US3348945A - Heat developable light-sensitive photographic material - Google Patents

Heat developable light-sensitive photographic material Download PDF

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Publication number
US3348945A
US3348945A US342528A US34252864A US3348945A US 3348945 A US3348945 A US 3348945A US 342528 A US342528 A US 342528A US 34252864 A US34252864 A US 34252864A US 3348945 A US3348945 A US 3348945A
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US
United States
Prior art keywords
transfer
heat
photographic material
photographic
silver halide
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
US342528A
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English (en)
Inventor
Mader Helmut
Ulrich Hans
Puschel Walter
Konig Anita Von
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.)
Agfa Gevaert NV
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Agfa AG
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Filing date
Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/32—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups bound to acyclic carbon atoms and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • 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

Definitions

  • the invention relates to a photographic material comprising a light sensitive silver halide emulsion layer, which material contains a silver halide developer substance and is developable by the application of heat without the use of a liquid developing solution.
  • a developer-containing, heat developable photographic material is known from British specification No. 930,572, which contains a 3-pyrazolidone silver halide developing agent and an alkaline substance for accelerating development of a latent image.
  • the invention has for its object to produce a heat developable photographic material which does not have the aforementioned disadvantages.
  • a heat-developable photographic material comprising a support bearing a light sensitive silver halide emulsion layer, which material contains a silver halide developer substance and a compound of the following general formula R1 R3 l l ⁇ R, OH H R in which R represents a hydrogen atom, or an alkyl or aryl group, such as a phenyl or naphthyl group, which groups may be substituted,
  • R an optionally substituted aryl radical or a heterocyclic radical
  • R and R together are moreover able to represent the ring members necessary for forming a ring system, preferably a carbocyclic ring system,
  • R represents a hydrogen atom or an optionally substituted alkyl or aryl radical
  • R represents an electron-attracting group, e.g. -NO or --CEN.
  • the preferred compounds are B-nitroethanols which are substituted in u-position by a phenyl radical or by a phenyl radical which is substituted by an alkyl group having preferably 1-5 carbon atoms, an alkoXy group having 1-5 C-atoms in the alkyl radical and/ or a halogen atom, such as chlorine and bromine.
  • alkalis or compounds which split off alkalis or water under the action of heat become substantially superfluous.
  • such compounds can of course be added, but the quantity necessary is so small that the photographic properties of the material and its stability in storage are notimpairecl.
  • Suitable compounds are for example:
  • Compound 6 is prepared in analogous manner by reacting cyclohexanone with nitromethane. A distillation of the crude product obtained after the working up is not possible because of decomposition.
  • Compound 7 is prepared by the following method: 60 g. of 4-methylbenzaldehyde and 58.5 g. of benzyl cyanide are dissolved in 300 ml. of absolute alcohol. At a temperature of 5 to 8 C., a sodium methylate solution prepared from 11.5 g. of sodium and 300 ml. of absolute methanol is introduced dropwise while stirring. Heating then takes place for 2 /2 hours to 50 C. On cooling, an orange-red precipitate is formed, and after this has been suction-filtered and washed with methanol, it is introduced into a mixture of 140 g. of ice, 280 ml. of Water.
  • a silver halide emulsion containing 0.050.5 g. mole of silver halide per liter has added thereto a developer substance, e.g. a 3-pyrazolidone, in quantities of 5-20 g. per liter and one of the condensation products according to the invention in quantities of about 10-50 g., advantageously 20-40 g. per liter, and the mixture is cast on to a suitable support, e.g. a paper or film support.
  • a developer substance e.g. a 3-pyrazolidone
  • These materials may usually contain 1-10 g. of said con-.
  • an inorganic salt which contains water of crystallisation or which has an alkaline reaction. e.g. sodium acetate, sodium carbonate or sodium sulphate.
  • the compounds used according to the invention may be dissolved in highest possible concentration in a suitable solvent such as methanol, ethanol, dimethylformamide and the like and added in this form to the casting solution.
  • a suitable solvent such as methanol, ethanol, dimethylformamide and the like
  • the compounds can be present in the emulsion layers or auxiliary layers in a dissolved or finely divided form.
  • the material After imagewise exposure, the material is heated for 1 to 3 seconds to temperatures of approximately 70-160 C., advantageously -150 C., the material being thus developed.
  • the fixing is then eifected in the usual manner with organic or inorganic fixing agents, e.g. sodium thiosulphate or mercapto compounds.
  • Such quickly developable photographic materials are of importance in all cases where a photographically recorded operation is tobe quickly evaluated, e.g. with recording papers.
  • Silver chloride or silver bromide or mixtures thereof, possibly with a small addition of silver iodide, are suitable as light-sensitive silver salts.
  • the layers can also be optically sensitised, for example, when processes registered on a cathode ray oscillograph are to be photographically recorded.
  • the degree of hardening of the layers is of subordinate importance as regards the efiicacy of the layers according to the invention, but it must be adapted to the actual purpose for which the layers are used.
  • binding agents for the photographic layers are all known layer-forming colloids, more especially gelatin, which can be wholly or partially replaced.
  • cellulose derivatives such as carboxymethyl cellulose, methyl hydroxyethyl cellulose, polyvinylalcohol, polyvinyl acetal, polyvinyl acetate, partially hydrolysed polyvinyl acetates, alginic acid derivatives such as alginates, alginic acid propylene glycol ester, polyvinyl pyrrolidone, zein and other natural or synthetic substances.
  • antifogging agents such as benztriazolc, 1-phenyl-S-mercaptotetrazole, 4-hydroxy-6-methyl- 1,2,3a,7-tetrazaindene and others.
