cadmium hydroxide, and magnesium hydroxide.
  • the above-mentioned metal oxide or hydroxide is also useful as an additive for improving the contrast between the image and the background.
  • the compound capable of releasing water by heating employed in this invention is a compound containing water of crystallization.
  • metal salts of acetic acid such as lead acetate trihydrate, zinc acetate dihydrate, manganese acetate tetrahydrate, and magnesium acetate tetrahydrate are very effective. These compounds may be used alone or as a mixture thereof.
  • the light-sensitive element of the present invention containing these compounds capable of releasing water by heating can provide a good photographic image as compared with those not containing such compounds.
  • the above-mentioned compound containing water of crystallization releases a part of the water of crystallization when heated to a temperature lower than 100 C. with the remaining water of crystallization being released at about l00 C.
  • the temperatures are 50 C. and 100 C. for lead acetate trihydrate, 65 C. and 100 C. for cadmium acetate dihydrate, and C. and l00 C. for zinc acetate dihydrate.
  • the reducing agent suitable employed in the present invention may be: an aromatic monoor poly-hydroxyl compound or a derivative thereof, or an aromatic monopoly-amino compound or a derivative thereof.
  • a developer used for usual photographic processing may be effectively used.
  • Particularly effective examples of such reducing agents are hydroquinone, methylhydroquinone, chlorohydroquinone, bromohydroquinone, phenylhydroquinone, catechol, pyrogallol, hydroquinone monosulfonate, resorcinol, paminophenol, o-aminophenol, N-methyl-aminophenol onehalf sulfate, 2-methoxy-4-aminophenol hydrochloride, 2,4- diaminophenol hydrochloride, sodium l-amino-2-naphthol-6- sulfonate, p-oxyphenyl glycine, 2-hydroxyethyl-4- aminophenol, N,N-diethyl-p
  • l-phenyl'3- pyrazolidone hydroxylamine hydrochloride
  • reducing saccharides glucose, lactose, etc.
  • the oxidation reduction potential must be less than 500 m.v. (a standard hydrogen electrode).
  • the composition containing the above-mentioned ingredients may contain, if necessary, a color sensitizer, a hardening agent, a developing accelerator, a matting agent, and a coating aid.
  • composition containing the above-mentioned components is applied to a support, such as wood pulp paper, ragcontaining paper, photographic paper, baryta paper, films, metal foils, dry glass plates, and the like.
  • a support such as wood pulp paper, ragcontaining paper, photographic paper, baryta paper, films, metal foils, dry glass plates, and the like.
  • a part of or the entire composition may be coated on the support in separate layers. Further, in order to form a uniform and smooth coating of the composition on the support, it is preferable to use a suitable binder.
  • the binder which may be used in this invention is preferably translucent or transparent one so as not to lower the transmission of light therethrough. It is particularly preferable to employ photographic gelatin a solid high molecular weight material or resin.
  • Suitable high molecular weight materials and resins include polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, polyvinyl pyrrolidone, ethyl cellulose, polyethylene glycol, polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene, a copolymer of butadiene and styrene, a copolymer of vinyl chloride and vinyl acetate, a copolymer of vinyl chloride, vinyl acetate and maleic acid, methacrylic resin, polyvinyl alcohol and derivatives thereof such as polyvinyl acetate.
  • the color sensitizer, coating aid, color-toning agent, matting agent, hardening agent, etc. may be any of those which are used for the preparation of conventional silver halide photographic sensitive elements.
  • a tungsten lamp an ultraviolet lamp, heated in a suitable manner such as by passing the elements through two heated rollers, by placing the elements between two heated plates or by the irradiation of the elements with infrared rays.
  • the compound capable of releasing water by heating releases water to wet the coating medium and simultaneously the compound capable of being decomposed by heating into a basic material is thermally decomposed to provide basicity to the coating medium. Consequently, the reducing agent, such as an aromatic monoor poly-hydroxy compound, is activated and hence the exposed portion of the light-sensitive silver halide having a latent image acts as a reducing catalyst, whereby the light-insensitive silver salt is reduced to provide an image.
