EP0286116A2 - Heat-sensitive recording material - Google Patents

Heat-sensitive recording material Download PDF

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Publication number
EP0286116A2
EP0286116A2 EP88105625A EP88105625A EP0286116A2 EP 0286116 A2 EP0286116 A2 EP 0286116A2 EP 88105625 A EP88105625 A EP 88105625A EP 88105625 A EP88105625 A EP 88105625A EP 0286116 A2 EP0286116 A2 EP 0286116A2
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EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
parts
material according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88105625A
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German (de)
French (fr)
Other versions
EP0286116B1 (en
EP0286116A3 (en
Inventor
Tochimi Central Research Laboratory Satake
Toshiaki Central Research Laboratory Minami
Tomoaki Central Research Laboratory Nagai
Fumio Central Research Laboratory Fujimura
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Jujo Paper Co Ltd
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Jujo Paper Co Ltd
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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
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • the invention relates to a thermosensitive recording material which has superior optical readability in the near ultra-red range.
  • Heat-sensitive recording sheets in which a color reaction between a colorless or slightly colored or chromogenic substance and a phenolic substance or an organic acid takes place due to the action of heat or heat include in Japanese Patent Publications No. 4160/1968 and 14039/1970 and in JP-OLS No. 27736/1973. They are used in many different ways in practice.
  • a heat-sensitive recording sheet is generally prepared by applying to the surface of a support such as paper, film, etc., a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, mixing the dispersions obtained with one another and adding a binder, filler, Sensitizer, lubricant and other aids has been obtained. When exposed to heat or heat, the coating immediately undergoes a chemical reaction with color formation.
  • heat-sensitive recording sheets include use in medical and technical recording devices, terminal printers for computers and information systems, printers for facsimile or copying machines and electronic calculating machines, ticket machines and the like.
  • the heat sensitive recording sheets containing a leuco dye and a coloring agent are used as thermal labels in the field of POS systems.
  • the color development occurs in the visible range, so that the color development when a semiconductor laser beam is used in the near ultra-red range cannot be read by the bar code scanner.
  • Metal chelate color development type heat sensitive recording sheets are used as heat sensitive sheets for POS systems, etc., but have the disadvantage that the legibility is insufficient when using a semiconductor laser beam operating in the near-red range as a bar code measuring point scanner.
  • the invention has for its object to provide a heat-sensitive recording sheet which has superior optical readability in the near ultraviolet range in color development with chelating agents using metal compounds.
  • a near-infrared absorbing fluoran dye of the following general formula (I) is used in a heat-sensitive recording material which has a heat-sensitive recording layer of a chelating agent type on a support: wherein at least one of the radicals R1, R2, R3, R4, R5, R6, R7, R8, and R9 is a group of the general formula: means wherein T1, T2 and T3 are the same or different and each represents a hydrogen atom, a C1-C8 alkyl, C3-C9 alkenyl or C3-C9 alkynyl group; T4 represents a hydrogen atom, a C1-C8 alkyl, C3-C9 alkenyl, C3-C9 alkynyl or phenyl group; T3 and T4 may also be connected to an adjacent nitrogen atom to form a morpholino, pyrrolidino, piperidino or hexamethyleneimino group; and the radical
  • the alkyl groups preferably have 1 to 6 carbon atoms
  • the cycloalkyl groups preferably have 3 to 6 carbon atoms
  • the substitution of the amino groups preferably consists of a mono- or di-C1-C6-alkyl substitution
  • the aryl groups are preferably phenyl radicals.
  • the choice of the electron acceptor according to the invention is not subject to any particular restrictions; the known electron acceptors, preferably the metal double salts of the higher fatty acids, can be used.
  • the metal double salts of higher fatty acids according to the invention are double salts which have at least two types of metal atoms per molecule. They therefore differ significantly in their physicochemical properties from the previous metal salts of higher fatty acids, which only contain one type of metal atom in their molecule.
  • These metal double salts of the higher fatty acids are prepared by reacting at least two inorganic metal salts with an alkali metal salt or ammonium salt of the selected higher fatty acid.
  • the type and the mixing ratio of the metal atoms of the at least two inorganic metal salts can be easily adjusted and controlled in this way.
  • the zinc-iron double salt of behenic acid with iron and zinc in a ratio of 2: 1 can be prepared by reacting sodium behenate with an aqueous solution of ferrichloride and zinc chloride in a molar ratio of 2: 1.
  • Suitable metals for the double salt formation of the higher fatty acids are polyvalent metals, for example iron, zinc, calcium, magnesium, aluminum, barium, lead, manganese, tin, nickel, cobalt, copper, silver, mercury, etc .; preferably iron, zinc, calcium, aluminum, magnesium and silver.
  • Suitable fatty acids for the double salt formation are saturated and / or unsaturated aliphatic fatty acids with 16 to 35 carbon atoms.
  • the electron donors according to the invention which are used with the metal double salt of a higher fatty acid, are preferably polyvalent aromatic hydroxyl compounds, diphenylcarbazide, diphenylcarbazone, hexamethylenetetramine, spirobenzopyran and 1-formyl-4-phenylsemicarbazide; most preferred are the polyvalent aromatic hydroxyl compounds of the general formula (I): in the R an alkyl group with 18 to 35 (wherein R1 represents an alkyl group having 18 to 35 carbon atoms); n represents an integer from 2 to 3; and "-X-" for ⁇ CH2 ⁇ , ⁇ CO2 ⁇ , ⁇ CO ⁇ , ⁇ O ⁇ , ⁇ CONH ⁇ , -C - (wherein R ⁇ is an alkyl group having 5 to 30 carbon atoms), -SO2-, -SO3- or -SO2NH-.
  • the heat-sensitive recording layer according to the invention which contains an electron acceptor and an electron donor, also contains a near-infrared absorbing fluoran dye of the general formula (I).
  • the dyes of the following general formula (II) prefers.
  • the fluorine leuco dyes according to the invention are not subject to any particular restrictions; the following can be used, for example: 2-methyl-6-p- (p-dimethylaminophenyl) aminoani linofluoran, 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, ⁇ -nitro-6-p- (p-di ethylaminophenyl) aminoanilinofluoran, 2- Amino-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-diethylamino-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-phenyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2-benzyl-6-p - (
  • the fluorantypleuco dyes of the general formula (I) according to the invention are used alone or in a mixture.
  • Binders according to the invention are, for example, completely saponified polyvinyl alcohol, degree of polymerization: 200-1900, partly saponified polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl cellulose styrene, methyl malolymethyl copolymer, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methylcellulose, methylcellulose Copolymers, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrene, copoly mers of the above compounds, polyamide resin, silicone resin, petroleum resin
  • the type and amount of the electron acceptor according to the invention such as the metal double salt of the saturated higher fatty acid, the electron donor such as the polyhydric phenol, the near-infrared absorbing leuco dye, the binder and the other additives, which are chosen depending on the desired effect and suitability for recording purposes, are not particularly limited.
  • the heat sensitive material of the present invention made by applying the coating composition to a base material such as paper, synthetic paper, film, plastic, etc.
  • the electron acceptor according to the invention, the electron donor according to the invention and the basic colorless chromogenic dye according to the invention are ground to a particle size of several microns or smaller by means of a grinding device, such as a ball mill, attrition mill, sand grinder, etc., or by means of a suitable emulsifying machine: binders are added, if appropriate , various additives to produce the coating composition of the invention.
  • the additives which can be used according to the invention are, for example, the following: Fillers; Anti-sticking releasing agents such as metal salts of fatty acids; Mottling prevention lubricants such as fatty acid amide, ethylene bisamide, montan wax, polyethylene wax, etc .; Dispersants such as sodium dioctyl sulfosuccinic acid, sodium dodecyl benzene sulfonate, sodium lauryl alcohol sulfate, sodium alginate, etc .; UV absorbers of the benzophenone and triazole series; Anti-foaming agents; water mooring agents, etc.
  • fillers according to the invention are alumina, talc, silicon dioxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, barium sulfate, kaolin, titanium dioxide, zinc oxide, calcium carbonate, aluminum oxide, urea-formaldehyde resin, polystyrene resin, phenolic resin, etc.
  • the reason for the superior optical legibility in the near-red range of the heat-sensitive recording sheet according to the invention is based on the fact that during color development with complex formation by melting reaction between a metal double salt as an electron acceptor and an electron donor such as polyvalent phenol derivative, a colored image in the visible and near-red range (wavelength range 700 -1500 nm) arises.
  • the fluoranleuco dye of the present invention is added to this combination, which can more effectively absorb the near-ultraviolet rays in the melting reaction with an electron donor such as phenolic derivatives. In this way, a thermosensitive recording sheet is obtained which has superior optical readability in the near ultraviolet range.
  • Double metal salt of a higher fatty acid See Table 1.
  • Solution C (dispersion of a near-infrared absorbing leuco dye)
  • Leuco dye See Table 1.
  • Solution A 25.0 parts
  • Solution B 29.5 parts
  • Solution C 2.5 parts Kaolin clay (5% aqueous dispersion) 12.0 parts
  • the above coating composition was applied in a coating amount of 6.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to set a smoothness of 200-600 seconds.
  • a heat sensitive recording sheet was obtained.
  • Metal double salt of a higher fatty acid See Table 1.
  • Solution D 25.0 parts
  • Solution F 29.5 parts Kaolin clay (50% aqueous dispersion) 12.0 parts
  • a heat-sensitive recording sheet was obtained in the same manner as in Example 1.
  • the recording material of the present invention has superior optical readability in the near ultra-red range.

