EP0782043B1 - Wärmeempfindliches Aufzeichnungsmaterial mit verbesserter Tonwiedergabe - Google Patents

Wärmeempfindliches Aufzeichnungsmaterial mit verbesserter Tonwiedergabe Download PDF

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Publication number
EP0782043B1
EP0782043B1 EP19960203640 EP96203640A EP0782043B1 EP 0782043 B1 EP0782043 B1 EP 0782043B1 EP 19960203640 EP19960203640 EP 19960203640 EP 96203640 A EP96203640 A EP 96203640A EP 0782043 B1 EP0782043 B1 EP 0782043B1
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EP
European Patent Office
Prior art keywords
recording material
layer
agos
colloidal particles
material according
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EP19960203640
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English (en)
French (fr)
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EP0782043A1 (de
Inventor
Bartholomeus Horsten
An Vankeerberghen
Luc Leenders
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C1/4989—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
    • G03C1/32—Matting 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • 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
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • 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
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • 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
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
    • G03C2001/7488—Sliding layers or means
    • 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
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • G03C2001/7628—Back layer

Definitions

  • the present invention relates to a thermographic material suitable for thermal development.
  • it concerns improvements in tonal reproduction due to its thermosensitive element having a particular composition.
  • 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.
  • the image quality is strongly dependent upon the tone response of the direct thermal recording material to the heating pulses image-wise applied to the heat source and in particular the dependence of image density upon the power input to the heat source. Fine tuning of the response of the material enables image quality to be obtained whether continuous tone images are desired, for which a fairly large number of grey levels are required and therefore a moderately flat response is necessary, or graphics imaging is desired, requiring a single image tone and a very strong dependence of image density upon the power input to the heat source.
  • a recording material comprising at least one thermosensitive element, comprising a layer comprising at least one substantially light-insensitive organic silver salt in at least one binder and in thermal working relationship therewith an organic reducing agent therefor, on a support, characterized in that the recording material is light-insensitive and the layer contains colloidal particles comprising silicon dioxide at a coating weight given by expression (1): 0.015 x B AGOS ⁇ S AGOS ⁇ 1.2 ( B AGOS - 0.4) wherein B represents the weight of all binders in the layer, AGOS represents the weight of all organic silver salts in the layer and S represents the weight of the colloidal particles in the layer.
  • thermo image forming process for producing high contrast images comprising the steps of: (i) bringing an outermost layer of a recording material as described above; (2) applying heat from a heat source image-wise to the recording material while maintaining mutual contact to the heat source; and (3) separating the recording material from the heat source.
  • a thermal image forming process is realized, wherein the heat source is a thermal head.
  • a thermal image forming process is realized, wherein the heat source is a thin film thermal head.
  • the layer contains the colloidal particles at a coating weight given by expression (2): 0.1 x B AGOS ⁇ S AGOS ⁇ 1.0 ( B AGOS - 0.4) wherein B represents the weight of all binders in the layer, AGOS represents the weight of all organic silver salts in the layer and S represents the weight of colloidal particles in the layer.
  • the layer contains the colloidal particles at a coating weight given by expression (3): 0.2 x B AGOS ⁇ S AGOS ⁇ 0.8 ( B AGOS - 0.4) wherein B represents the weight of all binders in the layer, AGOS represents the weight of all organic silver salts in the layer and S represents the weight of the collidal particles in the layer.
  • the recording material has a haze value, determined according to ASTM standard D1003 procedure B, of less than 35%.
  • Colloidal particles comprising silicon dioxide
  • Preferred types of colloidal particles comprising silicon dioxide are those that are hydrophobized thereby making them readily dispersible in the binders of the layer comprising at least one light-insensitive organic silver salt without substantially reducing the transparency of the recording layer of the present invention.
  • Preferred types of colloidal particles comprising silicon dioxide, according to the present invention have specific surface areas of less than 100m 2 /g.
  • colloidal particles comprising silicon dioxide are hydrophobized grades of amorphous flame hydrolyzed silica for example AerosilTM R812 and AerosilTM R972 from Degussa AG.
  • the outermost layer of the recording material may in different embodiments of the present invention be the outermost layer of the thermosensitive element, a protective layer applied to the thermosensitive element or a layer on the opposite side of the support to the thermosensitive element.
  • the outermost layer surface layer of the recording material according to the present invention may be a protective layer applied to the thermosensitive element to avoid local deformation of the thermosensitive element and to improve resistance against abrasion.
  • the protective layer preferably comprises a binder, which may be hydrophobic (solvent soluble) of hydrophilic (water soluble).
  • a binder which may be hydrophobic (solvent soluble) of hydrophilic (water soluble).
  • hydrophobic binders polycarbonates as described in EP-A 614 769 are particularly preferred.
  • hydrophilic binders are preferred for the protective layer, as coating can be performed from an aqueous composition and mixing of the hydrophilic protective layer with the immediate underlayer can be avoided by using a hydrophobic binder in the immediate underlayer.
  • a protective layer according to the present invention may comprise in addition 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 may 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 outermost layer of the recording material may comprise a hydrophilic binder.
  • 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.
  • the outermost layer according to the present invention may be 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 outermost 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.
  • the element may comprise a layer system in which the ingredients may be 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.