  • the reducing agent such as an aromatic monoor poly-hydroxy compound
  • the compound capable of becoming basic by heating provides the coating medium basicity and the oxidation reduction potential of the reducing agent is lowered to give photographic activity theretofAccordingly, the exposed portion of the light-sensitive silver halide having a latent image acts as a reducing catalyst to reduce the light-insensitive silver salt, whereby an image is obtained.
  • the period of exposure is influenced by the kind and intensity of the light source and developing conditions, the kinds of reducing agent and other additives employed as well as the sensitivity of the light-sensitive silver salt, it may vary by a considerably wide range but the deviation is generally from 0.001 second to 5 minutes.
  • the development of the thus-exposed light-sensitive ele ment is conducted by heating said element for l to 30 seconds at temperature above 80 (3., preferably from 120 C. to 170 C.
  • washing effect may usually be weak, methanol or ethanol may be replaced with water for hastening the drying after the treatment.
  • the developing temperature is comparatively higher, part or all of the reducing agent will be removed from the system by melting, evaporating or sublimating and hence even if the light-sensitive element subjected to the high-temperature development is allowed to stand as is or without the washing treatment, the density increase of the background is scarcely observed or is not observed at all.
  • the density increase of the background when exposed in a bright place after development may be effectively prevented by incorporating in the emulsion layer of the heatdevelopable light-sensitive element an oxidizing catalyst capable of destroying the reducing agent by heating, such as titanium oxide, stannic chloride, antimony chloride, gallium azide, cadmium sulfide, cadmium selenide, etc., in an amount of 0.1 to 5 g. per 1 g. of the reducing agent.
  • an oxidizing catalyst capable of destroying the reducing agent by heating such as titanium oxide, stannic chloride, antimony chloride, gallium azide, cadmium sulfide, cadmium selenide, etc.
  • the light-sensitive elements of the present invention may be developed after exposure by the dry method and stable images can be obtained without the need of conducting fixing and other processing steps, it is now apparent that because of the present invention the reproduction process can be hastened and simplified.
  • EXAMPLE 1 Into a suitable amount of water were added 2 g. of the silver salt of benzotriazole, 7.5 g. of gelatin, 0.002 g. of strontium iodide, 1 g. of morpholine oxalate, 25 g. of lead acetate trihydrate, and 0.5 g. of hydroquinone and the resulting emulsion was, after the further addition of suitable amounts of a color sensitizer, an antifoggant, a coating aid, and a hardening agent, applied to a photographic paper. After exposure, the photographic element was developed by heating for 10 seconds at C., immersed in tap water for 2 minutes, and dried.
  • EXAMPLE 2 The following coating compositions were applied successively to a photographic paper per 25 square meters thereof;
  • These coating liquids contained suitable amounts of a color sensitizer, a coating aid and a hardening agent.
  • the resulting photographic element was developed by heating for 30 seconds at 160 C., immersed for 5 minutes in methanol and then dried. Thus, a stable image causing no printout by direct exposure to sunlight was obtained.
  • EXAMPLE 3 into a suitable amount of water were added 2 g. of the silver salt of benzotriazole, 7.5 g. of gelatin, 0.0005 g. of silver iodide, 2.5 g. of piperidine oxalate, 25 g. of lead acetate trihydrate, and 0.5 g. of monomethyl hydroquinone and the resulting coating liquid was, after the further addition of suitable amounts of a color sensitizer, an antifoggant, a coating aid, and a hardening agent, applied to a photographic paper.
  • the thus-obtained photographic element was developed by heating at 160 C. for 10 seconds to provide a stable image causing no printout by the direct exposure to sunlight.
  • EXAMPLE 4 into a suitable amount of water were added 2.5 g. of the silver salt of benzotriazole, 7.5 g. of gelatin, 0.002 g. of barium iodide, l g. of piperidine oxalate, and 25 g. of maltose and the resulting coating liquid was, after the further addition of a color sensitizer, an antifoggant and a coating aid, applied to a photographic paper. After exposure, the photographic element was developed by heating for seconds at 160 C., immersed in water for 10 minutes, and then dried. Thus, a stable image causing no printout by the direct exposure thereof to sunlight was obtained.