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

Abstract

Es wird ein wärmeempfindliches Aufzeichnungsmaterial beschrieben, das in der Farbentwicklungsschicht einen Elektronenakzeptor, einen Elektronendonator und einen besonderen, im nahen Ultrarot absorbierenden Leukofarbstoff enthält, wobei der Elektronenakzeptor und der Elektronendonator unter Chelatbildung miteinander reagieren. Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial weist eine überlegene optische Lesbarkeit im nahen ultraroten Bereich auf.A heat-sensitive recording material is described which contains an electron acceptor, an electron donor and a special leuko dye which absorbs in the near infrared in the color development layer, the electron acceptor and the electron donor reacting with one another to form a chelate. The heat sensitive recording material of the present invention has superior optical readability in the near ultra-red range.

Description

Die Erfindung betrifft ein wärmeempfindliches Aufzeich­nungsmaterial, das eine überlegene optische Lesbarkeit im nahen ultraroten Bereich aufweist.The invention relates to a thermosensitive recording material which has superior optical readability in the near ultra-red range.

Wärmeempfindliche Aufzeichnungsblätter, bei denen durch Wärme- oder Hitzeeinwirkung eine Farbreaktion zwischen einem farblosen oder schwachfarbigen oder chromogenen Stoff und einer phenolischen Substanz oder einer orga­nischen Säure stattfindet, sind u.a. in den japanischen Patentpublikationen Nr. 4160/1968 und 14039/1970 und in JP-OLS Nr. 27736/1973 beschrieben. Sie finden vielfältige Anwendung in der Praxis.Heat-sensitive recording sheets in which a color reaction between a colorless or slightly colored or chromogenic substance and a phenolic substance or an organic acid takes place due to the action of heat or heat include in Japanese Patent Publications No. 4160/1968 and 14039/1970 and in JP-OLS No. 27736/1973. They are used in many different ways in practice.

Ein wärmeempfindliches Aufzeichnungsblatt wird im allge­meinen hergestellt, indem man auf die Oberfläche eines Trägers wie Papier, Film usw. eine Beschichtungsmasse aufbringt, die durch Feinvermahlen und Dispergieren eines farblosen chromogenen Stoffes und eines Farbentwicklungs­materials, Vermischen der erhaltenen Dispersionen mitein­ander und Zugeben eines Bindemittels, Füllstoffs, Sensi­bilisierungsmittels, Gleitmittels und anderer Hilfsmittel erhalten worden ist. Bei Wärme- oder Hitzeeinwirkung erfolgt in der Beschichtung augenblicklich eine chemi­sche Umsetzung unter Farbbildung.A heat-sensitive recording sheet is generally prepared by applying to the surface of a support such as paper, film, etc., a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, mixing the dispersions obtained with one another and adding a binder, filler, Sensitizer, lubricant and other aids has been obtained. When exposed to heat or heat, the coating immediately undergoes a chemical reaction with color formation.

Die vielfältige praktische Verwendung dieser wärme­empfindlichen Aufzeichnungsblätter umfaßt die Anwendung bei medizinischen und technischen Aufzeichnungsgeräten, Terminaldruckern von Computern und Informationssystemen, Druckern von Faksimilier- oder Kopiermaschinen und elek­tronischen Rechenmaschinen, Fahrscheinautomaten und dgl.The various practical uses of these heat-sensitive recording sheets include use in medical and technical recording devices, terminal printers for computers and information systems, printers for facsimile or copying machines and electronic calculating machines, ticket machines and the like.

Die wärmeempfindlichen Aufzeichnungsblätter, die einen Leukofarbstoff und ein Färbungsmittel enthalten, werden auf dem Gebiet der POS-Systeme als thermische Zettel angewandt. Dabei tritt die Farbentwicklung im sichtbaren Bereich auf, so daß die Farbentwicklung bei der Verwen­dung eines Halbleiter - Laserstrahls im nahen ultra­roten Bereich vom Strichcode-Abtaster nicht lesbar ist.The heat sensitive recording sheets containing a leuco dye and a coloring agent are used as thermal labels in the field of POS systems. The color development occurs in the visible range, so that the color development when a semiconductor laser beam is used in the near ultra-red range cannot be read by the bar code scanner.

Im Gegensatz zum obigen wärmeempfindlichen Farbentwick­lungssystem, das farblose Farbstoffe verwendet, ist auch ein wärmeempfindliches Farbentwicklungssystem bekannt, das Metallverbindungen verwendet. Beispielsweise ist in der japanischen Patentpublikation 8787/1957 die kombi­ nierte Verwendung von Eisenstearat als Elektronenakzep­tor mit Tanninsäure oder Gallussäure als Elektronendona­tor beschrieben, und in der japanischen Patentpublikation 6485/1959 ist die kombinierte Verwendung von einem Elek­tronenakzeptor wie Silberstearat, Eisenstearat, Gold­stearat, Kupferstearat oder Quecksilberbehenat mit einem Elektronendonator wie Methylgallat, Äthylgallat, Propyl­gallat, Butylgallat oder Dodecylgallat beschrieben.In contrast to the above heat-sensitive color development system that uses colorless dyes, a heat-sensitive color development system that uses metal compounds is also known. For example, in Japanese patent publication 8787/1957, the combi The use of iron stearate as an electron acceptor with tannic acid or gallic acid as an electron donor is described, and Japanese patent publication 6485/1959 describes the combined use of an electron acceptor such as silver stearate, iron stearate, gold stearate, copper stearate or mercury behenate with an electron donor such as methyl gallate, ethyl gallate, ethyl gallate, ethyl gallate or dodecyl gallate.

Schilderung der Erfindung.Description of the invention.

Wärmeempfindliche Aufzeichnungsblätter des Metall­chelatfarbentwicklungstyps werden als wärmeempfindliche Zettel für POS-Systeme usw. verwendet, haben jedoch den Nachteil, daß die Lesbarkeit bei der Verwendung eines im nahen ultraroten Bereich als Strichcode-Meßstellen­abtaster arbeitenden Halbleiter-Laserstrahls ungenügend ist.Metal chelate color development type heat sensitive recording sheets are used as heat sensitive sheets for POS systems, etc., but have the disadvantage that the legibility is insufficient when using a semiconductor laser beam operating in the near-red range as a bar code measuring point scanner.

