EP1211091A1 - Matériau thermographique d'enregistrement avec ton de l'image amélioré - Google Patents

Matériau thermographique d'enregistrement avec ton de l'image amélioré Download PDF

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Publication number
EP1211091A1
EP1211091A1 EP01000599A EP01000599A EP1211091A1 EP 1211091 A1 EP1211091 A1 EP 1211091A1 EP 01000599 A EP01000599 A EP 01000599A EP 01000599 A EP01000599 A EP 01000599A EP 1211091 A1 EP1211091 A1 EP 1211091A1
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EP
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Prior art keywords
group
recording material
thermographic recording
formula
thermographic
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EP01000599A
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German (de)
English (en)
Inventor
Carlo c/o AGFA-GEVAERT Uyttendaele
René c/o AGFA-GEVAERT De Keyzer
Johan c/o AGFA-GEVAERT Loccufier
Ivan c/o AGFA-GEVAERT Hoogmartens
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Agfa HealthCare NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP01000599A priority Critical patent/EP1211091A1/fr
Publication of EP1211091A1 publication Critical patent/EP1211091A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • 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

Definitions

  • the present invention relates to thermographic recording materials whose prints have improved archival properties.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of thermal energy.
  • direct thermal thermography a visible image pattern is formed by image-wise heating of a recording material.
  • JN 07-248 567 discloses a thermosensitive recording material having a thermosensitive recording layer containing at least: a) an organic silver salt; b) a reducing agent; c) a water-soluble binder; d) a development accelerator such as phthalazinones; and e) a hardening agent for c).
  • hardening agents as particularly preferred were the compounds 1,3,5-triacryloylhexahydro-s-triazine and 1,2-bis vinylsulfonylmethane, 1,3-bis(vinylsulfonylmethyl)propanal-2, bis( ⁇ -vinyl sulfonyl acetoamido)ethane, 2,4-dichloro-6-hydroxy-s-triazine/sodium salt, 2,4,6-triethylene imino-s-triazine, boric acid etc., the added amount being preferably 0.5-5 wt% with respect to the water-soluble binder.
  • thermographic recording materials undergo during the thermal printing process require the use of hardened polymers and hence of hardening agents to harden the polymers.
  • hardening agents not only harden the polymer, but can also have a prohibitive effect on image tone, which is undesirable.
  • hardening agents and polymer-hardening agent systems for hardening thermographic recording materials which have substantially no effect on the image tone of prints produced with such hardened thermographic recording materials.
  • divinylsulfone compounds are well-known hardeners for amino-group-containing polymers, it would be expected that all divinylsulfone compounds would be equally effective as hardeners of amino-group-containing polymers in substantially light-insensitive thermographic recording materials, see JN 07-248 567.
  • substantially light-insensitive thermographic recording materials comprising amino-group-containing polymers hardened with particular divinylsulfone compounds are capable of providing prints whose image tone is substantially unaffected by the divinylsulfone compound used, whereas prints produced with thermographic recording materials hardened with other divinylsulfone compounds exhibit image tones which have been substantially affected by the divinylsulfone compound used.
  • thermographic recording material comprising a thermosensitive element and a support, the thermosensitive element containing a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith and a binder, characterized in that the thermographic recording material comprises a reaction product of an amino-group containing polymer and a compound according to formula (I): wherein each of R 1 , R 2 , R 3 and R 4 is independently hydrogen or an optionally substituted alkyl, aryl, heteroaryl, alkoxy or aryloxy group; L is a divalent linking group selected from the group consisting of oxygen and optionally substituted alkyl, aryl, heteroaryl, alkenyl and alkynyl groups; and m is either 0 or 1; and n is either 0 or 1.
  • thermosensitive element for coating a support with the above-described thermosensitive element comprising the steps of: applying a solution or dispersion containing the compound according to formula (I) to a support; and reacting the compound according to formula (I) with an amino-group-containing polymer, the compound according to formula (I) and the amino-group-containing polymer being either in the same layer or in immediately adjacent layers.
  • each of R 1 , R 2 , R 3 and R 4 is independently hydrogen or an optionally substituted alkyl, aryl, heteroaryl, alkoxy or aryloxy group;
  • L is a divalent linking group selected from the group consisting of oxygen and optionally substituted alkyl, aryl, heteroaryl, alkenyl and alkynyl groups; and
  • m is either 0 or 1; and
  • n is either 0 or 1, in the preparation of thermographic recording materials containing a substantially light-insensitive organic silver salt.