  • EXAMPLE 5 Into a suitable amount of water were added 1 g. of the silver salt of benzotriazole, 4.5 g. of gelatin, 0.03 g. of strontium iodide, 0.5 g. of aluminum oxide, g. of lead acetate trihydrate, and 0.2 g. of hydroquinone and the resulting coating liquid was, after the further addition of suitable amounts of a color sensitizer, an antifoggant, a coating aid and a hardening agent, applied to a photographic paper per 2 square meters thereof.
  • the photographic light-sensitive element was developed for 5 seconds at 160 C. to provide a reproduction showing almost no density increase of background when exposed to direct sunlight. Moreover, when the sample was immersed for more than 1 second in water after development followed by drying, a stable image causing no density increase by the direct exposure to sunlight was obtained.
  • aqueous solution containing 50 g. of gelatin, 200 g. of cadmium'acetate dihydrate, and 0.3 g. of barium chloride.
  • coating liquids contained suitable amounts of a color sensitizer, a coating aid and a hardening agent.
  • the thus-prepared photographic light-sensitive element was developed by heating for 30 seconds at 140 C., immersed for 5 minutes in methanol and then dried. The thus-processed sample showed no background density increase when exposed to direct sunlight.
  • EXAMPLE 7 Into a suitable amount of water were added 1 g. of the silver salt of benzotriazole silver, 4.5 g. of gelatin, 0.01 g. of silver iodide, 0.25 g. of aluminum oxide, 15 g. of zinc acetate, 0.2 g. of methyl hydroquinone, and 0.02 g. of titanium dioxide and the resulting coating composition was, after the addition of suitable amounts of a color sensitizer, an antifoggant, a coating aid and a hardening agent, applied to a photographic paper per 2 square meters thereof. After exposure, the thus-obtained light-sensitive element was developed for 5 seconds at 150 C. When the thus-developed sample was exposed to direct sunlight, no background density increase was observed.
  • EXAMPLE 8 The following coating liquids were applied in two layers to a polyethylene terephthalate film per 2 square meters thereof:
  • coating liquids further contained suitable amounts of a color sensitizer, a coating aid and a hardening agent.
  • the thus-prepared light-sensitive element was developed by heating for 10 seconds at 170 C. immersed in water for 5 seconds and then dried to provide a stable image causing no background density increase when exposed to direct sunlight.
  • EXAMPLE 9 Into a suitable amount of an aqueous acetic acid solution were added 2 g. of the silver salt of benzotriazole, 9 g. of ethyl cellulose, 0.02 g. of strontium iodide, 0.5 g. of zinc oxide, 0.3 g. of hydroquinone, and 0.01 g. of titanium dioxide and the resulting dispersion was, after the addition of suitable amounts of a color sensitizer and an antifoggant, applied to a polyethylene terephthalate film per 4 square meters.
  • the thus-obtained light-sensitive element was developed by heating for 10 seconds at C. to provide a reproduction causing almost no background density increase when exposed to direct sunlight.
  • EXAMPLE l0 Into a suitable amount of water were added l g. of the silver salt of benzotriazole, 9 g. of gelatin, 0.1 g. of strontium iodide, 0.6 g. of hydroquione, and 2 g. of aluminum hydroxide and the resulting coating composition was, after the addition of suitable amounts of a color sensitizer, an antifoggant, a coating aid, and a hardening agent, applied to a photographic paper per 4 square meters.
  • the thus-obtained light-sensitive element was developed by heating for 10 seconds at C. to provide a reproduction causing almost no background density increase when allowed to stand in situ in a bright place.
  • a heat-developable light-sensitive element comprising a support bearing at least one layer thereon, said layer comprismg:
  • M represents a member selected from the group consisting of a hydrogen atom, an ammonium group and a metal
  • X represents a halogen atom
  • n is the valency of M
  • a. compound capable of releasing a basic material upon heating comprising at least one member selected from a group consisting of an oxalate of an organic amine, a metal oxide and metal hydroxide, said metal being a member selected from the group consisting of metals of groups 2 and 3 of the periodic table;
