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EP0809142B1 - Herstellungsverfahren für ein thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton - Google Patents

Herstellungsverfahren für ein thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton Download PDF

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Publication number
EP0809142B1
EP0809142B1 EP97201443A EP97201443A EP0809142B1 EP 0809142 B1 EP0809142 B1 EP 0809142B1 EP 97201443 A EP97201443 A EP 97201443A EP 97201443 A EP97201443 A EP 97201443A EP 0809142 B1 EP0809142 B1 EP 0809142B1
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EP
European Patent Office
Prior art keywords
recording material
image
thermosensitive element
heterocyclic ring
thermal
Prior art date
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Expired - Lifetime
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EP97201443A
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English (en)
French (fr)
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EP0809142A1 (de
Inventor
Bartholomeus Horsten
Johan Loccufier
Geert Defieuw
Luc Leenders
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP97201443A priority Critical patent/EP0809142B1/de
Publication of EP0809142A1 publication Critical patent/EP0809142A1/de
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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
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G03C1/49854—Dyes or precursors of dyes
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

  • the present invention relates to a thermographic material with a protective layer suitable for thermal development. In particular, it concerns improvements in the stabilization thereof.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated thermal energy.
  • Direct thermal thermography is concerned with materials which are substantially not photosensitive, but are sensitive to heat or thermosensitive. Imagewise applied heat is sufficient to bring about a visible change in a thermosensitive imaging material.
  • 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 typical heat-sensitive (thermographic) copy paper includes in the heat-sensitive layer a thermoplastic binder, e.g ethyl cellulose, a water-insoluble silver salt, e.g. silver stearate and an appropriate organic reducing agent, of which 4-methoxy-1-hydroxy-dihydronaphthalene is a representative.
  • a thermoplastic binder e.g ethyl cellulose
  • a water-insoluble silver salt e.g. silver stearate
  • an appropriate organic reducing agent of which 4-methoxy-1-hydroxy-dihydronaphthalene is a representative.
  • a heterocyclic organic toning agent such as phthalazinone is added to the composition of the heat-sensitive layer.
  • Thermo-sensitive copying paper is used in "front-printing” or “back-printing” using infra-red radiation absorbed and transformed into heat in contacting infra-red light absorbing image areas of an original as illustrated in Figures 1 and 2 of US-P 3,074,809.
  • DOS 2 400 224 and US-P 3,708,378 each disclose in its example 1 the incorporation of benzotriazole in the thermosensitive element of a thermographic recording material comprising silver behenate, methyl gallate as co-reactant and tetrachlorophthalic acid anhydride.
  • thermographic imaging element comprising a substrate having coated on at least one surface thereof a thermographic imaging system comprising a least one layer comprising light-insensitive organic silver salt; reducing agent for silver ion; binder; toner; and a dye which absorbs radiation in the wavelength range of 750-1100 nm, wherein said at least one layer comprising said light-insenstive organic silver salt forms an image density greater than about 1.0 when exposed to 0.10 - 2.0 J/cm 2 of said radiation in 0.20 to 200 ⁇ s.
  • light stabilizers such as benzotriazole, phenylmercaptotetrazole, and other light stabilizers known in the art may be added to the thermographic silver emulsion.
  • WO 94/16361 discloses a multilayer heat-sensitive material for direct thermal recording for which no intermediate drying of organic noble metal salts is necessary and which is coatable from aqueous dispersions.
  • This material comprises: a colour-forming amount of finely divided, solid colourless noble metal or iron salt of an organic acid distributed in a carrier composition; a color-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 said 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.