  • thermographic imaging process comprising the steps of: providing the above-described monosheet black and white substantially light-insensitive thermographic recording material; and image-wise applying heat to said thermographic recording material under substantially water-free conditions.
  • the heat source is a thermal head with a thin film thermal head being particularly preferred.
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
  • substantially light-insensitive is meant not intentionally light sensitive.
  • thermographic recording material includes substantially light-insensitive thermographic recording materials and photothermographic recording materials in which a photosensitizing material such as photosensitive silver halide is present in the thermosensitive element.
  • Heating in a substantially water-free condition means heating at a temperature of 80 to 250°C.
  • substantially water-free condition means that the reaction system is approximately in equilibrium with water in the air, and water for inducing or promoting the reaction is not particularly or positively supplied from the exterior to the element. Such a condition is described in T.H. James, "The Theory of the Photographic Process", Fourth Edition, Macmillan 1977, page 374.
  • thermoplastic recording materials of the present invention wherein each of R 1 , R 2 , R 3 and R 4 is independently hydrogen or an optionally substituted alkyl, aryl, heteroaryl, alkoxy or aryloxy group; L is a divalent linking group selected from the group consisting of oxygen and optionally substituted alkyl, aryl, heteroaryl, alkenyl and alkynyl groups; and m is either 0 or 1; and n is either 0 or 1.
  • Preferred substituents of the alkyl, aryl, heteroaryl, alkenyl and alkynyl groups representing L are alkyleneoxyalkyl, alkyl, aryl, sulphonylvinyl, hydroxy, alkoxy and aryloxy groups.
  • Preferred substituents of the alkyl, aryl, heteroaryl, alkoxy or aryloxy groups representing the R 1 to R 4 groups are alkyleneoxyalkyl, alkyl, aryl, sulphonylvinyl, hydroxy, alkoxy and aryloxy groups.
  • L is preferably an alkylene group, an alkyleneoxyalkylene group, an alkylene group substituted with at least one hydroxy-group, an alkylene group substituted with at least one methylene-sulphonylvinyl-group, an alkyleneoxyalkyl-substituted alkyl group, an oxyalkyleneoxyalkyl-substituted alkyl group, a phenylene group, a carboxy-substituted alkyl group, a carboxyalkyl-substituted alkyl group, an acyloxy-substituted alkyl group and a 3,5-dihydrodioxole group.
  • Suitable compounds according to formula (II) for use in the substantially light-insensitive thermographic recording materials of the present invention are compounds DVS-1 to DVS-18 below:
  • Particularly preferred compounds according to formula (I) are selected from the group consisting of: 1,1-bis-(vinylsulfonyl)-methane (DVS-1), 1,2-bis-(vinylsulfonyl)-ethane (DVS-3), 1,2-bis-(vinylsulfonyl)propane, 1,3-bis-(vinylsulfonyl)propane, 1,3-bis-(vinylsulfonyl)-2-hydroxy-propane (DVS-3), 3,3-bis-(vinylsulfonyl)-n-propyl-methyl-ether (DVS-4), tetrakis-(vinylsulphonylmethylene)-methane (DVS-7) and 1,5-bis-(vinylsulfonyl)-3-oxy-n-pentane (DVS-11) .
  • thermosensitive element as used herein is that element which contains all the ingredients which contribute to image formation.
  • the thermosensitive element contains 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 above-mentioned ingredients may be dispersed in different layers, with the proviso that the substantially light-insensitive organic silver salt is in reactive association with the reducing agent 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 particles of substantially light-insensitive organic silver salt so that reduction to silver can occur.
  • thermosensitive element may optionally contain a reaction product of an amino-group-containing polymer and a compound according to formula (I). Furthermore, in a preferred embodiment of the thermographic recording material of the present invention, the reaction product of an amino-group-containing polymer and a compound according to formula (I) is substantially present in the thermosensitive element.
  • Preferred organic silver salts for use in the thermographic recording materials of the present invention are substantially light-insensitive silver salts of an organic carboxylic acid.
