EP0903628B1 - Matériau d'enregistrement thermographique à stabilité augmentée - Google Patents

Matériau d'enregistrement thermographique à stabilité augmentée Download PDF

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Publication number
EP0903628B1
EP0903628B1 EP98202655A EP98202655A EP0903628B1 EP 0903628 B1 EP0903628 B1 EP 0903628B1 EP 98202655 A EP98202655 A EP 98202655A EP 98202655 A EP98202655 A EP 98202655A EP 0903628 B1 EP0903628 B1 EP 0903628B1
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EP
European Patent Office
Prior art keywords
thermographic recording
recording material
substantially light
insensitive
silver salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98202655A
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German (de)
English (en)
Other versions
EP0903628A2 (fr
EP0903628A3 (fr
Inventor
Carlo Uyttendaele
Jan Gilleir
Ingrid Geuens
Ivan Hoogmartens
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Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
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Filing date
Publication date
Priority claimed from EP97203834A external-priority patent/EP0848286B1/fr
Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Priority to EP98202655A priority Critical patent/EP0903628B1/fr
Publication of EP0903628A2 publication Critical patent/EP0903628A2/fr
Publication of EP0903628A3 publication Critical patent/EP0903628A3/fr
Priority to EP99201317A priority patent/EP0964299A3/fr
Priority to US09/306,318 priority patent/US6184179B1/en
Priority to JP11158572A priority patent/JP2000062323A/ja
Application granted granted Critical
Publication of EP0903628B1 publication Critical patent/EP0903628B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • 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
    • G03C1/49827—Reducing agents
    • 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
    • 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
    • G03C1/49863—Inert additives, e.g. surfactants, binders
    • 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
    • G03C1/49872—Aspects relating to non-photosensitive layers, e.g. intermediate protective layers
    • 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
    • G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means

Definitions

  • the present invention relates to a substantially light-insensitive thermographic recording material with improved stability.
  • Thermography is concerned with materials which are substantially light-insensitive, but are sensitive to heat or thermographic. Most of the "direct" thermographic recording materials are of the chemical type. On heating to a certain conversion temperature, an irreversible chemical reaction takes place and a coloured image is produced.
  • a wide variety of chemical systems has been suggested some examples of which have been given on page 138 of the book "Imaging Systems” by Kurt I. Jacobson-Ralph E. Jacobson, The Focal Press - London and New York (1976), describing the production of a silver metal image by means of a thermally induced oxidation-reduction reaction of a silver soap with a reducing agent.
  • WO 94/16361 discloses a multilayer heat-sensitive material which comprises: a colour-forming layer comprising: a colour-forming amount of finely divided, solid colourless noble metal or iron salt of an organic acid distributed in a carrier composition; a colour developing amount of a cyclic or aromatic organic reducing agent, which at thermal copy and printing temperatures is capable of a colour-forming reaction with the noble metal or iron salt; and an image-toning agent; characterized in that (a) the carrier composition comprises a substantially water-soluble polymeric carrier and a dispersing agent for the noble metal or iron salt and (b) the material comprises a protective overcoating layer for the colour-forming layer.
  • thermographic recording materials from aqueous media are preferred over coating from solvent for ecological and economic reasons.
  • the inventors of the present invention found that the choice of surfactants used in the production of thermographic recording materials using aqueous dispersions and solutions had a substantial effect upon the stability of the thermographic recording materials produced and on prints produced therewith.
  • thermographic recording materials coated from aqueous media which exhibit improved stability.
  • thermographic recording materials which are capable of producing thermographic prints which exhibit improved stability.
  • thermographic recording materials coated from aqueous media can be as high as 500ppm without adversely affected the light-stability of thermographic recording materials coated from aqueous media.
  • thermographic recording material substantially exclusive of cationic surfactants in which at least one non-cationic surfactant is present
  • said thermographic recording material comprises a support and a thermosensitive element containing a substantially light-insensitive silver salt of an aliphatic carboxylic acid known as a fatty acid, a reducing agent therefor in thermal working relationship therewith and a binder, comprising the steps of: producing an aqueous dispersion of said substantially light-insensitive silver salt of an aliphatic carboxylic acid known as a fatty acid; producing one or more aqueous coating compositions containing together said aqueous dispersion of the substantially light-insensitive silver salt of an aliphatic carboxylic acid known as a fatty acid, said reducing agent and said binder; and applying said one or more aqueous coating compositions to said support thereby forming after drying said thermosensitive element, characterized in that one or more of said aqueous dispersion of said substantially light-in
  • thermographic recording material obtained by the above-mentioned process is also provided.
  • thermographic recording materials of the present invention are black and white thermographic recording materials.
  • aqueous for the purposes of the present invention includes mixtures of water with water-miscible organic solvents such as alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol etc.; glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc.
  • alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol etc.
  • glycols e.g. ethylene glycol
  • glycerine glycerine
  • N-methyl pyrrolidone methoxypropanol
  • ketones e.g. 2-propanone and 2-butanone etc.
  • substantially light-insensitive is meant not intentionally light sensitive.
  • substantially solvent-free aqueous medium is meant that solvent, if present, is present in amounts below 10% by volume of the aqueous medium.