  • suitable antifoggants for use in the invention are well-known photographic antifoggants such as 2-mercaptobenzo-triazole, chromate, oxalate, carbonate, benzotriazole (BZT), 5-methylbenzotriazole, 5,6-dimethylbenzotriazole, 5-bromobenzotriazole, 5-chlorobenzo-triazole, 5-nitrobenzotriazole, 4-nitro-6-chlorobenzotriazole, 5-nitro-6-chlorobenzotriazole, 4-hydroxy-6-methyl-1,3,3a,7-tetraaza-indene, benzimidazole, 2-methylbenzimidazole, 5-nitrobenzimidazole, 1-phenyl-5-mercaptotetrazole (PMT), 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptothiazoline, 2-mercapto-4-methyl-6,6'-dimethyl
  • the colour neutrality of black monochrome images can be quantified by spectrophotometric measurements according to ASTM Norm E179-90 in a R(45/0) geometry with evaluation according to ASTM Norm E308-90 to produce the CIELAB a* and b* coordinates and the colour neutrality of the maximum density can be quantified using the numerical colour value (NCV).
  • thermosensitive element comprising a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith and a binder
  • thermosensitive element further comprises in reactive association with said substantially light-insensitive organic silver salt and said organic reducing agent a substituted, exclusive of groups having an exclusively electron withdrawing character, or unsubstituted compound with an unsaturated 5-membered heterocyclic ring annulated with an aromatic ring system, said heterocyclic ring consisting of nitrogen and carbon atoms with at least one of said nitrogen atoms having a hydrogen atom and none of said carbon atoms being directly linked to a sulfur atom or being part of a carbonyl-group, characterized in that said protective layer is crosslinked and comprises a binder, which is water-soluble or water-dispersible, a thermomeltable particle and particulate material.
  • thermosensitive element for producing a recording material as described above comprising the steps of: (i) providing a support; (ii) coating the support with a thermosensitive element; and (iii) coating the thermosensitive element with a protective layer from an aqueous medium, the protective layer being crosslinked and comprising a binder, which is water-soluble or water-dispersible, a thermomeltable particle and particulate material.
  • a thermal image recording process comprising the steps of: (i) providing a recording material as described above; (ii) bringing an outermost layer of the recording material into proximity with a heat source; (iii) applying heat from the heat source image-wise to the recording material while maintaining proximity to the heat source to produce an image; and (iv) removing the recording material from the heat source.
  • a thermal image forming process is realized, wherein the heat source is a thermal head, in particular a thin film thermal head.
  • the 5-membered heterocyclic ring contains three nitrogen atoms.
  • the 5-membered heterocyclic ring compound is benzotriazole, 5-methylbenzotriazole or 6-methylbenzotriazole.
  • Groups having an exclusively electron withdrawing character means, for the purposes of the present invention, electron withdrawing groups such as nitro, carboxy, sulfo groups etc which have no electron donating character and can be additionally characterized by their influence on benzene ring substitution, their directing a second substituent to a position meta to the group with exclusively electron withdrawing character.
  • Halide groups do not have an exclusively electron withdrawing character, having both an electron accepting and an electron donating character, and have a different influence on benzene ring substitution, directing a second substituent ortho or para to the halide group.
  • thermosensitive element is coated from an aqueous medium with a protective layer to avoid local deformation of the thermosensitive element and to improve resistance against abrasion.
  • the protective layer comprises a binder which is water-soluble or water dispersible.
  • the binder may be hydrophobic or hydrophilic.
  • hydrophobic binders polycarbonates as described in EP-A 614 769 are particularly preferred.
  • hydrophilic binders are preferred for the protective layer.
  • Suitable hydrophilic binders for the outermost layer are, for example, gelatin, polyvinylalcohol, cellulose derivatives or other polysaccharides, hydroxyethylcellulose, hydroxypropylcellulose etc., with hardenable binders being preferred and polyvinylalcohol being particularly preferred.
  • a protective layer according to the present invention in addition comprises a thermomeltable particle optionally with a lubricant present on top of the protective layer as described in WO 94/11199.
  • a thermomeltable particle optionally with a lubricant present on top of the protective layer as described in WO 94/11199.