  • Preferred substantially light-insensitive silver salts of an organic carboxylic acid 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, which silver salts are also called "silver soaps".
  • Other silver salts of an organic carboxylic acid 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 silver salt of an organic carboxylic acids may also be used in the present invention, as disclosed in EP-A 964 300.
  • Organic silver salts may be dispersed by standard dispersion techniques e.g. using ball mills, bead mills, microfluidizers, ultrasonic apparatuses, rotor stator mixers etc. have been found to be useful in this regard. Mixtures of organic silver salt dispersions produced by different techniques may also be used to obtain the desired thermographic properties e.g. of coarser and a more finely ground dispersions of organic silver salts.
  • Suitable organic reducing agents for the reduction the substantially light-insensitive organic silver salt 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.
  • 1,2-dihydroxybenzene derivatives 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, e.g. ethyl 3,4-dihydroxybenzoate and n-butyl 3,4-dihydroxybenzoate, and EP-A 903 625, e.g. 3,4-dihydroxybenzonitrile, being particularly preferred.
  • 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 mixed crystals of two or more organic silver salts.
  • 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 5,635,339; and 2-substituted malonodialdehyde compounds as disclosed in US-P 5,654,130.
  • each and every reducing agent in said thermosensitive element is a 1,2-dihydroxybenzene derivative.
  • the amino-group-containing polymer is selected from the group consisting of natural and synthetic polymers.
  • Suitable natural polymers include gelatine and gelatine derivatives.
  • Suitable synthetic polymers include melamine-formaldehyde resins, melamine-poly(vinyl alcohol) reaction products, aniline-formaldehyde resins and urea-formaldehyde resins.
  • Polymer latex particles with surface amino groups were disclosed online on October 17, 2000 by I. Miraballes-Martinez and J. Forcada in Journal of Polymer Science: Part A: Polymer Chemistry, volume 38, pages 4230-4237, herein incorporated by reference.
  • Such latex particles were prepared by a two-step emulsion polymerization.
  • the seeds were synthesized by batch emulsion polymerization of styrene; and in the second step, two different amino-functionalized monomers [aminoethyl methacrylate hydrochloride and vinylbenzylamine hydrochloride], two different initiator systems (K 2 S 2 O 8 and K 2 S 2 O 8 /NaS 2 O 5 and mixtures of emulsifiers sodium dodecylsulfate and TweenTM 21 were used to synthesize the final latexes.
  • the binder of the thermosensitive element and/or the binder of a protective layer may, according to the present invention, comprise a reaction product of an amino-group containing polymer and a compound according to formula (I).
  • thermosensitive element Binder of the thermosensitive element
  • the film-forming binder of the thermosensitive element may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, in which the substantially light-insensitive organic silver salt can be dispersed homogeneously either in aqueous or solvent media: 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.
  • Binders are preferred which do not contain additives or impurities which adversely affect the thermographic properties of the thermographic recording materials in which they are used.
  • thermosensitive element preferably further contains a so-called toning agent.
  • Suitable toning agents are the phthalimides and phthalazinones within the scope of the general formulae described in US 4,082,901. Further reference is made to the toning agents described in US 3,074,809, 3,446,648 and 3,844,797.
  • Other particularly useful toning agents are the heterocyclic toning compounds of the benzoxazine dione or naphthoxazine dione type as disclosed in GB 1,439,478, US 3,951,660 and US 5,599,647.
  • Stabilizers may be incorporated into the substantially light-insensitive thermographic recording materials of the present invention in order to obtain improved shelf-life and reduced fogging.
  • Preferred stabilizers are a compound according to formula (I): wherein R 1 is hydrogen, an alkali metal ion, an ammonium ion, a phosphonium ion, a sulphonium ion, an alkaline earth ion or an aryl, substituted aryl, alkyl or substituted alkyl group; R 2 is an alkyl, substituted alkyl, alkaryl, substituted alkaryl, aralkyl, substituted aralkyl, aryl, substituted aryl group, heteroaryl or substituted heteroaryl group; and X is hydrogen, an alkali metal ion, an ammonium ion or an alkaline earth ion.
  • stabilizers are sterically hindered monophenols; benzotriazole; substituted benzotriazoles; tetrazoles; mercaptotetrazoles, such as 1-phenyl-5-mercapto-tetrazole; and aromatic polycarboxylic acids, such as ortho-phthalic acid, 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid, and anhydrides thereof.