  • Surfactants are surface active agents which are soluble compounds which reduce the interfacial tension between a liquid and a solid. Cationic surfactants have not been found to be useful for this application due to their photographic activity and the use of halide counterions in most commercial surfactants.
  • Non-cationic surfactants aid the dispersion of ingredients which are insoluble in the particular dispersion medium.
  • the thermographic recording materials of the present invention contain at least one non-cationic surfactant, which may be anionic, non-ionic or amphoteric.
  • all the non-cationic surfactants present in the thermographic recording material together have a non-fluoro-halide ion concentration of 1000ppm or less, with 500ppm or less being particularly preferred and 200ppm being especially preferred. It is also preferred that all the non-cationic surfactants present in the thermographic recording material together have a metal ion concentration of 500 ppm or less with 200 ppm or less being particularly preferred and specially preferably that all the non-cationic surfactants present in the thermographic recording material together have an alkali metal ion concentration of 200 ppm or less.
  • the alkali metal ions are: sodium, potassium, lithium, rubidium and caesium.
  • HOSTAPALTM B supplied as a 50% concentrate of a sodium trisalkylphenyl-polyethyleneglycol(EO 7-8)sulphate by HOECHST
  • Surfactant Nr. S02 MARLONTM A-365, supplied as a 65% concentrate of a sodium alkyl-phenylsulfonate by HÜLS
  • Surfactant Nr. S03 4-dodecylbenzene sulfonic acid from ;
  • Surfactant Nr. S04 ULTRAVONTM W, supplied as a 75-85% concentrate of a sodium arylsulfonate by CIBA-GEIGY; Surfactant Nr.
  • S05 HOSTAPURTMSAS, supplied as a 60% concentrate of a secondary alkanesulfonate by HOECHST;
  • Surfactant Nr. S06 MARLONTM AS3, supplied as a 98% concentrate of an alkylphenylsulfonic acid by HÜLS;
  • Surfactant Nr. S07 ANTAROXTM CO 880,a nonyl-phenyl-oxy-polyethyleneglycol(EO 30), from GAF;
  • Surfactant Nr. S08 SURFYNOLTM CT111, a nonionic surfactant supplied by AIR PRODUCTS; Surfactant Nr.
  • S09 ARKOPALTM N060 (previously HOSTAPALTM W), a nonylphenylpolyethylene-glycol from HOECHST.
  • Surfactant Nr. S10 GAFACTM RM710, a complex organic phosphate ester from GAF.
  • Surfactant Nr. S11 ALKANOLTM XC, supplied as a 90% concentrate of a sodium nonylnaphthalene-sulfonate by DU PONT;
  • Surfactant Nr. S12 sodium dodecyl sulphate from Surfactant Nr.
  • S13 DOWFAXTM 2A1, supplied as a 45% concentrate of a disodium salt of di(decyl-sulfo-phenyl)ether by DOW CORNING;
  • Surfactant Nr. S14 NIAPROOF ANIONICTM 4, supplied as a 27% concentrate of a sodium 1-(2'-ethylbutyl)-4-ethylhexylsulphate by NIACET;
  • Surfactant Nr. S15 HOSTA, supplied as a 95% concentrate of purified sodium salt of N-methyl-N-2-sulfoethyloleylamide, from HOECHST; Surfactant Nr.
  • MERSOLATTM H76 (previously MERSOLATTM H80), supplied as a 76% concentrate of a sodium pentadecylsulfonate by BAYER;
  • Surfactant Nr. S17 HOSTAPONTM T, supplied as a 40% concentrate of a sodium salt of N-methyl-N-2-sulfoethyloleylamide by HOECHST;
  • Surfactant Nr. S18 AKYPOTM OP80, supplied as an 80% concentrate of an octyl-phenyl-oxy-polyethyleneglycol(EO 8)acetic acid by CHEMY;
  • Surfactant Nr. S19 AKYPOTM RLM45, supplied as a 85% concentrate of a monoethanolamine salt of a polyethyleneglycol-substituted fatty acid, by CHEMY;
  • thermographic recording materials of the present invention surfactants S11 to S19 can only be used in combination with much larger quantities of surfactants with much lower chloride ion concentration, so that the overall chloride ion concentration in the surfactants present does not exceed 500ppm.
  • a substantially light-insensitive thermographic recording material comprising a thermosensitive element including a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith and a binder.
  • the element may comprise a layer system in which the ingredients are dispersed in different layers, with the proviso that the substantially light-insensitive organic silver salt and the organic reducing agent are in thermal working relationship with one another i.e. during the thermal development process the reducing agent must be present in such a way that it is able to diffuse to the substantially light-insensitive organic silver salt particles so that reduction of the organic silver salt can take place.
  • the thickness of the thermosensitive element is preferably in the range of 1 to 50 ⁇ m.
  • Preferred substantially light-insensitive silver salts of aliphatic carboxylic acids known as fatty acids have an aliphatic carbon chain with at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called "silver soaps".
  • Silver salts of modified aliphatic carboxylic acids with thioether group as described e.g. in GB-P 1,111,492 and other organic silver salts as described in GB-P 1,439,478, e.g. silver benzoate may likewise be used to produce a thermally developable silver image. Combinations of different organic silver salts may also be used in the present invention.