  • at least one solid lubricant having a melting point below 150 ⁇ C and at least one liquid lubricant in a binder is present, wherein at least one of the lubricants is a phosphoric acid derivative.
  • suitable lubricating materials are surface active agents, liquid lubricants, solid lubricants which do not melt during thermal development of the recording material, solid lubricants which melt (thermomeltable) during thermal development of the recording material or mixtures thereof.
  • the lubricant may be applied with or without a polymeric binder.
  • the surface active agents may be any agents known in the art such as carboxylates, sulfonates, aliphatic amine salts, aliphatic quaternary ammonium salts, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, fluoroalkyl C 2 -C 20 aliphatic acids.
  • Examples of liquid lubricants include silicone oils, synthetic oils, saturated hydrocarbons and glycols.
  • solid lubricants include various higher alcohols such as stearyl alcohol and fatty acids.
  • Such protective layers also comprise particulate material, e.g. talc particles, optionally protruding from the protective outermost layer as described in WO 94/11198.
  • Other additives can also be incorporated in the protective layer e.g. colloidal particles such as colloidal silica.
  • the protective layer according to the present invention is crosslinked.
  • Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495 for protective layers, e.g. tetra-alkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins etc., with tetraalkoxysilanes such as tetramethylorthosilicate and tetraethylorthosilicate being preferred.
  • the protective layer of the recording material according to the present invention may comprise a matting agent.
  • Suitable matting agents are described in WO 94/11198 and include e.g. talc particles and optionally protrude from the outermost layer.
  • Solid or liquid lubricants or combinations thereof are suitable for improving the slip characteristics of the recording materials according to the present invention.
  • Solid lubricants which can be used according to the present invention are polyolefin waxes e.g. polypropylene waxes, ester waxes e.g. fatty acid esters, polyolefin-polyether block copolymers, amide waxes e.g. fatty acid amides, polyglycols e.g. polyethylene glycol, fatty acids, fatty alcohols, natural waxes and solid phosphoric acid derivatives.
  • polyolefin waxes e.g. polypropylene waxes
  • ester waxes e.g. fatty acid esters
  • polyolefin-polyether block copolymers amide waxes e.g. fatty acid amides
  • polyglycols e.g. polyethylene glycol
  • fatty acids fatty alcohols
  • natural waxes and solid phosphoric acid derivatives.
  • Preferred solid lubricants are thermomeltable particles such as those described in WO 94/11199 e.g. fatty acid esters, polyolefin-polyether block copolymers and fatty acid amides.
  • Preferred fatty acid esters are glycerine monostearate, glycerine monopalmitate and mixtures of glycerine monostearate and glycerine monopalmitate.
  • Preferred fatty acid amides are selected from the group consisting of ethylenebisstearamide, stearamide, oleamide, myristamide and erucamide.
  • Liquid lubricants which can be used according to the present invention according to the present invention are fatty acid esters such as glycerine trioleate, sorbitan monooleate and sorbitan trioleate, silicone oil derivatives and phosphoric acid derivatives such as ⁇ mono[isotridecyl polyglycolether (3 EO)]phosphate ⁇ , ⁇ mono[isotridecyl polyglycolether (6 EO)]phosphate ⁇ , ⁇ mono[oleyl polyglycolether (7 EO)]phosphate ⁇ and ⁇ mono[oleyl polyglycolether (7 EO)]phosphate ⁇ .
  • fatty acid esters such as glycerine trioleate, sorbitan monooleate and sorbitan trioleate
  • silicone oil derivatives and phosphoric acid derivatives such as ⁇ mono[isotridecyl polyglycolether (3 EO)]phosphate ⁇ , ⁇ mono[isotridecyl polygly
  • thermosensitive element comprises a substantially light-insensitive organic silver salt and an organic reducing agent therefor in thermal working relationship therewith in reactive association with a substituted, exclusive of groups having an exclusively electron withdrawing character, or unsubstituted compound with an unsaturated 5-membered heterocyclic ring annulated with an aromatic ring system, the ring consisting of nitrogen and carbon atoms with at least one of the nitrogen atoms having a hydrogen atom and none of the carbon atoms being part of a thione- or carbonyl-group.