Der Erfindung liegt die Aufgabe zugrunde, ein wärme­empfindliches Aufzeichnungsblatt zu schaffen, das bei der Farbentwicklung mit Chelatbildnern unter Ver­wendung von Metallverbindungen eine überlegene opti­sche Lesbarkeit im nahen ultraroten Bereich aufweist.The invention has for its object to provide a heat-sensitive recording sheet which has superior optical readability in the near ultraviolet range in color development with chelating agents using metal compounds.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß in einem wärmeempfindlichen Aufzeichnungsmaterial, das auf einem Träger eine wärmeempfindliche Aufzeichnungsschicht vom Typ eines Chelatbildners hat, ein im nahen Ultrarot absorbie­render Fluoranfarbstoff der folgenden allgemeinen Formel (I) verwendet wird:

Figure imgb0001
worin mindestens einer der Reste R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, und R₉ eine Gruppe der allgemeinen Formel:
Figure imgb0002
 bedeutet, worin T₁, T₂ und T₃ gleich oder verschieden sind, und jeweils ein Wasserstoffatom, eine C₁-C₈-Alkyl-, C₃-C₉-­Alkenyl- oder C₃-C₉-Alkinylgruppe bedeuten; T₄ ein Wasser­stoffatom, eine C₁-C₈ Alkyl-, C₃-C₉-Alkenyl-, C₃-C₉-Alki­nyl- oder Phenylgruppe bedeutet; außerdem T₃ und T₄ mit einem benachbarten Stickstoffatom verbunden sein können unter Bildung einer Morpholino-, Pyrrolidino-, Piperidino- ­oder Hexamethyleniminogruppe;
und die reste R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ und R₉ gleich und verschieden sind, und jeweils ein Wasserstoff- oder Halogenatom, eine Alkyl- ­ Alkoxy-, Cycloalkyl-, Nitro-, Hydroxy-, Amino-, substituier­te Amino-, Aralkyl-, substituierte Aralkyl-, Aryl- oder substituierte Arylgruppe bedeuten;
und n eine ganze Zahl von 0 bis 4 bedeutet.This object is achieved according to the invention in that a near-infrared absorbing fluoran dye of the following general formula (I) is used in a heat-sensitive recording material which has a heat-sensitive recording layer of a chelating agent type on a support:
Figure imgb0001
 wherein at least one of the radicals R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is a group of the general formula:
Figure imgb0002
 means wherein T₁, T₂ and T₃ are the same or different and each represents a hydrogen atom, a C₁-C₈ alkyl, C₃-C₉ alkenyl or C₃-C₉ alkynyl group; T₄ represents a hydrogen atom, a C₁-C₈ alkyl, C₃-C₉ alkenyl, C₃-C₉ alkynyl or phenyl group; T₃ and T₄ may also be connected to an adjacent nitrogen atom to form a morpholino, pyrrolidino, piperidino or hexamethyleneimino group;
and the radicals R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ and R₉ are the same and different, and each represents a hydrogen or halogen atom, an alkyl Alkoxy, cycloalkyl, nitro, hydroxy, amino, substituted amino, aralkyl, substituted aralkyl, aryl or substituted aryl group;
and n represents an integer from 0 to 4.

In den obigen Resten weisen die Alkylgruppen vorzugsweise 1 bis 6 C-Atome auf, die Cycloalkylgruppen haben vorzugswei­se 3 bis 6 C-Atome, die Substitution der Aminogruppen besteht vorzugsweise in einer mono- oder di-C₁-C₆-Alkyl- Substitution und die Arylgruppen sind vorzugsweise Phenylreste.In the above radicals, the alkyl groups preferably have 1 to 6 carbon atoms, the cycloalkyl groups preferably have 3 to 6 carbon atoms, the substitution of the amino groups preferably consists of a mono- or di-C₁-C₆-alkyl substitution and the aryl groups are preferably phenyl radicals.

Die Wahl der erfindungsgemäßen Elektronenakzeptors unterliegt keinen besonderen Einschränkungen, man kann die bekannten Elektronenakzeptoren, vorzugsweise die Metalldoppelsalze der höheren Fettsäuren verwenden.The choice of the electron acceptor according to the invention is not subject to any particular restrictions; the known electron acceptors, preferably the metal double salts of the higher fatty acids, can be used.

Die erfindungsgemäßen Metalldoppelsalze höherer Fettsäuren sind Doppelsalze, die pro Molekül mindestens zwei Arten von Metallatomen haben. Sie unterscheiden sich daher deutlich in ihren physikalisch-chemischen Eigenschaften von den bisherigen Metallsalzen der höheren Fettsäuren, die nur eine Metallatomart in ihrem Molekül enthalten.The metal double salts of higher fatty acids according to the invention are double salts which have at least two types of metal atoms per molecule. They therefore differ significantly in their physicochemical properties from the previous metal salts of higher fatty acids, which only contain one type of metal atom in their molecule.

Diese Metalldoppelsalze der höheren Fettsäuren werden hergestellt, indem man mindestens zwei anorganische Metallsalze mit einem Alkalimetallsalz oder Ammoniumsalz der gewählten höheren Fettsäure umsetzt. Die Art und das Mischungsverhältnis der Metallatome der mindestens zwei anorganischen Metallsalze kann auf diese Weise leicht eingestellt und kontrolliert werden. Beispielsweise kann das Zink-Eisen-Doppelsalz der Behensäure mit Eisen und Zink im Verhältnis 2:1 hergestellt werden, indem man Natriumbehenat mit einer wäßrigen Lösung von Ferrichlorid und Zinkchlorid in einem Molverhältnis von 2:1 umsetzt.These metal double salts of the higher fatty acids are prepared by reacting at least two inorganic metal salts with an alkali metal salt or ammonium salt of the selected higher fatty acid. The type and the mixing ratio of the metal atoms of the at least two inorganic metal salts can be easily adjusted and controlled in this way. For example, the zinc-iron double salt of behenic acid with iron and zinc in a ratio of 2: 1 can be prepared by reacting sodium behenate with an aqueous solution of ferrichloride and zinc chloride in a molar ratio of 2: 1.

Geeignete Metalle für die Doppelsalzbildung der höheren Fettsäuren sind mehrwertige Metalle, beispielsweise Eisen, Zink, Calcium, Magnesium, Aluminium, Barium, Blei, Mangan, Zinn, Nickel, Kobalt, Kupfer, Silber, Quecksilber usw.; vorzugsweise Eisen, Zink, Calcium, Aluminium, Magnesium und Silber.Suitable metals for the double salt formation of the higher fatty acids are polyvalent metals, for example iron, zinc, calcium, magnesium, aluminum, barium, lead, manganese, tin, nickel, cobalt, copper, silver, mercury, etc .; preferably iron, zinc, calcium, aluminum, magnesium and silver.

Geeignete Fettsäuren für die Doppelsalzbildung sind gesättigte und/oder ungesättigte aliphatische Fettsäuren mit 16 bis 35 Kohlenstoffatomen.Suitable fatty acids for the double salt formation are saturated and / or unsaturated aliphatic fatty acids with 16 to 35 carbon atoms.

Die Wahl des erfindungsgemäßen Metalldoppelsalzes einer höheren Fettsäure unterliegt keinen besonderen Einschränkungen, man kann beispielsweise folgende verwenden.

  • 1) Eisen-Zink-Doppelsalz der Stearinsäure
  • 2) Eisen-Zink-Doppelsalz einer Montansäure
  • 3) Eisen-Zink-Dippelsalz einer Wachssäure
  • 4) Eisen-Zink-Doppelsalz der Behensäure
  • 5) Eisen-Calcium-Doppelsalz der Behensäure
  • 6) Eisen-Aluminium-Doppelsalz der Behensäure
  • 7) Eisen-Magnesium-Doppelsalz der Behensäure
  • 8) Silber-Calcium-Doppelsalz der Behensäure
  • 9) Silber-Aluminium-Doppelsalz der Behensäure
  • 10) Silber-Magnesium-Doppelsalz der Behensäure
  • 11) Calcium-Aluminium-Dopelsalz der Behensäure
The choice of the metal double salt of a higher fatty acid according to the invention is not subject to any particular restrictions, for example the following can be used.
  • 1) Iron-zinc double salt of stearic acid
  • 2) Iron-zinc double salt of a montanic acid
  • 3) Iron-zinc-dippel salt of a wax acid
  • 4) Iron-zinc double salt of behenic acid
  • 5) Double iron-calcium salt of behenic acid
  • 6) Iron-aluminum double salt of behenic acid
  • 7) Iron-magnesium double salt of behenic acid
  • 8) Silver-calcium double salt of behenic acid
  • 9) Silver-aluminum double salt of behenic acid
  • 10) Silver-magnesium double salt of behenic acid
  • 11) Calcium aluminum double salt of behenic acid

Solche Metalldoppelsalze höherer Fettsäuren können als Elektronenakzeptor allein oder im Gemisch verwendet werden.Such metal double salts of higher fatty acids can be used as an electron acceptor alone or in a mixture.