  • the aqueous dispersion of the substantially light-insensitive salt is preferably produced using a production process for a dispersion of particles of substantially light-insensitive organic silver salt including silver behenate in an aqueous medium comprising the steps of: i) producing an aqueous dispersion of one or more organic acids including behenic acid and a salt of an alkylarylsulfonate; ii) substantially neutralizing the organic acids with aqueous alkali thereby forming organic acid salts including a behenic acid salt; (iii) adding an aqueous solution of a silver salt to completely convert the organic acid salts into their silver salts including silver behenate, characterized in that the anionic surfactant is present in a molar ratio with respect to organic acid greater than 0.15 and the silver salt is added at a rate between 0.025mol/mol organic silver salt ⁇ min and 2.25mol/mol organic silver salt ⁇ min.
  • the anionic surfactant is present in a molar ratio with respect to organic carboxylic acid greater than 0.25 and the silver salt is added at a rate between 0.03mol/mol organic silver salt ⁇ min and 0.7mol/mol organic silver salt ⁇ min, with a molar ratio of anionic surfactant with respect to organic acid greater than 0.3 and a rate of silver salt addition of between 0.04mol/mol organic silver salt ⁇ min and 0.3mol/mol organic silver salt ⁇ min being particularly preferred.
  • step (iii) of the production process of the present invention is carried out such that part the solution of acid salts produced in step (ii) of the process is present in the reaction vessel prior to silver salt solution addition and part thereof is added simultaneously with the addition of the silver salt solution, with about 25 to 50% of the solution of acid salts produced in step (ii) being in the reaction vessel prior to silver salt addition being particularly preferred.
  • the pH used must be sufficiently low to avoid the oxidation of silver ions to silver oxide or silver hydroxide for which a pH below 10 is usually required
  • the process temperature is chosen such that it is above the melting point of the organic acid(s) used which in the case of behenic acid means a temperature of about 80 to 85°C, must be carried out with stirring, the stirring rate being dependent upon the size of the stirrer relative to the reaction vessel, the type of stirrer used, avoidance of silver oxide or silver hydroxide formation due to insufficient mixing and avoidance of foaming, and being usually between 200 and 1000rpm and a slight excess of an organic acid, for example behenic acid with e.g. 2 mol% excess being preferred.
  • the size of the silver acid salts particles containing silver behenate can be varied by varying the rate of silver salt addition, the concentration of anionic surfactant and the temperature, the equivalent diameter of the particles increasing with decreasing addition rate, decreasing anionic surfactant concentration and increasing temperature.
  • thermosensitive element Film-forming binders of the thermosensitive element
  • the layer containing the organic silver salt is applied from an aqueous medium containing a water-dispersible binder and/or a water dispersible binder.
  • Suitable water-soluble film-forming binders for use in thermosensitive element according to the present invention are: polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polyethyleneglycol, proteinaceous binders such as gelatin, modified gelatins such as phthaloyl gelatin, polysaccharides, such as starch, gum arabic and dextran and water-soluble cellulose derivatives.
  • a preferred water-soluble binder for use in the thermographic and photothermographic recording materials of the present invention is gelatin.
  • Suitable water-dispersible binders for use in the thermographic and photothermographic recording materials of the present invention may be any water-insoluble polymer It should be noted that there is no clear cut transition between a polymer dispersion and a polymer solution in the case of very small polymer particles resulting in the smallest particles of the polymer being dissolved and those slightly larger being in dispersion.
  • Preferred water-dispersible binders for use according to the present invention are water-dispersible film-forming polymers with covalently bonded ionic groups selected from the group consisting of sulfonate, sulfinate, carboxylate, phosphate, quaternary ammonium, tertiary sulfonium and quaternary phosphonium groups.
  • Further preferred water-dispersible binders for use according the the present invention are water-dispersible film-forming polymers with covalently bonded moieties with one or more acid groups.
  • the weight ratio of binder used according to the present invention to organic silver salt weight is preferably in the range of 0.2 to 6.
  • binders or mixtures thereof may be used in conjunction with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
  • heat solvent in this invention is meant a non-hydrolyzable organic material which is in a solid state in the recording layer at temperatures below 50°C, but upon heating becomes a plasticizer for the recording layer and/or a liquid solvent for at least one of the redox-reactants.
  • Suitable organic reducing agents for the reduction of organic silver salt particles containing silver stearate are organic compounds containing at least one active hydrogen atom linked to O, N or C, such as is the case with, aromatic di- and tri-hydroxy compounds; aminophenols; METOL (tradename); p-phenylene-diamines; alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-P 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
  • PHENIDONE (tradename); pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids; hydroxytetronimides; hydroxylamine derivatives such as for example described in US-P 4,082,901; hydrazine derivatives; and reductones e.g. ascorbic acid; see also US-P 3,074,809, 3,080,254, 3,094,417 and 3,887,378.
  • Catechol-type reducing agents i.e. reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position, such as catechol, 3-(3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybenzoic acid, gallic acid and esters e.g. methyl gallate, ethyl gallate, propyl gallate, tannic acid, and 3,4-dihydroxy-benzoic acid esters are preferred, with those described in EP-B 692 733 and unpublished European Patent Application EP 97202872.4 being particularly preferred.