  • the element may comprise a layer system in which the ingredients may be dispersed in different layers, with the proviso that all three ingredients are in reactive association with one another i.e.
  • the reducing agent and the compound with an unsaturated 5-membered heterocyclic ring annulated with an aromatic ring system must be present in such a way that they are able to diffuse to said substantially light-insensitive organic silver salt particles so that reduction of the organic silver salt to silver giving the desired image-tone can take place.
  • the compound with an unsaturated 5-membered heterocyclic ring annulated with an aromatic ring system must be present in such a way that the thermosensitive element can be stabilized against the influence of light.
  • Preferred organic silver salts according to the present invention are silver salts of aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, with silver behenate being particularly preferred.
  • Such silver salts are also called "silver soaps”.
  • Suitable organic reducing agents for the reduction of said substantially light-insensitive organic silver salts are organic compounds containing at least one active hydrogen atom linked to 0, N or C, such as is the case with, aromatic di- and tri-hydroxy compounds; aminophenols; METOL (tradename); p-phenylenediamines; 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.
  • aromatic di- and tri-hydroxy compounds having at least two hydroxy groups in para- or ortho-position on the same aromatic nucleus, e.g. benzene nucleus, hydroquinone and hydroquinone derivatives, and catechol and catechol derivatives respectively.
  • catechol-type reducing agents i.e. reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position
  • catechol pyrogallol
  • 3-(3,4-dihydroxyphenyl) propionic acid 1,2-dihydroxybenzoic acid
  • gallic acid gallic acid esters e.g.
  • the silver image density depends on the coverage of the above defined reducing agent(s) and organic silver salt(s) and has to be preferably such that, on heating above 100 °C, an optical density of at least 2.5 can be obtained. Preferably at least 0.10 moles of reducing agent per mole of organic silver salt is used.
  • auxiliary reducing agents are e.g. sterically hindered phenols, that on heating become reactive partners in the reduction of the substantially light-insensitive organic silver salt such as silver behenate, such as described in US-P 4,001,026; or are bisphenols, e.g. of the type described in US-P 3,547,648.
  • the auxiliary reducing agents may be present in the imaging layer or in a polymeric binder layer in thermal working relationship thereto.
  • auxiliary reducing agents are sulfonamidophenols as 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.
  • auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are organic reducing metal salts, e.g. stannous stearate described in US-P 3,460,946 and 3,547,648.
  • the thermosensitive element may comprise in addition at least one polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 20 with respect to all said organic silver salt(s) present and in thermal working relationship therewith.
  • the polycarboxylic acid may be aliphatic (saturated as well as unsaturayed 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.
  • saturated aliphatic dicarboxylic acids containing at least 4 carbon atoms e.g. : succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane-dicarboxylic acid, decane-dicarboxylic acid, undecane-dicarboxylic acid.
  • Suitable unsaturated dicarboxylic acids are : maleic acid, citraconic acid, itaconic acid and aconitic acid.
  • Suitable polycarboxylic acids are citric acid and derivatives thereof, acetonedicarboxylic acid, iso-citric acid and ⁇ -ketoglutaric acid.
  • Preferred aromatic polycarboxylic acids are ortho-phthalic acid and 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid and the anhydrides thereof.
  • thermosensitive element Film-forming binders of the thermosensitive element
  • the film-forming binder of the thermosensitive element containing the substantially light-insensitive organic silver salt may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously: e.g. cellulose derivatives such as ethylcellulose, cellulose esters, e.g.
  • cellulose nitrate carboxymethylcellulose, starch ethers, galactomannan
  • polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof.