  • Particularly preferred stabilizers are 3,5-di-tert-butyl-4-hydroxybenzoic acid, 2-phosphono-1,2,3-propanetricarboxylic acid, the calcium salt of 4-ethylphosphomethyl-2,5-di-t-butylphenol, benzotriazole, 1-phenyl-5-mercapto-tetrazole, tetrachlorophthalic acid and tetrachlorophthalic acid anhydride.
  • thermosensitive element may comprise in addition at least one optionally substituted 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) and 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.
  • thermographic recording materials of the present invention may contain one or more surfactants, which may be anionic, non-ionic or cationic surfactants and/or one or more dispersants.
  • the recording material may contain in addition to the ingredients mentioned above other additives such as 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. BAYSILONTM MA (from BAYER AG, GERMANY).
  • 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. BAYSILONTM MA (from BAYER AG, GERMANY).
  • the support for the thermosensitive element according to the present invention may be transparent, translucent or opaque and is a thin flexible carrier made of transparent resin film, e.g. made of a cellulose ester, cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. polyethylene terephthalate.
  • transparent resin film e.g. made of a cellulose ester, cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. polyethylene terephthalate.
  • the support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermosensitive element. It may be pigmented with a blue pigment as so-called blue-base.
  • One or more backing layers may be provided to control physical properties such as curl and static.
  • the thermosensitive element is provided with a protective layer to avoid local deformation of the thermosensitive element and to improve resistance against abrasion.
  • the reaction product of the amino-group-containing polymer and the compound according to formula (I) is substantially present in the protective layer.
  • the protective layer preferably comprises a binder, which may be solvent-soluble, solvent-dispersible, water-soluble or water-dispersible.
  • a binder which may be solvent-soluble, solvent-dispersible, water-soluble or water-dispersible.
  • solvent-soluble binders polycarbonates as described in EP-A 614 769 are particularly preferred.
  • water-soluble or water-dispersible binders are preferred for the protective layer, as coating can be performed from an aqueous composition and mixing of the protective layer with the immediate underlayer can be avoided by using a solvent-soluble or solvent-dispersible binder in the immediate underlayer.
  • the protective layer according to the present invention may be crosslinked. Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495.
  • Solid or liquid lubricants or combinations thereof are suitable for improving the slip characteristics of the thermographic recording materials according to the present invention.
  • Preferred solid lubricants are thermomeltable particles such as those described in WO 94/11199.
  • the protective layer of the thermographic recording material according to the present invention may comprise a matting agent. Preferred matting agents are described in WO 94/11198, e.g. talc particles, and optionally protrude from the protective layer.
  • 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 out under substantially water-free conditions 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, with a substantially light-insensitive thermographic material preferably containing an infra-red absorbing compound, or by direct thermal imaging with a thermal head.
  • an infra-red heat source for example with a Nd-YAG laser or other infra-red laser
  • 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 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 1.0ms, 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 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.
  • Activation of the heating elements can be power-modulated or pulse-length modulated at constant power.
  • EP-A 654 355 discloses 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.
  • 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 recording material can also be carried out using an electrically resistive ribbon incorporated into the material.
  • Image- or pattern-wise heating of the recording material may also proceed by means of pixel-wise modulated ultrasound.
  • Thermographic imaging can be used for the production of reflection type prints and transparencies, in particular for use in the medical diagnostic field in which black-imaged transparencies are widely used in inspection techniques operating with a light box.
  • Thermosensitive element is thermosensitive element
  • the silver behenate dispersion used in COMPARATIVE EXAMPLES 1 to 8 and INVENTION EXAMPLES 1 to 4 was produced as follows: 25kg (73.5M) behenic acid was dispersed with stirring at 80°C in 100L of a 10% solution of Surfactant Nr.
  • the support was a subbed 168 ⁇ m thick blue-pigmented polyethylene terephthalate support.
  • One side of the subbed support was coated with an aqueous dispersion containing 10.05% by weight of K16096, 0.08% by weight of a 6 ⁇ m poly(methyl methacrylate) matting agent, 0.07% by weight of R13311, 0.1% by weight of Surfactant Nr 5, 0.026% by weight of Surfactant Nr 6 and 0.32% by weight of DVS-1 to produce a layer with the following composition: K16096: 2.73g/m 2 6 ⁇ m poly(methyl methacrylate) matting agent: 0.025g/m 2 R13311: 0.022g/m 2 Surfactant Nr. 5: 0.03g/m 2 Surfactant Nr.