  • Other suitable reducing agents are sterically hindered phenols, bisphenols and sulfonamidophenols.
  • Combinations of reducing agents may also be used that on heating become reactive partners in the reduction of the substantially light-insensitive organic silver salt containing silver stearate.
  • combinations of reducing agents with sulfonamidophenols are described in the periodical Research Disclosure, February 1979, item 17842, in US-P 4,360,581 and 4,782,004, and in EP-A 423 891 and combinations of sterically hindered phenols with sulfonyl hydrazide reducing agents such as disclosed in US-P 5,464,738; trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in US-P 5,496,695; trityl hydrazides and formyl-phenyl-hydrazides with diverse auxiliary reducing agents such as disclosed in US-P 5,545,505, US-P 5.545.507 and US-P 5,558,983; acrylonitrile compounds as disclosed in US-P 5,545,515 and US-P 5,
  • Organic reducing metal salts e.g. stannous stearate
  • stannous stearate have also been used in such reducing agent combinations, as disclosed in US-P 3,460,946 and 3,547,648, as have sterically hindered phenols and bisphenols, as described in US-P 4,001,026 and US-P 3,547,648 respectively.
  • thermographic recording materials may contain one or more toning agents.
  • the toning agents should be in thermal working relationship with the substantially light-insensitive organic silver salt and reducing agents during thermal processing. Any known toning agent from thermography or photothermography may be used. Suitable toning agents are the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901 and the toning agents described in US-P 3,074,809, US-P 3,446,648 and US-P 3,844,797.
  • Particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type described in GB-P 1,439,478, US-P 3,951,660 and US-P 5,599,647.
  • Suitable dispersants are natural polymeric substances, synthetic polymeric substances and finely divided powders, for example finely divided non-metallic inorganic powders such as silica.
  • thermographic recording materials of the present invention In order to obtain improved shelf-life and reduced fogging, stabilizers and antifoggants may be incorporated into the thermographic recording materials of the present invention.
  • the thermosensitive element may comprise in addition at least one polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 15 with respect to all the organic silver salt(s) present and in thermal working relationship therewith.
  • the polycarboxylic acid may be aliphatic (saturated as well as unsaturated aliphatic and also cycloaliphatic) or an aromatic polycarboxylic acid. These acids may be substituted e.g. with alkyl, hydroxyl, nitro or halogen. They may be used in anhydride form or partially esterified on the condition that at least two free carboxylic acids remain or are available in the heat recording step.
  • the substantially light-insensitive thermographic recording material may contain other additives such as free fatty acids, silicone oil, ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, and/or optical brightening agents.
  • the support for the substantially light-insensitive thermographic recording material according to the present invention may be transparent, translucent or opaque and is preferably a thin flexible carrier made e.g. from paper, polyethylene coated paper or transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. polyethylene terephthalate.
  • the support may be in sheet, ribbon or web form.
  • the support may be made of an opacified resin composition.
  • a subbing layer may also be provided between the support and the thermosensitive element.
  • the subbing layer contains a binder, less than 20% by weight of silica and covalently bonded acid groups in the binder, if present, are either substantially present as free acid or substantially present as acid salts.
  • the subbing layer contains a non-cationic surfactant.
  • the subbing layer used in the thermographic recording materials of the present invention contain less than 40ppm of free choride ions, with less than 10ppm of free chloride ions being especially preferably.
  • Preferred ingredients for the subbing layer used in the thermographic recording materials of the present invention are a polymer latex, polyethylene wax and hydrolyzed polyalkoxysilanes.
  • polyalkoxysilane is meant a silane with a least two hydrolyzable alkoxy-groups.
  • thermosensitive element may also be provided for the thermosensitive element.
  • this protective layer contains a non-cationic surfactant.
  • the protective layer protects the thermosensitive element from atmospheric humidity and from surface damage by scratching etc. and prevents direct contact of printheads or heat sources with the recording layers.
  • Protective layers for thermosensitive elements which come into contact with and have to be transported past a heat source under pressure, have to exhibit resistance to local deformation and good slipping characteristics during transport past the heat source during heating.
  • the protective layer may comprise a dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding therefrom.
  • suitable lubricating materials are a surface active agent, a liquid lubricant, a solid lubricant or mixtures thereof, which may be used with or without a polymeric binder.
  • Suitable slipping layer compositions are described, for example, in US 5,587,350, US 5,536,696, US 5,547,914, WO 95/12495, EP-A 775 592 and EP-A 775 595.
  • any layer of the substantially light-insensitive thermographic recording materials of the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc., 220 East 23rd Street, Suite 909 New York, NY 10010, USA.
  • Thermographic imaging is carried out by the image-wise application of heat either in analogue fashion by direct exposure through an image of by reflection from an image, or in digital fashion pixel by pixel either by using an infra-red heat source, for example with a Nd-YAG laser or other infra-red laser, or by direct thermal imaging with a thermal head.
  • thermal printing image signals are converted into electric pulses and then through a driver circuit selectively transferred to a thermal printhead.
  • the thermal printhead consists of microscopic heat resistor elements, which convert the electrical energy via the Joule effect into heat, which is transferred to the surface of the thermographic recording material wherein the chemical reaction resulting in the development of a black and white image takes place.