  • a particularly suitable polyvinyl butyral containing a minor amount of vinyl alcohol units is marketed under the trade name BUTVARTM B79 of Monsanto USA and provides a good adhesion to paper and properly subbed polyester supports
  • the binder to organic silver salt weight ratio is preferably in the range of 0.2 to 6, and the thickness of the recording layer is preferably in the range of 5 to 50 ⁇ m.
  • 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 solid state in the recording layer at temperatures below 50°C but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic silver salt, at a temperature above 60°C.
  • the recording layer contains preferably in admixture with said organic silver salts and reducing agents a so-called toning agent known from thermography or photo-thermography.
  • Suitable toning agents are the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901. Further reference is made to the toning agents described in US-P 3,074,809, 3,446,648 and 3,844,797. Other particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type are described in GB-P 1,439,478 and US-P 3,951,660.
  • a toner compound particularly suited for use in combination with polyhydroxy benzene reducing agents is benzo[e][1,3]oxazine-2,4-dione described in US-P 3,951,660.
  • the recording layer may contain in addition to the ingredients mentioned above other additives such as free fatty acids, surface-active agents, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, silicone oil, e.g. BAYSILONETM ⁇ 1 A (from BAYER AG, GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments and/or optical brightening agents.
  • antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
  • silicone oil e.g. BAYSILONETM ⁇ 1 A (from BAYER AG, GERMANY)
  • ultraviolet light absorbing compounds e.g. BAYSILONETM ⁇ 1 A (from BAYER AG, GERMANY)
  • the support for the thermal imaging material according to the present invention may be transparent, translucent or opaque, e.g. having a white light reflecting aspect 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.
  • a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and said paper base substrate.
  • the support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermosensitive recording layer.
  • the support may be made of an opacified resin composition, e.g. polyethylene terephthalate opacified by means of pigments and/or micro-voids and/or coated with an opaque pigment-binder layer, and may be called synthetic paper, or paperlike film; information about such supports can be found in EP's 194 106 and 234 563 and US-P's 3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent base be used, said base may be colourless or coloured, e.g. having a blue colour.
  • One or more backing layers may be provided to control physical properties such as curl and static.
  • an antistatic layer is applied to the outermost layer not comprising at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder, wherein at least one of said lubricants is a phosphoric acid derivative.
  • any layer of the recording material 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, U.S.A.
  • Thermographic imaging is carried by the image-wise application of heat either in analogue fashion by direct exposure through an image or 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 direct thermal imaging with a thermal head.
  • an infra-red heat source for example with a Nd-YAG laser or other infra-red laser, or 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 into heat via Joule effect.
  • the electric pulses thus converted into thermal signals manifest themselves as heat transferred to the surface of the thermal paper wherein the chemical reaction resulting in colour development takes place.
  • 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 50ms or less, the pressure contact of the thermal printhead with the recording material being e.g. 100-500g/cm 2 to ensure a good transfer of heat.
  • the direct thermal image-wise heating of the recording material proceeds by Joule effect heating in that selectively energized electrical resistors of a thermal head array are used in contact or close proximity with said recording layer.
  • Suitable thermal printing heads are e.g. a Fujitsu Thermal Head (FTP-040 MCS001), a TDK Thermal Head F415 HH7-1089 and a Rohm Thermal Head KE 2008-F3.
  • the image signals for modulating the 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, e.g. magnetic disc or tape or optical disc storage medium, optionally linked to a digital image work station wherein the image information can be processed to satisfy particular needs.
  • an intermediary storage means e.g. magnetic disc or tape or optical disc storage medium
  • Activation of the heating elements can be power-modulated or pulse-length modulated at constant power.
  • Direct thermal imaging can be used for both the production of transparencies and reflection type prints.
  • Application of the present invention is envisaged in the fields of both graphics images requiring high contrast images with a very steep print density applied dot energy dependence and continuous tone images requiring a weaker print density applied dot energy dependence, such as required in the medical diagnostic field.