  • a reducing compound comprising a member selected from the group consisting of aromatic monoor polyhydroxyl compounds and derivatives thereof, and aromatic monoor poly-amino compounds and derivatives thereof.
  • said reducing agent is a member selected from the group consisting of unsubstituted dihydroxybenzene, unsubstituted trihydroxybenzene, halogen-substituted dihydroxybenzene, alkyl-substituted dihydroxybenzene, said alkyl having one to four carbon atoms, aryl-substituted dihydroxybenzene, and l-phenyl-3-pyrazolidone.
  • a heat-developable light-sensitive element comprising a support hearing at least one layer thereon, said layer comprismg:
  • b at least one member selected from the group consisting of a silver halide and an inorganic halide represented by the formula MX,,, .whereinM represents a member selected from the group consisting of a hydrogen atom, an ammonium group and a metal, X represents a halogen atom and n is the valency of M; a compound capable of releasing a basic material upon heating comprising at least one member selected from a group consisting of an oxalate of an organic amine, a metal oxide and metal hydroxide, said metal being a member selected from the group consisting of metals of groups 2 and 3 of the periodic table; a compound containing water of crystallization;
  • a reducing compound comprising a member selected from the group consisting of aromatic mono or poly hydroxyl compounds and derivatives thereof, and aromatic monoor poly-amino compounds and derivatives thereof;
  • said catalyst for accelerating the oxidation of the reducing compound is a member selected from the group consisting of titanium oxide, stannic chloride, antimony chloride, gallium azide, cadmium sulfide, and cadmium selenide.
  • said reducing compound is a member selected from the group consisting of unsubstituted dihydroxybenzene, unsubstituted trihydroxybenzene, halogen-substituted dihydroxybenzene, alkyl-substituted dihydroxybenzene, said alkyl having one to four carbon atoms, aryl-substituted dihydroxybenzene, and l-phenyl-3-pyrazolidone.
  • a process for obtaining a print comprising exposing to light for from 0.001 second to 5 minutes a heat-developable light-sensitive element comprising a support bearing thereon at least one layer comprising:
  • a the silver salt of benzotriazole; b. at least one member selected from the group consisting of a silver halide and an inorganic halide represented by the fonnula MX,, wherein M represents a member selected from the group consisting of a hydrogen atom, an ammonium group and a metal, X represents a halogen atom and n is the valency of M;
  • a compound capable of releasing a basic material upon heating comprising at least one member selected from a group consisting of an oxalate of an organic amine, a
  • metal oxide and metal hydroxide said metal being a member selected from the group consisting of metals of groups 2 and 3 of the periodic table;
  • a reducing compound comprising a member selected from the group consisting of aromatic mono or polyhydroxyl compounds and derivatives thereof, and aromatic monoor poly-amino compounds and derivatives thereof; and heating the exposed element for a period of time of from 1 to 30 seconds at a temperature of from to C.
  • a process for obtaining a print comprising exposing light for from 0.001 second to 5 minutes a heat-developable light-sensitive element comprising a support bearing thereon at least one layer comprising:
  • M represents a member selected from the group consisting of a hydrogen atom, an ammonium group and a metal
  • X represents a halogen atom
  • n is the valency of M
  • a compound capable or releasing a basic material upon heating comprising at least one member selected from the group consisting of dicyclohexylamine oxalate, benzylamine oxalate, piperidine oxalate, morpholine oxa late, a metal oxide and a metal hydroxide, said metal being a member selected from the group consisting of metals of group 2 and 3 of the periodic table;
  • a compound containing water of crystallization comprising a member selected from the group consisting of lead acetate trihydrate, zinc acetate dihydrate and cadmium acetate dihydrate;
  • a reducing compound comprising a member selected from the group consisting of aromatic monoor polyhydroxyl compounds and derivatives thereof, and aromatic monoor poly-amino compounds and derivatives thereof; and heating the exposed element for a period of time of from I to 30 seconds at a temperature of from I 20 to 170 C.