  • Such thermal printing heads may be used in contact or close proximity with the recording layer.
  • the operating temperature of common thermal printheads is in the range of 300 to 400°C and the heating time per picture element (pixel) may be less than 1.0 ms, the pressure contact of the thermal printhead with the recording material being e.g. 200-500g/cm 2 to ensure a good transfer of heat.
  • the image-wise heating of the recording layer with the thermal printing heads may proceed through a contacting but removable resin sheet or web wherefrom during the heating no transfer of recording material can take place.
  • the image signals for modulating the laser beam or current in the micro-resistors of a thermal printhead are obtained directly e.g. from opto-electronic scanning devices or from an intermediary storage means, optionally linked to a digital image work station wherein the image information can be processed to satisfy particular needs.
  • Activation of the heating elements can be power-modulated or pulse-length modulated at constant power.
  • EP-A 654 355 describes a method for making an image by image-wise heating by means of a thermal head having energizable heating elements, wherein the activation of the heating elements is executed duty cycled pulsewise.
  • thermographic recording materials When used in thermographic recording operating with thermal printheads the thermographic recording materials are not suitable for reproducing images with fairly large number of grey levels as is required for continuous tone reproduction.
  • EP-A 622 217 discloses a method for making an image using a direct thermal imaging element producing improvements in continuous tone reproduction.
  • Image-wise heating of the thermographic recording material can also be carried out using an electrically resistive ribbon incorporated into the material.
  • Image- or pattern-wise heating of the thermographic recording material may also proceed by means of pixelwise modulated ultra-sound, using e.g. an ultrasonic pixel printer as described e.g. in US-P 4,908,631.
  • Substantially light-insensitive thermographic recording materials according to the present invention may be used for both the production of transparencies, for example in the medical diagnostic field in which black-imaged transparencies are widely used in inspection techniques operating with a light box, and reflection type prints, for example in the hard copy field.
  • the support will be transparent or opaque, i.e. having a white light reflecting aspect.
  • the base may be colourless or coloured, e.g. with a blue colour for medical diagnostic applications.
  • thermosensitive element ingredients ii) thermosensitive element ingredients:
  • a 0.34mm thick polyethylene terephthalate sheet was coated to a thickness of 0.1mm with a composition which after drying and longitudinal and transverse stretching produced a 175 ⁇ m thick support coated on with the following subbing-layer composition expressed as the coating weights of the ingredients present: # copolymer of terephthalic acid/isophthalic acid/sulfoisophthalic acid/ethylene glycol (26.5/20/3.5/50) 37.0mg/m 2 # copolymer latex of ethyl acrylate/methacrylic acid (80/20) 3.0mg/m 2 # HORDAMERTM PE02 1.0mg/m 2 # PAREZ RESINTM 707 7.0mg/m 2
  • the tone modifier dispersion was prepared by first dissolving 8.8g of K7598 in 71.4g of deionized water by first adding the gelatin, then allowing the gelatin to swell for 30 minutes and finally heating to 50°C. 20 g of T01 was added with ULTRA-TURRAXTM stirring to this gelatin solution at 50°C, and the stirring continued for a further 5 minutes. Finally the resulting dispersion was pumped through a DYNOMILLTM for 2 hours to produce the final tone modifier dispersion containing: 20% of T01 and 8.8% of K7598.
  • thermographic recording materials of REFERENCE EXAMPLES 1 to 10 and COMPARATIVE EXAMPLES 1 & 2 were prepared by first dissolving 1.927g of K7598 in deionized water at 38°C (for the quantity of water see table 1), then adding with stirring to the warm K7598 solution: first 19.0g of the silver behenate dispersion, then 5.68g of the tone modifier dispersion as flakes followed by 15 minutes stirring, then the latex dispersion (for quantity, concentration and type see table 1), then 11.23g of an aqueous ethanol solution containing 0.92g of R01 and 0.62g of boric acid and finally 1.310g of a 3.7% by weight solution of formaldehyde to produce 60g of a dispersion containing: 7.47% of silver behenate, 0.75% of Surfactant Nr S02, 4.04% of K7598, 2.98% of polymer latex, 1.53% of R01, 1.03% of boric acid, 1.92% of T01 and 0.0
  • the resulting emulsions were then doctor blade-coated to a wet thickness of 60 ⁇ m at a blade setting of 100 ⁇ m onto the 175 ⁇ m thick subbed polyethylene terephthalate support and dried for 10 minutes at 50°C, producing a silver behenate coverage of about 4.0g/m 2 .
  • the printer was equipped with a thin film thermal head with a resolution of 300 dpi and was operated with a line time of 19ms (the line time being the time needed for printing one line). During this line time the printhead received constant power.
  • the average printing power being the total amount of electrical input energy during one line time divided by the line time and by the surface area of the heat-generating resistors was 1.6 mJ/dot being sufficient to obtain maximum optical density in each of the substantially light-insensitive thermographic recording materials of REFERENCE EXAMPLES 1 to 10 and COMPARATIVE EXAMPLES 1 & 2.
  • the maximum densities, D max , and minimum densities, D min , of the prints given in table 2 were measured through visible or blue filters with a MACBETHTM TR924 densitometer in the grey scale step corresponding to data levels of 64 and 0 respectively and are given in table 2.