  • In the hard copy field recording materials on a white opaque base are used, whereas in the medical diagnostic field black-imaged transparencies are widely used in inspection techniques operating with a light box.
  • thermosensitive elements with the compositions given in table 1 for comparative examples 1 to 9 and invention examples 1 to 4.
  • thermosensitive element was then coated with an aqueous composition.
  • the pH of the coating composition was adjusted to a pH of 4 by adding 1N nitric acid.
  • Those lubricants which were insoluble in water, were dispersed in a ball mill with, if necessary, the aid of a dispersion agent.
  • composition was coated to a wet layer thickness of 85 ⁇ m and then dried at 40°C for 15 minutes and hardened at 57°C and a relative humidity of 34% for 2 days to produce a layer with the following composition expressed as the coating weight of the ingredients present: # polyvinylalcohol (MowiviolTM WX 48 20, Wacker Chemie) 4.9g/m 2 # dispersion agent (UltravonTM W from Ciba Geigy) 0.075g/m 2 # colloidal silica (LevasilTM VP AC 4055 from Bayer AG, a 15% aqueous dispersion of colloidal silica) 1.05g/m 2 # mono[isotridecyl polyglycolether (3 EO)] phosphate (ServoxylTM VPDZ 3/100 from Servo Delden) 0.075g/m 2 # mixture of monolauryl and dilauryl phosphates (Servoxyl VPAZ 100 from Servo Delden) 0.075g/m 2 # talc
  • 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 said line time the print head 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 1.5mJ/dot being sufficient to obtain maximum optical density in each of said recording materials.
  • the optical maximum and minimum densities of the prints given in table 2 were measured through a visual filter with a MacbethTM TR924 densitometer in the grey scale step corresponding to data levels of 255 and 0 respectively.
  • NCV values were determined at optical densities (D) with a visual filter of 1, 2 and 3 for the fresh materials and for the same materials after being heated at 57°C in a relative humidity of 34% for 3 days for the materials of comparative examples 1 to 5 and invention examples 1 to 8 and the NCV-values obtained summarized in table 2.
  • the NCV-values in table 2 enable materials with different stabilizing compounds at different concentrations to be compared on the basis of their colour neutrality, the dependence of their colour neutrality upon image optical density and the pre-exposure evolution in colour neutrality.
  • the stability of the image background of the materials of comparative examples 1 to 7 and invention examples 1 to 6 to post-image development exposure was evaluated by first thermally treating the materials for 3 days at 57°C and 34% relative humidity, next producing images in the materials by image-wise thermal development and finally exposing the images formed in the materials for 3 days on top of the white PVC window of a specially constructed light-box placed in a Votsch conditioning cupboard set at 30°C and a relative humidity 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.
  • the suitability of a material was assessed on the basis of the initial background density determined through a blue filter using a MacBethTM TR924 densitometer, the background density through a blue filter after exposure in the lightbox for 3 days at 30°C and 85% relative humidity and the L*, a* and b* CIELAB-values of the background after 3 days and 6 days exposure in the lightbox at 30°C and 85% relative humidity.
  • the L*, a* and b* CIELAB-values of the background were determined by spectrophotometric measurements according to ASTM Norm E179-90 in a R(45/0) geometry with evaluation according to ASTM Norm E308-90.
  • Colour neutrality on the basis of CIELAB-values corresponds to a* and b* values of zero, with a negative a*-value indicating a greenish image-tone becoming greener as a* becomes more negative, a positive a*-value indicating a reddish image-tone becoming redder as a* becomes more positive, a negative b*-value indicating a bluish image-tone becoming bluer as b* becomes more negative and a positive b*-value indicating a yellowish image-tone becoming yellower as b* becomes more positive.
  • the degree of transparency of the materials of invention examples 1 to 6, as indicated by their L*-values, at ⁇ 85 was significantly higher than that of the materials of comparative examples 1 to 7 which varied between 77 and 84.