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)
US570768A 1965-08-05 1966-08-08 Heat developable light-sensitive elements Expired - Lifetime US3635719A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4715865 1965-08-05
JP7657865 1965-12-13

Publications (1)

Publication Number Publication Date
US3635719A true US3635719A (en) 1972-01-18

Family

ID=26387313

Family Applications (1)

Application Number Title Priority Date Filing Date
US570768A Expired - Lifetime US3635719A (en) 1965-08-05 1966-08-08 Heat developable light-sensitive elements

Country Status (3)

Country Link
US (1) US3635719A (ja)
BE (1) BE685116A (ja)
DE (1) DE1547850A1 (ja)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3881938A (en) * 1972-04-26 1975-05-06 Fuji Photo Film Co Ltd Thermally developable light-sensitive material with dimercapto substituted tetrazapentalene toners
US4128428A (en) * 1974-04-10 1978-12-05 Fuji Photo Film Co., Ltd. Heat developable light-sensitive material
US4390617A (en) * 1980-03-18 1983-06-28 Konishiroku Photo Industry Co., Ltd. Method for the formation of photographic images
US5071740A (en) * 1985-01-31 1991-12-10 Konishiroku Photo Industry Co., Ltd. Heat developable color photosensitive material
US5258281A (en) * 1990-11-14 1993-11-02 Canon Kabushiki Kaisha Heat-developable photosensitive material
US5482814A (en) * 1993-07-15 1996-01-09 Canon Kabushiki Kaisha Thermal developing photosensitive member and image forming method using the thermal developing photosensitive member
US5529889A (en) * 1992-03-02 1996-06-25 Canon Kabushiki Kaisha Heat developable photosensitive material and image forming method which uses the same
US5543286A (en) * 1993-11-12 1996-08-06 Canon Kabushiki Kaisha Dry process silver salt photosensitive material and image forming method making use of the dry process silver salt photosensitive material
EP0751006A1 (en) 1995-06-27 1997-01-02 Agfa-Gevaert N.V. New method for the formation of a heat mode image
US5864406A (en) * 1990-11-22 1999-01-26 Canon Kabushiki Kaisha Method and apparatus for forming halftone images on organic-silver-salt-based printing plates
US5948600A (en) * 1993-09-13 1999-09-07 Agfa-Gevaert N.V. Method and material for the formation of a heat mode image
US6037115A (en) * 1996-05-22 2000-03-14 Eastman Kodak Company Photothermographic and thermographic films containing low levels of formate to prevent fog
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
US20080026323A1 (en) * 2006-07-28 2008-01-31 Fujifilm Corporation Heat-sensitive transfer image-receiving sheet

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3589903A (en) * 1968-02-28 1971-06-29 Minnesota Mining & Mfg Silver halide,heat-developable image sheet containing mercuric ion

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB943476A (en) * 1959-12-07 1963-12-04 Werner Zindler Improvements in and relating to the preparation of photographic images
US3152904A (en) * 1959-12-21 1964-10-13 Minncsota Mining And Mfg Compa Print-out process and image reproduction sheet therefor
US3429706A (en) * 1959-04-30 1969-02-25 Minnesota Mining & Mfg Radiation-sensitive 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429706A (en) * 1959-04-30 1969-02-25 Minnesota Mining & Mfg Radiation-sensitive system
GB943476A (en) * 1959-12-07 1963-12-04 Werner Zindler Improvements in and relating to the preparation of photographic images
US3152904A (en) * 1959-12-21 1964-10-13 Minncsota Mining And Mfg Compa Print-out process and image reproduction sheet therefor
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