  • the stability of the image background of the prints made with the substantially light-insensitive thermographic recording materials of REFERENCE EXAMPLES 1 to 10 and COMPARATIVE EXAMPLES 1 & 2 was evaluated on the basis of the change in minimum (background) density measured through a blue filter using a MACBETHTM TR924 densitometer upon exposure on top of the white PVC window of a specially constructed light-box placed for 3 days in a V ⁇ TSCH conditioning cupboard set at 30°C and a relative humidity (RH) of 85%. Only a central area of the window 550mm long by 500mm wide was used for mounting the test materials to ensure uniform exposure.
  • the stainless steel light-box used was 650mm long, 600mm wide and 120mm high with an opening 610mm long and 560mm wide with a rim 10mm wide and 5mm deep round the opening, thereby forming a platform for a 5mm thick plate of white PVC 630mm long and 580mm wide, making the white PVC-plate flush with the top of the light-box and preventing light loss from the light-box other than through the white PVC-plate.
  • This light-box was fitted with 9 PlaniluxTM TLD 36W/54 fluorescent lamps 27mm in diameter mounted length-wise equidistantly from the two sides, with the lamps positioned equidistantly to one another and the sides over the whole width of the light-box and with the tops of the fluorescent tubes 30mm below the bottom of the white PVC plate and 35mm below the materials being tested.
  • Table 2 The results are summarized in table 2.
  • Aqueous dispersions of the silver behenate types VI to IX of REFERENCE EXAMPLES 19 to 22 and of silver behenate types X & XI of COMPARATIVE EXAMPLES 6 & 7 respectively were produced as described for silver behenate types I to V of REFERENCE EXAMPLES 12 to 16 except as mentioned in table 7 below.
  • the volume average particle size as determined by a Coulter LS230 diffractometer is also given in table 7.
  • thermographic recording materials comprising thermographic elements coated from aqueous media.
  • thermographic recording materials of REFERENCE EXAMPLES 19 to 22 and COMPARATIVE EXAMPLES 6 & 7 were printed and the prints evaluated as described for REFERENCE EXAMPLES 1 to 10 and COMPARATIVE EXAMPLES 1 & 2.
  • the maximum and minimum densities of the prints obtained with the thermographic recording materials of REFERENCE EXAMPLES 19 to 22 and COMPARATIVE EXAMPLES 6 & 7 measured through a blue filter with a MACBETHTM TR924 densitometer for grey scale steps corresponding to data levels of 255 and 0 respectively are also given in table 9.
  • thermographic evaluation of the thermographic recording material of REFERENCE EXAMPLES 19 to 22 show lower increases in D min in archivability and light box tests, indicating higher stability, than those for the thermographic recording materials of COMPARATIVE EXAMPLES 6 & 7 which contain Surfactants with high chloride-ion concentrations (S18 and S12 respectively) in addition to Surfactant Nrs S01 and S08.
  • Silver behenate was added with stirring to an aqueous solution of different surfactants (for surfactant used see table 10) and the mixtures stirred for 30 minutes with a KOTTHOFFTM stirrer. The resulting dispersions were then ball milled to obtain a finely divided aqueous silver behenate dispersion with the quantities of surfactant with respect to silver behenate given in table 10.
  • thermographic recording materials of REFERENCE EXAMPLES 23 to 26 and COMPARATIVE EXAMPLES 8 to 13 were printed and the prints evaluated as described for REFERENCE 1 to 10 and COMPARATIVE EXAMPLES 1 & 2.
  • the maximum and minimum densities of the prints obtained with the thermographic recording materials of REFERENCE EXAMPLES 23 to 26 and COMPARATIVE EXAMPLES 8 to 13 measured through a blue filter with a MACBETHTM TR924 densitometer for grey scale steps corresponding to data levels of 255 and 0 respectively are also given in table 12.
  • thermographic evaluation of the thermographic recording material of REFERENCE EXAMPLES 23 to 26 show lower increases in D min in archivability and light box tests, indicating higher stability, than those for the thermographic recording materials of COMPARATIVE EXAMPLES 8 to 13 which contain Surfactants with high chloride-ion concentrations (S16, S11, S18, S17, S12 and S15 respectively)in addition to Surfactant Nrs S01 and S09 from the subbing layer of the support.
  • Silver behenate was added with stirring to an aqueous solution of different surfactants (for surfactant used see table 16) and the mixtures stirred for 30 minutes with a KOTTHOFFTM stirrer. The resulting dispersions were then ball-milled to obtain a finely divided aqueous silver behenate dispersion with the quantities of surfactant with respect to silver behenate given in table 16.
  • the resulting silver behenate dispersions were then doctor blade-coated onto a 175 ⁇ m thick subbed (subbing layer 1 described for COMPARATIVE EXAMPLE 5) polyethylene terephthalate support to produce the coating weights of silver given in table 17.
  • thermographic recording materials of REFERENCE EXAMPLES 27 and 28 and INVENTION EXAMPLES 1 and 2 were printed and the prints evaluated as described for REFERENCE EXAMPLES 1 to 10 and COMPARATIVE EXAMPLES 1 & 2.