Die erfindungsgemäßen Elektronendonatoren, die mit dem Metalldoppelsalz einer höheren Fettsäure verwendet werden, sind vorzugsweise mehrwertige aromatische Hydroxiverbindungen, Diphenylcarbazid, Diphenylcarbazon, Hexamethylentetramin, Spirobenzopyran und 1-Formyl-4-phenylsemicarbazid; am bevorzugtesten sind die mehrwertigen aromatischen Hydroxiverbindungen der allgemeinen Formel (I):

Figure imgb0003
in der R eine Alkylgruppe mit 18 bis 35
Figure imgb0004
 (worin R₁ eine Alkylgruppe mit 18 bis 35 Kohlenstoffatomen bedeutet); n eine ganze Zahl von 2 bis 3 bedeutet; und "-X-" für ―CH₂―, ―CO₂―, ―CO―, ―O―, ―CONH―, -C
Figure imgb0005
-

(worin Rʹ eine Alkyl­gruppe mit 5 bis 30 Kohlenstoffatomen bedeutet), -SO₂-, -SO₃- oder -SO₂NH- steht.The electron donors according to the invention, which are used with the metal double salt of a higher fatty acid, are preferably polyvalent aromatic hydroxyl compounds, diphenylcarbazide, diphenylcarbazone, hexamethylenetetramine, spirobenzopyran and 1-formyl-4-phenylsemicarbazide; most preferred are the polyvalent aromatic hydroxyl compounds of the general formula (I):
Figure imgb0003
 in the R an alkyl group with 18 to 35
Figure imgb0004
 (wherein R₁ represents an alkyl group having 18 to 35 carbon atoms); n represents an integer from 2 to 3; and "-X-" for ―CH₂―, ―CO₂―, ―CO―, ―O―, ―CONH―, -C
Figure imgb0005
-

(wherein Rʹ is an alkyl group having 5 to 30 carbon atoms), -SO₂-, -SO₃- or -SO₂NH-.

Bei der Herstellung der Beschichtungsmasse durch Dispergieren dieses mehrwertigen Phenolderivats in einem wäßrigen oder lösungsmittellöslichen Bindemittel ist es nötig, eine Reaktion dieses Phenolderivats mit einem Elektronendonator zu vermeiden und die Lösungsmittel- und Dispersionsstabilität dieses Phenols zu erhöhen. Dabei ist es wünschenswert, daß der von der Farbentwicklungsgruppe verschiedene Substituent eine große Zahl von Kohlenstoffatomen, nämlich 18 bis 35, hat, 2 bis 3 OH-Gruppen vorhanden sind, und diese OH-­Gruppen nahe beieinander liegen. Das mehrwertige Phenolderivat kann allein oder in Mischung verwendet werden.When preparing the coating composition by dispersing this polyvalent phenol derivative in an aqueous or solvent-soluble binder, it is necessary to react it Avoid phenol derivative with an electron donor and increase the solvent and dispersion stability of this phenol. It is desirable that the substituent other than the color developing group has a large number of carbon atoms, namely 18 to 35, 2 to 3 OH groups are present, and these OH groups are close to each other. The polyvalent phenol derivative can be used alone or in a mixture.

Die erfindungsgemäße wärmeempfindliche Aufzeichnungs­schicht, die einen Elektronenakzeptor und einen Elektronendonator enthält, enthält außerdem einem im nahen Ultrarot absorbierenden Fluoranfarbstoff der allgemeinen Formel (I).The heat-sensitive recording layer according to the invention, which contains an electron acceptor and an electron donor, also contains a near-infrared absorbing fluoran dye of the general formula (I).

Von den Fluoranleukofarbstoffen der allgemeinen Formel (I) sind die Farbstoffe der folgenden allgemeinen Formel (II)

Figure imgb0006
bevorzugt.Of the fluorine leuco dyes of the general formula (I), the dyes of the following general formula (II)
Figure imgb0006
 prefers.

Unter Berücksichtigung der Herstellbarkeit, Kosten und Leistungsfähigkeit sind 2-methyl-6-p-(p-dimethyl­aminophenyl)aminoanilinofluoran (Schmelzpunkt: 197-203 °C) der folgenden Formel (III) und 2-Chlor-3-methyl-6-p-­(p-phenylaminophenyl) aminoanilinofluoran (Schmelzpunkt: 191,5- 196°C) der folgenden Formel (IV) am stärksten bevorzugt.

Figure imgb0007
Taking into account the manufacturability, costs and performance, 2-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluoran (melting point: 197-203 ° C.) of the following formula (III) and 2-chloro-3-methyl-6-p - (p-phenylaminophenyl) aminoanilinofluoran (melting point: 191.5-196 ° C) of the following formula (IV) most preferred.
Figure imgb0007