  • 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 the substantially light-insensitive organic silver salts 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-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 ortho- or para-position on the same aromatic nucleus
  • aromatic nucleus e.g. benzene nucleus, hydroquinone and substituted hydroquinones, catechol, pyrogallol, gallic acid and gallic acid esters
  • polyhydroxy spiro-bis-indane compounds especially these corresponding to the following general formula (I): wherein :
  • polyhydroxy-spiro-bis-indane compounds described in US-P 3,440,049 as photographic tanning agent, more especially 3,3,3',3'-tetramethyl-5,6,5',6'-tetrahydroxy-1,1'-spiro-bis-indane (called indane I) and 3,3,3'.3'-tetramethyl-4,6,7,4',6',7'-hexahydroxy-1,1'-spiro-bis-indane (called indane II).
  • Indane is also known under the name hydrindene.
  • catechol-type reducing agents i.e. reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position
  • 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.
  • catechol-type reducing agents are benzene compounds in which the benzene nucleus is substituted by no more than two hydroxy groups which are present in 3,4-position on the nucleus and have in the 1-position of the nucleus a substituent linked to the nucleus by means of a carbonyl group.
  • 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 corresponding to the following general formula : Aryl-SO 2 -NH-Arylene-OH in which :
  • 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 the 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.
  • the layer containing the organic silver salt is commonly coated onto a support in sheet- or web-form from an organic solvent containing the binder dissolved therein, but may be applied from an aqueous medium as a latex, i.e. as an aqueous polymer dispersion.
  • a latex the dispersible polymer has preferably some hydrophilic functionality.
  • Polymers with hydrophilic functionality for forming an aqueous polymer dispersion (latex) are described e.g. in US-P 5,006,451, but serve therein for forming a barrier layer preventing unwanted diffusion of vanadium pentoxide present as an antistatic agent.
  • 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.
  • redox-reactants e.g. the reducing agent for the organic silver salt
  • the recording layer contains preferably in admixture with the 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 within the scope of following general formula : in which:
  • a toner compound particularly suited for use in combination with polyhydroxy benzene reducing agents is 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine 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 ⁇ l 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 ⁇ l A (from BAYER AG, GERMANY)
  • ultraviolet light absorbing compounds e.g. BAYSILONETM ⁇ l 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 the 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, the 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 the lubricants is a phosphoric acid derivative.
  • Suitable antistatic layers therefor are described in EP-A 440 957.
  • 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.
  • 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 imagewise heating of the recording material 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 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 the 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
  • 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.
  • a subbed polyethylene terephthalate support having a thickness of 175 ⁇ m was doctor blade-coated from a coating composition containing butanone as a solvent and the following ingredients so as to obtain thereon, after drying for 1 hour at 50°C, layers with the compositions given in tables 1 and 2 for the COMPARATIVE EXAMPLE and INVENTION EXAMPLES respectively.
  • the coating quality of the resulting coatings was evaluated using haze and gloss measurements to ascertain whether the presence of relatively large quantities of finely divided silicon dioxide had an adverse effect on their transparency.
  • 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 the 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 the recording materials.
  • the print head was separated from the imaging layer by a thin intermediate material contacted with a slipping layer of a separable 5 ⁇ m thick polyethylene terephthalate ribbon coated successively with a subbing layer, heat-resistant layer and the slipping layer (anti-friction layer) giving the ribbon with a total thickness of 6 ⁇ m.
  • the optical maximum and minimum densities of the prints given in table II were measured through a visual filter with a MacbethTM TD904 densitometer in the grey scale step corresponding to data levels of 255 and 0 respectively.
  • the numerical gradation value (NGV) corresponding to the expression: (2.5 - 0.06)/(E 2.5 - E 0.06 ) was determined; where E 2.5 is that energy in Joule applied to a dot area of 87 ⁇ m x 87 ⁇ m of the recording material required to obtain an optical density value of 2.5 as measured with a MacbethTM TD904 densitometer, and E 0.06 is that energy in Joule applied to a dot area of 87 ⁇ m x 87 ⁇ m of the recording material required to obtain an optical density value of 0.06 as measured with a MacbethTM TD904 densitometer.
  • the applied energy in Joule is actually the electrical input energy measured for each resistor of the thermal head.
  • NCV values were determined at optical densities (D) of 1, 2 and 3.
  • the recording materials of INVENTION EXAMPLE 4 and COMPARATIVE EXAMPLES 2 to 4 were produced as described for INVENTION EXAMPLES 1 to 3 and COMPARATIVE EXAMPLE 1, but with different quantities of the same ingredients in the thermosensitive element as summarised in tables 5 and 6 for the COMPARATIVE EXAMPLES and INVENTION EXAMPLE respectively.
  • the ingredient quantities for the thermosensitive element of the recording material of INVENTION EXAMPLE 3 are included in table 6 for the sake of comparison.
  • the recording materials of INVENTION EXAMPLE 7 and COMPARATIVE EXAMPLES 7 and 8 were produced as described for INVENTION EXAMPLES 1 to 3 and COMPARATIVE EXAMPLE 1, but with different quantities of the same ingredients in the thermosensitive element as summarised in tables 13 and 14 for the COMPARATIVE EXAMPLES and INVENTION EXAMPLE respectively.
  • the ingredient quantities for the thermosensitive element of the recording material of COMPARATIVE EXAMPLE 2 are included in table 13 for the sake of comparison.
  • thermosensitive element transparency in the range above this value and below 1.2 of the PVB/AgBeh weight ratio less 0.4 at which a loss of thermosensitive element transparency was observed, a significant increase in the numerical gradation value, NGV, was observed without any adverse effect on the thermosensiti0-ve element transparency and on imaging characteristics such as the numerical color value, maximum print density and minimum print density.