  • the maximum and minimum densities of the prints obtained with the thermographic recording materials of REFERENCE EXAMPLES 27 and 28 and INVENTION EXAMPLES 1 and 2 measured through a blue filter with a MACBETHTM TR924 densitometer for grey scale steps corresponding to data levels of 255 and 0 respectively are also given in table 117.
  • thermographic evaluation of the thermographic recording material of REFERENCE EXAMPLES 27 and 28 and INVENTION EXAMPLES 1 and 2 show low increases in D min in archivability, indicating high stability, particularly in view of the subbing layer used which contains S16 with a very high concentration of chloride-ion. There is no significant diffference in light stability between the thermographic recording materials of REFERENCE EXAMPLES 27 and 28 and INVENTION EXAMPLES 1 and 2 indicating that up to a concentration of 524ppm the total chloride ion concentration in the surfactants present has no significant influence on the light stability of thermographic recording materials.

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Claims (14)

  1. Procédé pour la production d'un matériau d'enregistrement thermographique essentiellement non photosensible dans lequel on exclut essentiellement des agents tensioactifs cationiques et dans lequel est présent au moins un agent tensioactif non cationique, ledit matériau d'enregistrement thermographique comprenant un support et un élément thermosensible contenant un sel d'argent essentiellement non photosensible d'un acide carboxylique aliphatique désigné par l'expression « acide gras », un agent de réduction pour ledit sel en relation de travail thermique avec lui et un liant, comprenant les étapes consistant à : procurer une dispersion aqueuse dudit sel d'argent essentiellement non photosensible d'un acide carboxylique aliphatique désigné par l'expression « acide gras » ; produire une ou plusieurs compositions d'enduction aqueuses contenant, de manière conjointe, ladite dispersion aqueuse du sel d'argent essentiellement non photosensible d'un acide carboxylique aliphatique désigné par l'expression « acide gras », ledit agent de réduction et ledit liant ; et appliquer ladite ou lesdites compositions d'enduction aqueuse sur ledit support pour ainsi obtenir, après le séchage, ledit élément thermosensible, caractérisé en ce qu'une ou plusieurs desdites dispersions aqueuses dudit sel d'argent essentiellement non photosensible d'un acide carboxylique aliphatique désigné par l'expression acide gras et lesdites une ou plusieurs compositions d'enduction aqueuse contenant un agent tensioactif non cationique et la totalité desdits agents tensioactifs non cationiques présents dans le matériau d'enregistrement thermographique possèdent ensemble une concentration en ions halogénures de type non fluoro de 1500 à 200 ppm.
  2. Procédé de protection selon la revendication 1, dans lequel ladite dispersion aqueuse dudit sel d'argent organique essentiellement non photosensible est une dispersion aqueuse de particules d'un sel d'argent essentiellement non photosensible d'un acide carboxylique aliphatique désigné par l'expression « acide gras », y compris le béhénate d'argent, dans un milieu aqueux, que l'on obtient via un procédé comprenant les étapes consistant à : i) préparer une dispersion aqueuse d'un ou de plusieurs acides organiques, y compris l'acide béhénique, et d'un agent tensioactif anionique ; ii) soumettre lesdits acides organiques à une neutralisation substantielle avec des alcalis aqueux pour ainsi obtenir des sels d'acides organiques, y compris un sel d'acide béhénique ; iii) ajouter une solution aqueuse d'un sel d'argent pour transformer complètement lesdits sels d'acides organiques en leurs sels d'argent, y compris le béhénate d'argent, caractérisé en ce que ledit agent tensioactif anionique est présent dans un rapport molaire par rapport à l'acide organique supérieur à 0,15, et ledit sel d'argent est ajouté à un débit entre 0,025 mole/mole de sel d'argent organique par minute et 2,25 moles/mole de sel d'argent organique par minute.
  3. Matériau d'enregistrement thermographique essentiellement non photosensible que l'on obtient via le procédé selon la revendication 1 ou 2.
  4. Matériau d'enregistrement thermographique essentiellement non photosensible selon la revendication 3, dans lequel tous lesdits agents tensioactifs non cationiques présents possèdent ensemble une concentration en ions halogénures de type non fluoro de 1000 ppm ou moins.
  5. Matériau d'enregistrement thermographique essentiellement non photosensible selon la revendication 3 ou 4, dans lequel tous lesdits agents tensioactifs non cationiques présents possèdent ensemble une concentration en ions métalliques de 500 ppm ou moins.
  6. Matériau d'enregistrement thermographique essentiellement non photosensible selon l'une quelconque des revendications 3 à 5, dans lequel tous lesdits agents tensioactifs non cationiques présents possèdent ensemble une concentration en ions métalliques de 200 ppm ou moins.
  7. Matériau d'enregistrement thermographique essentiellement non photosensible selon l'une quelconque des revendications 3 à 6, dans lequel ledit ion halogénure de type non fluoro est un ion chlorure.
  8. Matériau d'enregistrement thermographique essentiellement non photosensible selon l'une quelconque des revendications 3 à 7, dans lequel ledit liant est de la gélatine.
  9. Matériau d'enregistrement thermographique essentiellement non photosensible selon l'une quelconque des revendications 3 à 8, dans lequel ledit élément thermosensible est muni d'une couche de protection.