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3881938A (en) * 1972-04-26 1975-05-06 Fuji Photo Film Co Ltd Thermally developable light-sensitive material with dimercapto substituted tetrazapentalene toners
US4128428A (en) * 1974-04-10 1978-12-05 Fuji Photo Film Co., Ltd. Heat developable light-sensitive material
US4390617A (en) * 1980-03-18 1983-06-28 Konishiroku Photo Industry Co., Ltd. Method for the formation of photographic images
US5071740A (en) * 1985-01-31 1991-12-10 Konishiroku Photo Industry Co., Ltd. Heat developable color photosensitive material
US5258281A (en) * 1990-11-14 1993-11-02 Canon Kabushiki Kaisha Heat-developable photosensitive material
US5864406A (en) * 1990-11-22 1999-01-26 Canon Kabushiki Kaisha Method and apparatus for forming halftone images on organic-silver-salt-based printing plates
US5529889A (en) * 1992-03-02 1996-06-25 Canon Kabushiki Kaisha Heat developable photosensitive material and image forming method which uses the same
US5482814A (en) * 1993-07-15 1996-01-09 Canon Kabushiki Kaisha Thermal developing photosensitive member and image forming method using the thermal developing photosensitive member
US5948600A (en) * 1993-09-13 1999-09-07 Agfa-Gevaert N.V. Method and material for the formation of a heat mode image
US5543286A (en) * 1993-11-12 1996-08-06 Canon Kabushiki Kaisha Dry process silver salt photosensitive material and image forming method making use of the dry process silver salt photosensitive material
EP0751006A1 (en) 1995-06-27 1997-01-02 Agfa-Gevaert N.V. New method for the formation of a heat mode image
US6037115A (en) * 1996-05-22 2000-03-14 Eastman Kodak Company Photothermographic and thermographic films containing low levels of formate to prevent fog
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
US20080026323A1 (en) * 2006-07-28 2008-01-31 Fujifilm Corporation Heat-sensitive transfer image-receiving sheet
US7906267B2 (en) * 2006-07-28 2011-03-15 Fujifilm Corporation Heat-sensitive transfer image-receiving sheet

Also Published As

Publication number Publication date
BE685116A (ja) 1967-01-16
DE1547850A1 (de) 1969-11-20

Similar Documents

Publication Publication Date Title
US3645739A (en) Thermally developable light-sensitive elements
US3457075A (en) Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide
US3635719A (en) Heat developable light-sensitive elements
US3152903A (en) Reproduction system
US3152904A (en) Print-out process and image reproduction sheet therefor
US3764329A (en) Heat activated dry silver
US3667959A (en) Photosensitive and thermosensitive element,compositions and process
US3782949A (en) Photographic element comprising a hydroxy substituted aliphatic carboxylic acid aryl hydrazide
US3447927A (en) Print-out silver halide emulsions capable of being chemically developed and/or photodeveloped
US3392020A (en) Photo-thermographic process and element
GB1339766A (en) Photosensitive heat-processable photographic materials
US3655383A (en) Method for reproducing images of a solid photocatalyst with an oxidizing agent
US3364024A (en) Photographic process
US3751252A (en) Photothermographic element and process
US3773512A (en) Photothermic material containing a light-insensitive silver salt and an indane-1,3-dione reducing agent
GB1342525A (en) Heat-processable photographic materials
US3756829A (en) Thermally developable lightsensitive elements
US3881938A (en) Thermally developable light-sensitive material with dimercapto substituted tetrazapentalene toners
US3753395A (en) Photo-thermographic recording process with 5-pyrazolane
GB1131238A (en) Radiation sensitive silver-dye compounds
US3615438A (en) Photographic processes compositions and products
US3885968A (en) Thermally developable light-sensitive material
US3320064A (en) Non-silver halide light sensitive materials
US3674489A (en) Photographic image amplifying with copper ions
EP0104351B1 (en) Gelatin silver halide photographic elements for tanning development