Die erfindungsgemäßen Fluoranleukofarbstoffe unterliegen keinen besonderen Einschränkungen; man kann z.B. folgende verwenden: 2-Methyl-6-p-(p-dimethylaminophenyl)aminoani­ linofluoran, 2-Methoxy-6-p-(p-dimethylaminophenyl)amino­anilinofluoran, 2-Chlor-6-p-(p-dimethylaminophenyl)amino­anilinofluoran, ρ-Nitro-6-p-(p-di äthylaminophenyl)amino­anilinofluoran, 2-Amino-6-p-(p-dimäthylaminophenyl)amino­anilinofluoran, 2-Diäthylamino-6-p-(p-dimäthylamino­phenyl)aminoanilinofluoran, 2-Phenyl-6-p-(p-phenylamino­phenyl)aminoanilinofluoran, 2-Benzyl-6-p-(p-phenylamino­phenyl)aminoanilinofluoran, 2-Hydroxy-6-p-(p-phenyl­aminophenyl)aminoanilinofluoran, 3-Methyl-6-p-(p-di­methylaminophenyl)aminoanilinofluoran, 3-Diäthylamino-6-­p-(p-diäthylaminophenyl)aminoanilinofluoran, 3-Diäthyl­amino-6-p-(p-dibutylaminophenyl)aminoanilino-fluoran, 3-­Methyl-7-p-(p-dimethylaminophenyl)aminoanilinofluoran, 3-­Methoxy-7-p-(p-dimethylaminophenyl)aminoanilinofluoran, 3-Chlor-7-p-(p-dimethylaminophenyl)aminoanilinofluoran, 3-Nitro-7-p-(p-diäthylaminophenyl)aminoanilinofluoran, 3-­Amino-7-p-(p-diäthylaminophenyl)aminoanilinofluoran, 3-­Diäthylamino-7-p-(p-diäthylaminophenyl)aminoanilino­fluoran, 3-Phenyl-7-p-(p-phenylaminophenyl)aminoanili­nofluoran, 3-Benzyl-7-p-(p-phenylaminophenyl)amino­anilinofluoran, 3-Hydroxy-7-p-(p-phenylaminophenyl)ami­noanilinofluoran, 2-Methyl-7-p-(p-dimethylaminophe­nyl)aminoanilinofluoran, 2-Diäthylamino-7-p-(p-diäthyl­ aminophenyl)aminoanilinofluoran, 2-Diäthylamino-7-p-(p-­dibutylaminophenyl)aminoanilinofluoran, 2-p-(p-­dimethylaminophenyl)aminoanilino-6-methylfluoran, 2-p-(p-­Dimethylaminophenyl)aminoanilino-6-methoxyfluoran, 2-p-­(p-Dimethylaminophenyl)aminoanilino-6-chlorofluoran, 2-p-­(p-diäthylaminophenyl)aminoanilino-6-nitrofluoran, 2-p-(p-diäthylaminophenyl)aminoanilino-6-aminofluoran, 2-p-(p-diäthylaminophenyl)aminoanilino-6-diäthylamino­fluoran, 2-p-(p-Phenylaminophenyl)aminoanilino-6-phenylfluoran, 2-p-(p-Phenylaminophenyl)aminoanilino-6-benzylfluoran, 2-p-(p-Phenylaminophenyl)aminoanilino-6-hydroxyfluoran, 2-p-(p-Dimethylaminophenyl)aminoanilino-6-methylfluoran, 2-p-(p-Diäthylaminophenyl)aminoanilino-6-diäthylfluoran, 2-p-(p-Phenylaminophenyl)aminoanilino-6-diäthylamino­fluoran, 3-p-(p-Dimethylaminophenyl)aminoanilino-7-methylfluoran, 3-p-(-p-Dimethylaminophenyl)aminoanilino-7-methoxyfluoran, 3-p-(p-Dimethylaminophenyl)aminoanilino-7-chlorfluoran, 3-p-(p-Diäthylaminophenyl)aminoanilino-7-nitrofluoran, 3-p-(p-Diäthylaminophenyl)aminoanilino-7-aminofluoran, 3-p-(p-Diäthylaminophenyl)aminoanilino-7-diäthylamino­fluoran, 3-p-(p-Phenylaminophenyl)aminoanilino-7-phenylfluoran, 3-p-(p-Phenylaminophenyl)aminoanilino-7-benzylfluoran, 3-p-(p-Phenylaminophenyl)aminoanilino-7-hydroxyfluoran, 3-p-(p-Dimethylaminophenyl)aminoanilino-7-methylfluoran, 3-p-(p-Diäthylaminophenyl)aminoanilino-7-diäthylamino­fluoran, und 3-p-(p-Phenylaminophenyl)aminoanilino-7-diäthylamino­fluoran.The fluorine leuco dyes according to the invention are not subject to any particular restrictions; the following can be used, for example: 2-methyl-6-p- (p-dimethylaminophenyl) aminoani linofluoran, 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, ρ-nitro-6-p- (p-di ethylaminophenyl) aminoanilinofluoran, 2- Amino-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-diethylamino-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-phenyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2-benzyl-6-p - (p-phenylaminophenyl) aminoanilinofluoran, 2-hydroxy-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 3-diethylamino-6-p- (p-diethylaminophenyl ) aminoanilinofluoran, 3-diethylamino-6-p- (p-dibutylaminophenyl) aminoanilino-fluoran, 3-methyl-7-p- (p-dimethylaminophenyl) aminoanilinofluoran, 3-methoxy-7-p- (p-dimethylaminophenyl) aminoanilinofluoran, 3-chloro-7-p- (p-dimethylaminophenyl) aminoanilinofluoran, 3-nitro-7-p- (p-diethylaminophenyl) aminoanilinofluoran, 3-amino-7-p- (p-diethylaminophenyl) aminoanilinofluoran, 3-diethylamino-7 -p- (p-diethylaminophenyl) aminoanilinofluoran, 3-pheny l-7-p- (p-phenylaminophenyl) aminoanilinofluoran, 3-benzyl-7-p- (p-phenylaminophenyl) aminoanilinofluoran, 3-hydroxy-7-p- (p-phenylaminophenyl) aminoanilinofluoran, 2-methyl-7-p - (p-dimethylaminophenyl) aminoanilinofluoran, 2-diethylamino-7-p- (p-diethyl aminophenyl) aminoanilinofluoran, 2-diethylamino-7-p- (p-dibutylaminophenyl) aminoanilinofluoran, 2-p- (p-dimethylaminophenyl) aminoanilino-6-methylfluoran, 2-p- (p-dimethylaminophenyl) aminoanilino-6-2-methoxy -p- (p-dimethylaminophenyl) aminoanilino-6-chlorofluorane, 2-p- (p-diethylaminophenyl) aminoanilino-6-nitrofluorane, 2-p- (p-diethylaminophenyl) aminoanilino-6-aminofluorane, 2-p- (p -diethylaminophenyl) aminoanilino-6-diethylaminofluoran, 2-p- (p-phenylaminophenyl) aminoanilino-6-phenylfluorane, 2-p- (p-phenylaminophenyl) aminoanilino-6-benzylfluorane, 2-p- (p-phenylaminophenyl) aminoanilino 6-hydroxyfluorane, 2-p- (p-dimethylaminophenyl) aminoanilino-6-methylfluorane, 2-p- (p-diethylaminophenyl) aminoanilino-6-diethylfluorane, 2-p- (p-phenylaminophenyl) aminoanilino-6-diethylaminofluorane, 3 -p- (p-dimethylaminophenyl) aminoanilino-7-methylfluorane, 3-p - (- p-dimethylaminophenyl) aminoanilino-7-methoxyfluorane, 3-p- (p-dimethylaminophenyl) aminoanilino-7-chlorofluorane, 3-p- ( p-diethylaminophenyl) aminoanilino-7-nitrofl uoran, 3-p- (p-diethylaminophenyl) aminoanilino-7-aminofluoran, 3-p- (p-diethylaminophenyl) aminoanilino-7-diethylaminofluoran, 3-p- (p-phenylaminophenyl) aminoanilino-7-phenylfluorane, 3-p- (p-phenylaminophenyl) aminoanilino-7-benzylfluorane, 3-p- (p-phenylaminophenyl) aminoanilino-7-hydroxyfluorane, 3-p- ( p-dimethylaminophenyl) aminoanilino-7-methylfluorane, 3-p- (p-diethylaminophenyl) aminoanilino-7-diethylaminofluorane, and 3-p- (p-phenylaminophenyl) aminoanilino-7-diethylaminofluorane.

Die erfindungsgemäßen Fluorantypleukofarbstoffe der allgemeinen Formel (I) werden allein oder im Gemisch verwendet.The fluorantypleuco dyes of the general formula (I) according to the invention are used alone or in a mixture.

Erfindungsgemäße Bindemittel sind z.B. völlig verseifter Polyvinylalkohol, Polymerisationsgrad: 200-1900, teilweise verseifter Polyvinylalkohol, karboxylierter Polyvinylalko­hol, amidmodifizierter Polyvinylalkohol, sulfonsäuremodi­fizierter Polyvinylalkohol, butyralmodifizierter Polyvinyl­alkohol, andere modifizierte Polyvinylalkohole, Hydroxy­äthylzellulose, Methylzellulose, Carboxymethylzellulose, Styrol-Maleinsäureanhydrid-Copolymere, Styrol-Butadien-­Copolymere, Zellulosederivate wie Äthylzellulose und Acetyl­zellulose, Polyvinylchlorid, Polyvinylazetat, Polyacrylamid, Polyacrylsäureester, Polyvinylbutyral, Polystyrol, Copoly­ mere von obigen Verbindungen, Polyamidharz, Siliconharz, Petroleumkunstharz, Terpenharz, Ketonharz und Cumaron­harz. Diese hochmolekularen Bindemittel können verwendet werden, nachdem sie in einem Lösungsmittel wie Wasser, Alkohol, Keton, Ester, Kohlenwasserstoff usw. gelöst oder in Wasser oder Lösungsmittel emulgiert und dispergiert wurden.Binders according to the invention are, for example, completely saponified polyvinyl alcohol, degree of polymerization: 200-1900, partly saponified polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl cellulose styrene, methyl malolymethyl copolymer, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methylcellulose Copolymers, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrene, copoly mers of the above compounds, polyamide resin, silicone resin, petroleum resin resin, terpene resin, ketone resin and coumarone resin. These high molecular weight binders can be used after being dissolved in a solvent such as water, alcohol, ketone, ester, hydrocarbon, etc., or emulsified and dispersed in water or solvent.

Die Art und Menge des erfindungsgemäßen Elektronenakzep­tors wie des Metalldoppelsalzes der gesättigten höheren Fettsäure, des Elektronendonators wie des mehrwertigen Phenols, des im nahen Ultrarot absorbierenden Leuko­farbstoffs, des Bindemittels und der anderen Additive, die je nach dem gewünschten Effekt und der Eignung für Aufzeichnungszwecke gewählt werden, sind nicht besondes beschränkt. Im allgemeinen ist es vorteilhaft, 1 bis 6 Gew.-Teile des Elektronendonators, 0,5 bis 5 Gew.-Teile des im nahem Ultrarot absorbierenden Leukofarbstoffs, 1 bis 20 Gew.-Teile Füllstoff, 0,5 bis 4 Gew.-Teile Bindemittel, und 5 bis 20 Gew.-Teile Füllstoff, bezogen auf 1 bis 9 Gew.-Teile des Elektronenakzeptors, zu verwenden.The type and amount of the electron acceptor according to the invention such as the metal double salt of the saturated higher fatty acid, the electron donor such as the polyhydric phenol, the near-infrared absorbing leuco dye, the binder and the other additives, which are chosen depending on the desired effect and suitability for recording purposes, are not particularly limited. In general, it is advantageous to use 1 to 6 parts by weight of the electron donor, 0.5 to 5 parts by weight of the near-infrared absorbing leuco dye, 1 to 20 parts by weight of filler, 0.5 to 4 parts by weight Binder, and 5 to 20 parts by weight of filler, based on 1 to 9 parts by weight of the electron acceptor.