  • Developer substances of the pyrazolidone series are excellently suitable for the light-sensitive material according to the present invention. Examples of these are the following compounds:
  • emulsion layer can be cast on to any suitable layer support which is durable at the temperatures of the heat development, e.g.
  • paper baryta-coated paper
  • filmforming synthetic polymers such as polycarbonate, more especially based on bis-hydroxyarylalkanes or polyesters based on terephthalic acid and ethylene glycol, as well as cellulose esters, fabrics or metal foils.
  • Negative materials with a content of the substances according to the invention can also be used for transfer processes, more especially with developer transfer processes.
  • the developer not used in the unexposed areas of the negative layer is transferred by heat into a transfer layer in contact therewith and are utilised therein for the production of coloured images.
  • the casting solution thus prepared is applied in the usual way to baryta-coated paper and dried.
  • the material After exposure to form an image, the material is heated to about 120 C. for 2 seconds in close contact with a heated metal plate or a pair of heated rollers. A blackishbrown image is obtained, which can be stabilised in the usual way with an acid fixing bath.
  • EXAMPLE 2 A photographic material as described in Example 1 is prepared by using 20 g. of compound 2 instead of compound 1. After the exposure to form a latent image, it is heated for, 2 /2 seconds to 100 C., a brownish-black image being formed. It is fixed in the usual way with an acid fixing bath.
  • the emulsion is cast on to baryta-coated paper. After exposure, it is heated for 2 seconds to 120 C. A violet black image is obtained.
  • EXAMPLE 4 An emulsion is prepared as described in Example 3, but 40 g. of the compound 6 are used instead of compound 7. After development, a brownish-black image is obtained.
  • the film obtained After being applied in the usual way to a suitable layer support (paper or film), the film obtained is exposed to form an image and heated for 2 seconds to 120 C. A black image is obtained.
  • Negative material To 1 liter of a silver chloride emulsion there are added:
  • the pH value is adjusted with sulphuric acid to 4.9.
  • the emulsion is applied in known manner to a layer support, e.g. paper, and dried.
  • the positive (transfer) material is prepared as follows: 1 gram of a cobalt leucophthalocyanine, such as Phthalogen'blau 1B of Far-benfabriken Bayer A.G., dissolved in 30 ml. of a polyethylene glycol having an average molecular weight of about 400, 2 ml. of lactic acid, 3 g. of tartaric acid and 5 ml. of a 30% aqueous solution of saponine are added to 1 liter of a 0.7% aqueous solution of a gallactomannan, for example Guar CSAA (trade name of Meypro A.G., Buchlingen, Switzerland). This solution is coated on a paper or film support and dried.
  • a cobalt leucophthalocyanine such as Phthalogen'blau 1B of Far-benfabriken Bayer A.G.
  • the negative material is brought into contact with the positive material. Both are then exposed for up to 10 seconds to a temperature of 170 C. by means of a developer apparatus as described in French Patent 1,346,705 or by means of a glazing press or a drying drum. After separation of the two materials, a blue image on a yellow background is obtained.
  • the negative material prepared according to the above prescription has also still not changed after a relatively long storage time, whereas a material without compound 7 is unsuitable for use after relatively short storage.
  • a heat developable photographic material comprising a support bearing a light sensitive silver halide emulsion layer and containing a silver halide developing substance, the improvement according to which the material also carries a compound of the following general formula wherein R and R represent a member of the group consisting of hydrogen atoms, an alkyl and an aryl radical,
  • R represents agfiiiember of the group consisting of an aryl and a heterocyclic radical
  • R and R together may represent the ring members forming a cyclohexyl ring
  • R represents a nitrile or nitro group.
  • a process for producing photographic silver images which comprises exposing to a subject to be reproduced a photographic material as claimed in claim 1 and subjecting the exposed material to heat to develop a silver image therein.
  • a process of producing photographic transfer images which comprises exposing to a subject to be reproduced a photographic material as claimed in claim 1, subjecting the exposed material to heat While it is in contact with a non-light sensitive transfer material to develop a silver image in said exposed material, to transfer developer substance from the unexposed areas of said exposed materials to the transfer layer and to produce a visible image in said transfer material by the action of said transferred developer substance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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)
US342528A 1963-02-18 1964-02-04 Heat developable light-sensitive photographic material Expired - Lifetime US3348945A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA42356A DE1174159B (de) 1963-02-18 1963-02-18 Waerme-Kopierverfahren unter Verwendung von lichtempfindlichen Materialien mit entwickler-haltigen Emulsionsschichten und photographisches Material hierfuer

Publications (1)

Publication Number Publication Date
US3348945A true US3348945A (en) 1967-10-24

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US342528A Expired - Lifetime US3348945A (en) 1963-02-18 1964-02-04 Heat developable light-sensitive photographic material

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US (1) US3348945A (en))
BE (1) BE643960A (en))
CH (1) CH456341A (en))
DE (1) DE1174159B (en))
GB (1) GB1053537A (en))

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2364017A (en) * 1941-06-13 1944-11-28 Du Pont Production of blue-black toned silver images
US3041170A (en) * 1959-10-29 1962-06-26 Eastman Kodak Co New class of development promoter precursors for dry processing self-developing silver halide coatings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2364017A (en) * 1941-06-13 1944-11-28 Du Pont Production of blue-black toned silver images
US3041170A (en) * 1959-10-29 1962-06-26 Eastman Kodak Co New class of development promoter precursors for dry processing self-developing silver halide coatings

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
DE1174159B (de) 1964-07-16
BE643960A (en)) 1964-08-18
CH456341A (de) 1968-07-15
GB1053537A (en))

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