  • the b*-values of the materials of invention examples 1 to 6 were much lower at ⁇ 15.43 i.e. much less yellow than those of the materials of comparative examples 1 to 7, which varied between 18.91 and 37.68.
  • Comparative examples 1 to 7 show by comparison with invention examples 1 to 6 that recording materials comprising a thermosensitive element comprising a substituted, exclusive of groups having an exclusively electron withdrawing character, or unsubstituted compound with an unsaturated 5-membered heterocyclic ring annulated with an aromatic ring system, said ring consisting of nitrogen and carbon atoms with at least one of said nitrogen atoms having a hydrogen atom and none of said carbon atoms being part of a thione- or carbonyl-group exhibit images with superior stability and/or images with superior colour neutrality and/or an image background with superior colour neutrality compared with materials without such compounds (comparative example 1), with materials with C01, an unsaturated 5-membered heterocyclic ring consisting of nitrogen and carbon atoms annulated with a substituted benzene ring and having a nitrogen with a hydrogen atom, but with an exclusively electron withdrawing substituent (comparative examples 2 and 3), with materials with C02, an unsaturated 5-membered heterocyclic ring
  • the recording materials of invention examples 7 and 8 and comparative example 8 were produced as described for invention examples 1 to 6 and comparative examples 1 to 7 except that the quantities of ingredients present in the materials were different.
  • the recording material of comparative example 8 was produced as described for comparative example 1.
  • the compositions of the thermosensitive elements are given in table 4.
  • Table 6 shows that the materials of the invention examples exhibit significantly lower D min -values after 3 days lightbox exposure than that comparative examples 8 without a stabilizing compound according to the present invention. Furthermore, the materials of the invention examples also exhibit backgrounds with a much higher degree of colour neutrality as adjudged by their a*- and b*-values after 3 days and 6 days lightbox exposure than those of comparative example 8 without a stabilizing compound according to the present invention, the latter exhibiting a marked yellow tone.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (10)

  1. Ein im Wesentlichen aus einem Träger, einem wärmeempfindlichen Element und einer Schutzschicht dafür bestehendes Aufzeichnungsmaterial, wobei das wärmeempfindliche Element ein wesentlich lichtunempfindliches organisches Silbersalz, ein organisches Reduktionsmittel dafür in thermischer wirksamer Beziehung dazu und ein Bindemittel enthält, dadurch gekennzeichnet, dass das wärmeempfindliche Element ferner in reaktiver Beziehung zum wesentlich lichtunempfindlichen organischen Silbersalz und dem organischen Reduktionsmittel eine gegebenenfalls, jedoch nicht durch eine ausschließlich elektronenanziehende Gruppe, substituierte Verbindung mit einem ungesättigten 5-gliedrigen heterocyclischen, mit einem aromatischen Ringsystem anellierten Ring enthält, wobei der heterocyclische Ring aus Stickstoffatomen und Kohlenstoffatomen besteht und zumindest eines der Stickstoffatome an ein Wasserstoffatom gebunden und keines der Kohlenstoffatome direkt an ein Schwefelatom gebunden oder Teil einer Carbonylgruppe ist, dadurch gekennzeichnet, dass die Schutzschicht vernetzt ist und ein wasserlösliches oder wasserdispergierbares Bindemittel, ein thermisch schmelzbares Teilchen und teilchenförmiges Material enthält.
  2. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass der 5-gliedrige heterocyclische Ring drei Stickstoffatome enthält.
  3. Aufzeichnungsmaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die 5-gliedrige heterocyclische Ringverbindung Benztriazol ist.
  4. Aufzeichnungsmaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die 5-gliedrige heterocyclische Ringverbindung 5-Methylbenztriazol ist.
  5. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das wesentlich lichtunempfindliche organische Silbersalz ein wesentlich lichtunempfindliches Fettsäuresilbersalz ist.