Das erfindungsgemäße wärmeempfindliche Material wird hergestellt, indem man die Beschichtungsmasse auf ein Basismaterial wie Papier, synthetisches Papier, Film, Kunststoff usw. aufträgt.The heat sensitive material of the present invention made by applying the coating composition to a base material such as paper, synthetic paper, film, plastic, etc.

Der erfindungsgemäße Elektronenakzeptor, der erfin­dungsgemäße Elektronendonator und der erfindungsgemäße basische farblose chromogene Farbstoff werden mittels einer Mahlvorrichtung, wie Kugelmühle, Reibungsmühle, Sandschleifmaschine usw., oder mittels einer geeigneten Emulgiermaschine bis zu einer Teilchengröße von mehreren Mikron oder kleiner zermahlen: Hierzu gibt man Binde­mittel, gegebenenfalls, verschiedene Additive, um die erfindungsgemäße Beschichtungsmasse herzustellen.The electron acceptor according to the invention, the electron donor according to the invention and the basic colorless chromogenic dye according to the invention are ground to a particle size of several microns or smaller by means of a grinding device, such as a ball mill, attrition mill, sand grinder, etc., or by means of a suitable emulsifying machine: binders are added, if appropriate , various additives to produce the coating composition of the invention.

Die Additive, die erfindungsgemäß verwendet werden können, sind z.B. folgende:
Füllstoffe; Trennmittel zur Verhütung des Anhaftens eines Blattes wie Metallsalze von Fettsäuren; Gleitmittel zur Mottling-Verhinderung, wie Fettsäureamid, Äthylenbisamid, Montanwachs, Polyäthylenwachs usw.; Dispergiermittel, wie Dioctylsulfobernsteinsäurenatrium­salz, Natriumdodecylbenzolsulfonat, Natriumlaurylalkohol­sulfat, Natrumalginat usw.; UV-Absorptionsmittel der Benzophenon- und Triazolreihe; Antischaummittel; wasser­ fest machende Mittel usw.The additives which can be used according to the invention are, for example, the following:
Fillers; Anti-sticking releasing agents such as metal salts of fatty acids; Mottling prevention lubricants such as fatty acid amide, ethylene bisamide, montan wax, polyethylene wax, etc .; Dispersants such as sodium dioctyl sulfosuccinic acid, sodium dodecyl benzene sulfonate, sodium lauryl alcohol sulfate, sodium alginate, etc .; UV absorbers of the benzophenone and triazole series; Anti-foaming agents; water mooring agents, etc.

Als erfindungsgemäße Füllstoffe können sowohl anorganische wie organische Füllstoffe, die auf dem Papierbearbeitungsgebiet angewendet werden, verwendet werden. Beispiele für erfindungsgemäße Füller sind Tonerde, Talk, Siliciumdioxid, Magnesiumcarbonat, Alumi­niumhydroxid, Magnesiumhydroxid, Bariumsulfat, Kaolin, Titandioxid, Zinkoxid, Calciumcarbonat, Aluminiumoxid, Harnstoff-Formalkehydharz, Polystyrolharz, Phenolharz usw.Both inorganic and organic fillers which are used in the paper processing field can be used as fillers according to the invention. Examples of fillers according to the invention are alumina, talc, silicon dioxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, barium sulfate, kaolin, titanium dioxide, zinc oxide, calcium carbonate, aluminum oxide, urea-formaldehyde resin, polystyrene resin, phenolic resin, etc.

Die Ursache für die überlegene optische Lesbarkeit im nahen ultraroten Bereich des erfindungsgemäßen wärme­empfindlichen Aufzeichnungsblattes gründet sich darauf, daß bei der Farbentwicklung unter Komplex­bildung durch Schmelzreaktion zwischen einem Metall­doppelsalz als Elektronenakzeptor und einem Elektronen­donator wie mehrwertigem Phenolderivat ein gefärbtes Bild im sichtbaren und nahen ultraroten Bereich (Wellenlänge­bereich 700-1500 nm) entsteht. In der Praxis ist die Ultrarot-Absorption einer derartigen Kombination von einem Elektronenakzeptor und einem Elektronendonator gering, was bei der praktischen Ver­wendung Schwierigkeiten bereitet. Daher wird zu dieser Kombination der erfindungsgemäße Fluoranleukofarb­stoff gegeben, der bei der Schmelzreaktion mit einem Elektronendonator, wie phenolischen Derivaten, die nahen ultraroten Strahlen wirksamer absorbieren kann. In dieser Weise erhält man ein wärmeempfindliches Aufzeichnungs­blatt, das eine überlegene optische Lesbarkeit im nahen ultraroten Bereich aufweist.The reason for the superior optical legibility in the near-red range of the heat-sensitive recording sheet according to the invention is based on the fact that during color development with complex formation by melting reaction between a metal double salt as an electron acceptor and an electron donor such as polyvalent phenol derivative, a colored image in the visible and near-red range (wavelength range 700 -1500 nm) arises. In practice, the infrared absorption of such a combination of an electron acceptor and one Electron donor small, which is difficult in practical use. Therefore, the fluoranleuco dye of the present invention is added to this combination, which can more effectively absorb the near-ultraviolet rays in the melting reaction with an electron donor such as phenolic derivatives. In this way, a thermosensitive recording sheet is obtained which has superior optical readability in the near ultraviolet range.

(Beispiele)(Examples)

Die Erfindung wird anhand der nachfolgenden Beispiele näher erläutert.
Als Abkürzung für Gewichtsteile wird "Teile" verwendet.The invention is illustrated by the following examples.
As an abbreviation for parts by weight, "parts" is used.

(Beispiel 1 (Test-Nr. 1-4))(Example 1 (Test No. 1-4)) Lösung A (Elektronenakseptordispersion)Solution A (electron acceptor dispersion)

Metalldoppelsalz einer höheren Fettsäure
(Siehe Tabelle 1.)      9,0 Teile
10%ige wäßrige Lösung von
Polyvinylalkohol      10,0 Teile
Wasser      6,0 Teile
Double metal salt of a higher fatty acid
(See Table 1.) 9.0 parts
10% aqueous solution of
Polyvinyl alcohol 10.0 parts
Water 6.0 parts

Lösung B (Elektronendonatordispersion)Solution B (electron donor dispersion)

Mehrwertiges Phenolderivat
(Siehe Tabelle 1.)      6,0 Teile
Zinkstearat      1,5 Teile
10%ige wäßrige Lösung von Polyvinylalkohol      13,75 Teile
Wasser      8,25 Teile
Polyvalent phenol derivative
(See Table 1.) 6.0 parts
Zinc stearate 1.5 parts
10% aqueous solution of polyvinyl alcohol 13.75 parts
Water 8.25 parts

Lösung C (Dispersion eines im nahen Ultrarot absorbierenden Leukofarbstoffes)Solution C (dispersion of a near-infrared absorbing leuco dye)

Leukofarbstoff (Siehe Tabelle 1.)      0,5 Teile
10%ige wäßrige Lösung von Polyvinylalkohol      12,5 Teile
Wasser      0,75 Teile
Leuco dye (See Table 1.) 0.5 parts
10% aqueous solution of polyvinyl alcohol 12.5 parts
Water 0.75 parts

Die Lösungen der obigen Zusammensetzungen wurden in einer Reibungsmühle einzeln bis zu einer Teilchengröße von 3 Mikron vermahlen.The solutions of the above compositions were individually milled to a particle size of 3 microns in an attritor.