  • thermographic recording materials Preparation of thermographic recording materials
  • the coating dispersion for the thermosensitive element was produced by first allowing 3.44g of K17881 to swell in 16.31g of deionized water over a period of 30 minutes. 0.7g of a first aqueous toning agent dispersion containing 20% of T01 and 12.5% of K17881 and 1.925g of a second toning agent dispersion containing 20% of T02 and 10% of R16875 were then added and the resulting dispersion heated with stirring up to 50°C.
  • thermosensitive elements of COMPARATIVE EXAMPLES 1 to 4 and INVENTION EXAMPLES 1 and 2 were obtained.
  • thermosensitive elements of the thermographic recording materials of COMPARATIVE EXAMPLES 1 to 4 and INVENTION EXAMPLES 1 and 2 were coated with an aqueous dispersion with the following ingredients which upon drying produced a protective layer with the following composition: Surfactant Nr.
  • thermographic recording materials of COMPARATIVE EXAMPLES 1 to 4 and INVENTION EXAMPLES 1 and 2 were printed using a DRYSTAR® 2000 printer from AGFA-GEVAERT equipped with a thin film thermal head with a resolution of 300 dpi and operated with a line time of 11.8ms (the line time being the time needed for printing one line). During this line time the print head received constant power. The printing power was 90mW and the thermal head resistors were time-modulated to produce different image densities.
  • the image tone of fresh prints made with the substantially light-insensitive thermographic recording materials of COMPARATIVE EXAMPLES 1 to 4 and INVENTION EXAMPLES 1 and 2 was assessed on the basis of the L*, a* and b* CIELAB-values.
  • the L*, a* and b* CIELAB-values 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.
  • a negative CIELAB a*-value indicates 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 CIELAB b*-value indicates a bluish tone which becomes increasingly bluer as b* becomes more negative and a positive b*-value indicates a yellowish image-tone becoming more yellow as b* becomes more positive.
  • the image tone of elements of the image with a density of 1.0 have a stronger effect than the image tone of elements with lower or higher optical.
  • thermographic recording materials of COMPARATIVE EXAMPLES 1 and 4 and INVENTION EXAMPLES 1 and 2 were comparable for the thermographic recording materials of COMPARATIVE EXAMPLES 1 and 4 and INVENTION EXAMPLES 1 and 2, but those for the thermographic recording materials of COMPARATIVE EXAMPLES 3 and 4 have insufficiently negative b* values, when the b* value without coating has a b* value of -16.6.
  • the D min values are mainly due to the density of the support, which had a D vis value of 0.19.
  • thermographic recording materials Preparation of thermographic recording materials
  • the coating dispersion for the thermosensitive element was produced by first allowing 3.44g of K17881 to swell in 16.33g of deionized water over a period of 30 minutes. 3.05g of a first aqueous toning agent dispersion containing 18.08% of T01 and 9.95% of K17881 and 0.8g of a second toning agent dispersion containing 20.12% of T02 and 8.88% of R16875 were then added and the resulting dispersion heated with stirring up to 50°C.
  • thermosensitive element of INVENTION EXAMPLE 3 was obtained.
  • thermographic recording material of INVENTION EXAMPLE 3 was printed and the maximum image density determined as described for the thermographic recording materials of COMPARATIVE EXAMPLES 1 to 4 and INVENTION EXAMPLES 1 and 2 except that during the thermographic printing the print head was separated from the imaging layer by a thin intermediate material separable from the thermographic recording material.
  • This intermediate material consisted 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 a ribbon with a total thickness of 6 ⁇ m. The printing head was contacted with the slipping layer. The results for fresh material are given in Table 4.

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EP01000599A 2000-11-30 2001-11-07 Matériau thermographique d'enregistrement avec ton de l'image amélioré Withdrawn EP1211091A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113563538A (zh) * 2021-09-23 2021-10-29 山东诺尔生物科技有限公司 一种抗温抗盐双敏聚合物驱油剂及其制备方法

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