  10. Matériau d'enregistrement thermographique essentiellement non photosensible selon la revendication 7, dans lequel ladite couche de protection contient un agent tensioactif non cationique.
  11. Matériau d'enregistrement thermographique essentiellement non photosensible selon l'une quelconque des revendications 3 à 10, dans lequel on prévoit une couche adhérente entre ledit élément thermosensible et ledit support.
  12. Matériau d'enregistrement thermographique essentiellement non photosensible selon la revendication 11, dans lequel ladite couche adhérente contient un agent tensioactif non cationique.
  13. Matériau d'enregistrement thermographique essentiellement non photosensible selon l'une quelconque des revendications 3 à 12, dans lequel ledit matériau d'enregistrement thermographique est un matériau d'enregistrement thermographique en noir et blanc.
  14. Matériau d'enregistrement thermographique essentiellement non photosensible selon la revendication 3, dans lequel tous lesdits agents tensioactifs non cationiques présents possèdent ensemble une concentration en ions de métaux alcalins de 200 ppm ou moins.
EP98202655A 1997-09-17 1998-08-06 Matériau d'enregistrement thermographique à stabilité augmentée Expired - Lifetime EP0903628B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98202655A EP0903628B1 (fr) 1997-09-17 1998-08-06 Matériau d'enregistrement thermographique à stabilité augmentée
EP99201317A EP0964299A3 (fr) 1998-06-06 1999-04-26 Matériau d'enregistrement thermographique à stabilité augmentée
US09/306,318 US6184179B1 (en) 1998-06-06 1999-05-06 Substantially thermographic recording materials with improved stability
JP11158572A JP2000062323A (ja) 1998-06-06 1999-06-04 改良された安定性を有する実質的にサ―モグラフィ性の記録材料

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Application Number Priority Date Filing Date Title
EP97202871 1997-09-17
EP97202876 1997-09-17
EP97202873 1997-09-17
EP97202877 1997-09-17
EP97202875 1997-09-17
EP97202877 1997-09-17
EP97202875 1997-09-17
EP97202873 1997-09-17
EP97202872 1997-09-17
EP97202876 1997-09-17
EP97202871 1997-09-17
EP97202872 1997-09-17
EP97203833 1997-12-06
EP97203833 1997-12-06
EP97203834 1997-12-06
EP97203834A EP0848286B1 (fr) 1996-12-10 1997-12-06 Produit d'enregistrement thermographique ayant un ton de l'image et/ou l'aptitude au stockage amélioré après developpement thermique
EP98201963 1998-06-06
EP98201963 1998-06-06
EP98202655A EP0903628B1 (fr) 1997-09-17 1998-08-06 Matériau d'enregistrement thermographique à stabilité augmentée

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US6579671B2 (en) * 1997-02-20 2003-06-17 Agfa-Gevaert Recording materials with improved shelf-life, image tone and/or stability upon thermal development
EP0964299A3 (fr) * 1998-06-06 2006-07-26 Agfa-Gevaert Matériau d'enregistrement thermographique à stabilité augmentée
JP3973798B2 (ja) * 1999-06-25 2007-09-12 富士フイルム株式会社 非感光性脂肪酸銀塩粒子の調製方法
US20040121273A1 (en) * 2002-12-03 2004-06-24 Hajime Nakagawa Photothermographic material
US7381520B2 (en) 2002-12-03 2008-06-03 Fujifilm Corporation Photothermographic material
JP4084645B2 (ja) * 2002-12-03 2008-04-30 富士フイルム株式会社 熱現像感光材料
EP1484641A1 (fr) * 2003-06-06 2004-12-08 Agfa-Gevaert Liants pour emploi dans les éléments sensibles à la chaleur de matériaux d' enregistrement thermographiques sensiblement non-sensibles à la lumière

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US2910377A (en) * 1956-06-28 1959-10-27 Minnesota Mining & Mfg Heat-sensitive copying-paper
EP0754969A2 (fr) * 1995-07-18 1997-01-22 Agfa-Gevaert N.V. Procédé pour produire une suspension aqueuse de particules contenant un sel d'argent d'un acide organique carboxylique substantiellement insensible à la lumière pour la production de matériaux (photo)thermographiques

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EP1327908A2 (fr) * 1996-06-01 2003-07-16 Agfa-Gevaert Matériau thermographique avec des capacités de transport améliorées
EP0848286B1 (fr) * 1996-12-10 2005-04-06 Agfa-Gevaert Produit d'enregistrement thermographique ayant un ton de l'image et/ou l'aptitude au stockage amélioré après developpement thermique
EP0851285B1 (fr) * 1996-12-30 2004-03-10 Agfa-Gevaert Produit d'enrégistrement pouvant être couché à partir d'un milieu aqueux

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2910377A (en) * 1956-06-28 1959-10-27 Minnesota Mining & Mfg Heat-sensitive copying-paper
EP0754969A2 (fr) * 1995-07-18 1997-01-22 Agfa-Gevaert N.V. Procédé pour produire une suspension aqueuse de particules contenant un sel d'argent d'un acide organique carboxylique substantiellement insensible à la lumière pour la production de matériaux (photo)thermographiques

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