Die Lösungen wurden dann im folgenden Verhältnis mitein­ander vermischt, um eine wärmeempfindliche Beschichtungs­masse zu erhalten.
Lösung A      25,0 Teile
Lösung B      29,5 Teile
Lösung C      2,5 Teile
Kaolinton (5%ige wäßrige Dispersion)      12,0 TeileThe solutions were then mixed together in the following ratio to obtain a heat sensitive coating composition.
Solution A 25.0 parts
Solution B 29.5 parts
Solution C 2.5 parts
Kaolin clay (5% aqueous dispersion) 12.0 parts

Die obige Beschichtungsmasse wurde in einer Beschich­tungsmenge von 6,0 g/m² auf ein Basispapier mit einem Gewicht von 50 g/m² aufgetragen, getrocknet und superka­landriert, um eine Glätte von 200-600 Sekunden einzustel­len. Man erhielt ein wärmeempfindliches Aufzeichnungs­blatt.The above coating composition was applied in a coating amount of 6.0 g / m² on a base paper with a weight of 50 g / m², dried and supercalendered to set a smoothness of 200-600 seconds. A heat sensitive recording sheet was obtained.

(Vergleichsbeispiele (Test-Nr. 5-8))(Comparative Examples (Test No. 5-8)) Lösung D (Elektronenakzeptordispersion)Solution D (electron acceptor dispersion)

Metalldoppelsalz einer höheren Fettsäure (Siehe Tabelle 1.)      9,0 Teile
10%ige wäßrige Lösung von Polyvinylalkohol      10,0 Teile
Wasser      6,0 Teile
Metal double salt of a higher fatty acid (See Table 1.) 9.0 parts
10% aqueous solution of polyvinyl alcohol 10.0 parts
Water 6.0 parts

Lösung F (Elektronendonatordispersion)Solution F (electron donor dispersion)

Mehrwertiges Phenolderivat (Siehe Tabelle 2.)      6,0 Teile
Zinkstearat      1,5 Teile
10%ige wäßrige Lösung von Polyvinylalkohol      13,75 Teile
Wasser      8,25 Teile
Polyvalent phenol derivative (See Table 2.) 6.0 parts
Zinc stearate 1.5 parts
10% aqueous solution of polyvinyl alcohol 13.75 parts
Water 8.25 parts

Die Lösungen wurden dann im folgenden Verhältnis mitein­ander vermischt, um eine wärmeempfindliche Beschichtungs­masse zu erhalten.
Lösung D      25,0 Teile
Lösung F      29,5 Teile
Kaolinton (50%ige wäßrige Dispersion)      12,0 TeileThe solutions were then mixed together in the following ratio to obtain a heat sensitive coating composition.
Solution D 25.0 parts
Solution F 29.5 parts
Kaolin clay (50% aqueous dispersion) 12.0 parts

Man erhielt in der gleichen Weise wie im Beispiel 1 ein wärmeempfindliches Aufzeichnungsblatt.A heat-sensitive recording sheet was obtained in the same manner as in Example 1.

Die in den Beispielen und Vergleichsbeispielen erhalte­nen Aufzeichnungsblätter wurden hinsichtlich der Qualität geprüft, die Ergebnisse sind in Tabelle 1 zusammengefaßt.

Figure imgb0008
The recording sheets obtained in the examples and comparative examples were checked for quality, and the results are summarized in Table 1.
Figure imgb0008

AnmerkungenRemarks

  • (1) Bilddichte: Ein wärmeempfindliches Aufzeichnungs­blatt wird bei einer angelegten Spannung von 18,03 V und einer Pulsbreite von 3,2 Millisekunden unter Verwendung einer Faksimiliermaschine (von TOSHIBA CORPORATION) mit einer Aufzeichnung versehen. Die Bilddichte wird mit einem Macbeth-Dichtemesser (RD-914, Verwendung des Amber-Filters; die unten beschriebenen Messungen erfolgen unter gleichen Bedingungen) bestimmt.(1) Image density: A thermosensitive recording sheet is recorded at an applied voltage of 18.03 V and a pulse width of 3.2 milliseconds using a facsimile machine (from TOSHIBA CORPORATION). The image density is determined using a Macbeth density meter (RD-914, using the amber filter; the measurements described below are carried out under the same conditions).
  • (2) Reflexionsgrad für ultrarotes Licht: Der Reflexionsgrad der in obiger Anmerkung (1) erwähnten Aufzeichnung wird mit einem Spektrometer bei einer Wellenlänge von 940 nm gemessen.(2) Reflectance for Ultra Red Light: The reflectance of the recording mentioned in Note (1) above is measured with a spectrometer at a wavelength of 940 nm.
(Vorteile der Erfindung)(Advantages of the Invention)

Das erfindungsgemäße Aufzeichnungsmaterial weist überlegene optische Lesbarkeit im nahen ultraroten Bereich auf.The recording material of the present invention has superior optical readability in the near ultra-red range.

Claims (8)

(1) Wärmeempfindliches Aufzeichnungsmaterial mit einer wärmeempfindlichen Farbentwicklungsschicht auf einem Träger, wobei die wärmeempfindliche Aufzeichnungs­schicht einen Elektronenakzeptor und einen Elektro­nendonator enthält, die unter Chelatbildung mitein­ander reagieren, dadurch gekennzeichnet, daß die wärmeempfindliche Aufzeichnungsschicht einen im nahen Ultrarot absorbierenden Fluoranfarbstoff der folgen­den allgemeinen Formel (I) enthält,
Figure imgb0009
 worin mindestens einer der Reste R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ und R₉ eine Gruppe der allgemeinen Formel
Figure imgb0010
 bedeutet, worin
T₁, T₂ und T₃ gleich oder verschieden sind, und jeweils ein Wasserstoffatom, eine C₁-C₈-Alkyl-, C₃-C₉-Alkenyl- ­oder C₃-C₉-Alkinylgruppe bedeuten;
T₄ ein Wasserstoffatom, eine C₁-C₈-Alkyl-, C₃-C₉-Alkenyl-, C₃-C₉-Alkinyl- oder Phenylgruppe bedeutet; außerdem T₃ und T₄ mit einem benachbarten STickstoffatom verbunden sein können unter Bildung einer Morpholino-, Pyrrolidino-, Piperidino- oder Hexamethyleniminogruppe;
und n eine ganze Zahl von 0 bis 4 bedeutet.(1) A heat-sensitive recording material having a heat-sensitive color developing layer on a support, the heat-sensitive recording layer containing an electron acceptor and an electron donor which react with one another to form a chelate, characterized in that the heat-sensitive recording layer is a near-infrared absorbing fluoran dye of the following general formula (I) contains
Figure imgb0009
 wherein at least one of the radicals R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ and R₉ is a group of the general formula
Figure imgb0010
 means what
T₁, T₂ and T₃ are the same or different and each represents a hydrogen atom, a C₁-C₈ alkyl, C₃-C₉ alkenyl or C₃-C₉ alkynyl group;
T₄ represents a hydrogen atom, a C₁-C₈ alkyl, C₃-C₉ alkenyl, C₃-C₉ alkynyl or phenyl group; T₃ and T₄ may also be connected to an adjacent nitrogen atom to form a morpholino, pyrrolidino, piperidino or hexamethyleneimino group;
and n represents an integer from 0 to 4. (2) Wärmeempfindliches Aufzeichnungsmaterial gemäß Anspruch 1, dadurch gekennzeichnet, daß der Elektro­nenakzeptor ein Metalldoppelsalz einer höheren Fettsäure mit 16 bis 35 Kohlenstoffatomen ist.(2) Heat-sensitive recording material according to claim 1, characterized in that the electron acceptor is a metal double salt of a higher fatty acid with 16 to 35 carbon atoms. (3) Wärmeempfindliches Aufzeichnungsmaterial gemäß Anspruch 2, dadurch gekennzeichnet, daß das Metall­doppelsalz einer höheren Fettsäure mindestens zwei Metalle aus der Gruppe Eisen, Zink, Calcium, Magnesium, Aluminium, Barium, Blei, Mangan, Zinn, Nickel, Kobalt, Kupfer, Silber und Quecksilber ent­hält.(3) Heat-sensitive recording material according to claim 2, characterized in that the metal double salt of a higher fatty acid contains at least two metals from the group iron, zinc, calcium, magnesium, aluminum, barium, lead, manganese, tin, nickel, cobalt, copper, silver and Contains mercury. (4) Wärmeempfindliches Aufzeichnungsmaterial gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeich­net, daß der Elektronendonator mindestens eine Sub­stanz ausgewählt aus mehrwertigen aromatischen Hydroxiverbindungen, Diphenylcarbazid, Diphenylcar­bazon, Hexamethylentetramin, Spirobenzopyran und 1-­Formyl-4-phenylsemicarbazid ist.(4) Heat-sensitive recording material according to one of the preceding claims, characterized in that the electron donor is at least one substance selected from polyvalent aromatic hydroxyl compounds, diphenylcarbazide, diphenylcarbazone, hexamethylenetetramine, spirobenzopyran and 1-formyl-4-phenylsemicarbazide. (5) Wärmeempfindliches Aufzeichnungsmaterial gemäß Anspruch 4, dadurch gekennzeich­net, daß der Elektronendonator mindestens eine mehr­wertige aromatische Hydroxiverbindung der allge­meinen Formel (I) ist :
Figure imgb0011
 (worin R₁ eine Alkylgruppe mit 18 bis 35 Kohlen­stoffatomen bedeutet); n eine ganze Zahl von 2 bis 3 bedeutet; und "-X-" für ―CH₂―, ―CO₂―, ―CO―, ―O―, ―CONH―, ―C
Figure imgb0012
―