  6. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das wärmeempfindliche Element ferner zumindest ein Tönungsmittel aus der Gruppe bestehend aus heterocyclischen Tonerverbindungen des Benzoxazindion-Typs enthält.
  7. Ein durch die nachstehenden Schritte gekennzeichnetes Verfahren zur Herstellung eines im Wesentlichen aus einem Träger, einem wärmeempfindlichen Element und einer Schutzschicht dafür bestehenden Aufzeichnungsmaterials : (i) Bereitstellen eines Trägers, (ii) Beschichten des Trägers mit einem wärmeempfindlichen Element, das ein wesentlich lichtunempfindliches organisches Silbersalz, ein organisches Reduktionsmittel dafür in thermischer wirksamer Beziehung dazu und eine gegebenenfalls, jedoch nicht durch eine ausschließlich elektronenanziehende Gruppe, substituierte Verbindung mit einem ungesättigten 5-gliedrigen heterocyclischen, mit einem aromatischen Ringsystem anellierten Ring enthält, wobei der heterocyclische Ring aus Stickstoffatomen und Kohlenstoffatomen besteht und zumindest eines der Stickstoffatome an ein Wasserstoffatom gebunden und keines der Kohlenstoffatome Teil einer Thiongruppe oder Carbonylgruppe in reaktiver Beziehung zum wesentlich lichtunempfindlichen organischen Silbersalz, dem organischen Reduktionsmittel und einem Bindemittel ist, und (iii) Beschichtung des wärmeempfindlichen Elements mit einer Schutzschicht aus einem wässrigen Medium, wobei die Schutzschicht vernetzt ist und ein wasserlösliches oder wasserdispergierbares Bindemittel, ein thermisch schmelzbares Teilchen und teilchenförmiges Material enthält.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das wärmeempfindliche Element aus einem nicht-wässrigen Medium aufgetragen wird.
  9. Ein durch die nachstehenden Schritte gekennzeichnetes thermisches Bilderzeugungsverfahren : (i) Bereitstellen eines Aufzeichnungsmaterials nach einem der Ansprüche 1 bis 6 oder nach einem Herstellungsverfahren nach einem der Ansprüche 7 und 8, (ii) Anordnen einer Außenschicht des Aufzeichnungsmaterials in der Nähe einer Heizquelle, (iii) bildmäßige Beaufschlagung des Aufzeichnungsmaterials mit von der Heizquelle gelieferter Wärme zur Herstellung eines Bildes, wobei das Aufzeichnungsmaterial in der Nähe der Heizquelle gehalten wird, und (iv) Entfernen des Aufzeichnungsmaterials von der Heizquelle.
  10. Thermisches Bilderzeugungsverfahren nach Anspruch 9, dadurch gekennzeichnet, dass die Heizquelle ein Thermokopf ist.
EP97201443A 1996-05-21 1997-05-14 Herstellungsverfahren für ein thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton Expired - Lifetime EP0809142B1 (de)

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US6348308B1 (en) 1997-09-03 2002-02-19 Agfa-Gevaert Substantially light-insensitive thermographic recording material with improved stability and image-tone
US6326331B1 (en) 1998-11-30 2001-12-04 Agfa-Gevaert Substantially light-insensitive black and white thermographic recording material with improved stability to direct sunlight
EP1006406B1 (de) * 1998-11-30 2003-08-27 Agfa-Gevaert Thermographisches Schwarz-Weiss-Aufzeichnungsmaterial mit verbesserter Stabilität gegenüber direkter Sonneneinstrahlung
US6337303B1 (en) 1999-06-04 2002-01-08 Agfa-Gevaert Thermographic recording materials with improved image tone
EP1059560A1 (de) * 1999-06-04 2000-12-13 Agfa-Gevaert N.V. Thermographisches Aufzeichnungsmaterial mit verbessertem Bildton

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