Claims (11)

  1. Ein Aufzeichnungsmaterial mit zumindest einem wärmeempfindlichen Element, das auf einem Träger eine Schicht mit zumindest einem wesentlich lichtunempfindlichen organischen Silbersalz in zumindest einem Bindemittel und in thermischer wirksamer Beziehung dazu einem organischen Reduktionsmittel dafür enthält, dadurch gekennzeichnet, daß das Aufzeichnungsmaterial lichtunempfindlich ist und die Schicht in einem der nachstehenden Formel (1) entsprechenden Schichtgewicht kolloidale Siliciumdioxidteilchen enthält : 0,015 x BAGOS < SAGOS < 1,2 (BAGOS - 0,4) in der B das Gewicht aller Bindemittel in der Schicht, AGOS das Gewicht aller organischen Silbersalze in der Schicht und S das Gewicht der kolloidalen Teilchen in der Schicht darstellt.
  2. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Schicht in einem der nachstehenden Formel (2) entsprechenden Schichtgewicht kolloidale Siliciumdioxidteilchen enthält : 0,1 x BAGOS < SAGOS < 1,0 (BAGOS - 0,4) in der B das Gewicht aller Bindemittel in der Schicht, AGOS das Gewicht aller organischen Silbersalze in der Schicht und S das Gewicht der kolloidalen Teilchen in der Schicht darstellt.
  3. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Schicht die kolloidalen Siliciumdioxidteilchen in einem der nachstehenden Formel (3) entsprechenden Schichtgewicht enthält : 0,2 x BAGOS < SAGOS < 0,8 (BAGOS - 0,4) in der B das Gewicht aller Bindemittel in der Schicht, AGOS das Gewicht aller organischen Silbersalze in der Schicht und S das Gewicht der kolloidalen Teilchen in der Schicht darstellt.
  4. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die kolloidalen Teilchen hydrophobiert sind.
  5. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die kolloidalen Teilchen eine spezifische Oberfläche von mehr als 100 m2/g aufweisen.
  6. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Aufzeichnungsmaterial einen nach der ASTM-Norm D1003 Methode B ermittelten Trübungswert von weniger als 35% aufweist.
  7. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das wärmeempfindliche Element weiterhin in einem Molverhältnis von zumindest 20, bezogen auf die Gesamtmenge des (der) enthaltenen organischen Silbersalze(s) und in thermischer wirksamer Beziehung dazu, zumindest eine Polycarbonsäure und/oder ein Polycarbonsäure-Anhydrid enthält.
  8. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das wesentlich lichtunempfindliche organische Silbersalz ein wesentlich lichtunempfindliches Silbersalz einer Fettsäure ist.
  9. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Reduktionsmittel eine aromatische Di- oder Trihydroxyverbindung mit zumindest zwei Hydroxylgruppen in ortho- oder para-Stellung auf demselben aromatischen Ring ist.
  10. Ein durch die nachstehenden Schritte gekennzeichnetes thermisches Bilderzeugungsverfahren zur Herstellung von kontrastreichen Bildern :
    (1) Anordnen einer Außenschicht eines Aufzeichnungsmaterials nach einem der vorstehenden Ansprüche,
    (2) bildmäßige Beaufschlagung des Aufzeichnungsmaterials mit von einer Heizquelle gelieferter Wärme, wobei zwischen dem Aufzeichnungsmaterial und der Heizquelle ein gegenseitiger Kontakt aufrechterhalten wird, und
    (3) die Abtrennung des Aufzeichnungsmaterials von der Heizquelle.
  11. Thermisches Bilderzeugungsverfahren nach Anspruch 10, dadurch gekennzeichnet, daß die Heizquelle ein Thermokopf ist.
EP19960203640 1995-12-27 1996-12-19 Wärmeempfindliches Aufzeichnungsmaterial mit verbesserter Tonwiedergabe Expired - Lifetime EP0782043B1 (de)

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EP95203634 1995-12-27
EP95203634 1995-12-27
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