(worin Rʹ eine Alkyl­gruppe mit 5 bis 30 Kohlenstoffatomen bedeutet),
-SO₂-, -SO₃- oder -SO₂NH- steht.(5) Heat-sensitive recording material according to claim 4, characterized in that the electron donor is at least one polyvalent aromatic hydroxyl compound of the general formula (I):
Figure imgb0011
 (wherein R₁ represents an alkyl group having 18 to 35 carbon atoms); n represents an integer from 2 to 3; and "-X-" for ―CH₂―, ―CO₂―, ―CO―, ―O―, ―CONH―, ―C
Figure imgb0012
-

(wherein Rʹ represents an alkyl group with 5 to 30 carbon atoms),
-SO₂-, -SO₃- or -SO₂NH- stands. (6) Wärmeempfindliches Aufzeichnungsmaterial gemäß einem der Ansprüche 1-5, dadurch gekennzeichnet, daß der Fluoranleukofarbstoff der allgemeinen Formel (I) 2-Chlor-3-methyl-6-p-(p-phenylamino-phenyl)ami­noanilinofluoran oder 2-Methyl-6-p-(p-dimethylamino­phenyl)aminoanilinofluoran ist,(6) Heat-sensitive recording material according to one of claims 1-5, characterized in that the fluoranleuco dye of the general formula (I) 2-chloro-3-methyl-6-p- (p-phenylamino-phenyl) aminoanilinofluoran or 2-methyl- 6-p- (p-dimethylaminophenyl) aminoanilinofluoran, (7) Wärmeempfindliches Aufzeichnungsmaterial gemäß einem der Ansprüche 1-6, dadurch gekennzeichnet, daß die Farbentwicklungsschicht 1 bis 6 Gewichtsteile Elektronendonator, 0,5 bis 5 Gewichtsteile des im nahen Ultrarot absorbierenden Leukofarbstoffs, 0,5 bis 4 Gewichtsteile Bindemittel, und 5 bis 20 Gewichts­teile Füllstoff, bezogen auf 1 bis 9 Gewichtsteile des Elektronenakzeptors enthält.(7) Heat-sensitive recording material according to one of claims 1-6, characterized in that the color developing layer 1 to 6 parts by weight of electron donor, 0.5 to 5 parts by weight of the near-infrared absorbing leuco dye, 0.5 to 4 parts by weight of binder, and 5 to 20 Parts by weight of filler, based on 1 to 9 parts by weight of the electron acceptor. (8) Wärmeempfindliches Aufzeichnungsmaterial gemäß einem der Ansprüche 1-7, dadurch gekennzeichnet, daß der Träger ein Papier, synthetisches Papier, ein Film oder ein Kunststoff ist.(8) Heat-sensitive recording material according to one of claims 1-7, characterized in that the carrier is a paper, synthetic paper, a film or a plastic.
EP88105625A 1987-04-09 1988-04-08 Heat-sensitive recording material Expired - Lifetime EP0286116B1 (en)

Applications Claiming Priority (2)

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JP87503/87 1987-04-09
JP62087503A JPH066392B2 (en) 1987-04-09 1987-04-09 Thermal recording

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EP0286116A3 EP0286116A3 (en) 1989-04-12
EP0286116B1 EP0286116B1 (en) 1991-12-11

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287121A2 (en) * 1987-04-17 1988-10-19 Jujo Paper Co., Ltd. Heat and light-sensitive recording material and recording method
EP0307836A2 (en) * 1987-09-14 1989-03-22 Jujo Paper Co., Ltd. Heat-sensitive recording material
EP0574879A1 (en) * 1992-06-17 1993-12-22 Mitsubishi Paper Mills, Ltd. Reversible heat-sensitive recording material
EP0599580A1 (en) * 1992-11-20 1994-06-01 Nippon Paper Industries Co., Ltd. Thermal recording sheet

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Publication number Priority date Publication date Assignee Title
US5200947A (en) * 1989-02-03 1993-04-06 Jujo Paper Co., Ltd. Optical recording medium, optical recording method, and optical recording device used in method
EP0381492B1 (en) * 1989-02-03 1998-04-15 Nippon Paper Industries Co., Ltd. Optical recording medium, optical recording method, and optical recording device used in method
JP2536917B2 (en) * 1989-02-06 1996-09-25 日本製紙株式会社 Optical recording material
JP4090154B2 (en) * 1999-07-23 2008-05-28 富士フイルム株式会社 Planographic printing plate manufacturing method
JP2012220883A (en) * 2011-04-13 2012-11-12 Casio Electronics Co Ltd Negatively chargeable decoloring electrophotographic toner and method for manufacturing the same

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US4004065A (en) * 1974-12-13 1977-01-18 General Company, Ltd. Coated heat sensitive recording member
JPS5993387A (en) * 1982-11-19 1984-05-29 Ricoh Co Ltd Thermal recording material

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JPH0713195B2 (en) * 1986-07-31 1995-02-15 日本曹達株式会社 Fluoran compound and chromogenic recording material using the same
JP2778701B2 (en) * 1988-09-12 1998-07-23 マナック株式会社 Decolorization accelerator for bleaching

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US4004065A (en) * 1974-12-13 1977-01-18 General Company, Ltd. Coated heat sensitive recording member
JPS5993387A (en) * 1982-11-19 1984-05-29 Ricoh Co Ltd Thermal recording material

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Title
PATENT ABSTRACTS OF JAPAN, Band 8, Nr. 203 (M-326)[1640], 18. September 1984; & JP-A-59 093 387 (RICOH K.K.) 29-05-1984 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287121A2 (en) * 1987-04-17 1988-10-19 Jujo Paper Co., Ltd. Heat and light-sensitive recording material and recording method
EP0287121A3 (en) * 1987-04-17 1990-07-11 Jujo Paper Co., Ltd. Heat and light-sensitive recording material and recording method
EP0307836A2 (en) * 1987-09-14 1989-03-22 Jujo Paper Co., Ltd. Heat-sensitive recording material
EP0307836A3 (en) * 1987-09-14 1990-09-19 Jujo Paper Co., Ltd. Heat-sensitive recording material
EP0574879A1 (en) * 1992-06-17 1993-12-22 Mitsubishi Paper Mills, Ltd. Reversible heat-sensitive recording material
US5395815A (en) * 1992-06-17 1995-03-07 Mitsubishi Paper Mills Limited Reversible heat-sensitive recording material
EP0599580A1 (en) * 1992-11-20 1994-06-01 Nippon Paper Industries Co., Ltd. Thermal recording sheet
US5446009A (en) * 1992-11-20 1995-08-29 Nippon Paper Industries Co., Ltd. Thermal recording sheet

Also Published As

Publication number Publication date
JPH066392B2 (en) 1994-01-26
US4853363A (en) 1989-08-01
JPS63252784A (en) 1988-10-19
EP0286116B1 (en) 1991-12-11
EP0286116A3 (en) 1989-04-12
DE3866752D1 (en) 1992-01-23

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