EP0938419B1 - Thermo-sensitive printing sheet comprising a back coating containing starch, an acrylate copolymer and an alkaline catalyst - Google Patents

Thermo-sensitive printing sheet comprising a back coating containing starch, an acrylate copolymer and an alkaline catalyst Download PDF

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Publication number
EP0938419B1
EP0938419B1 EP98946412A EP98946412A EP0938419B1 EP 0938419 B1 EP0938419 B1 EP 0938419B1 EP 98946412 A EP98946412 A EP 98946412A EP 98946412 A EP98946412 A EP 98946412A EP 0938419 B1 EP0938419 B1 EP 0938419B1
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EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording sheet
sheet according
alkaline catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98946412A
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German (de)
French (fr)
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EP0938419A1 (en
Inventor
Wolfgang Wagner
Jutta Berndt
Franz Wirnitzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi HiTech Paper Flensburg GmbH
Original Assignee
Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
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Filing date
Publication date
Priority claimed from DE1997140072 external-priority patent/DE19740072A1/en
Priority claimed from DE1997148258 external-priority patent/DE19748258A1/en
Application filed by Mitsubishi HiTech Paper Flensburg GmbH, Stora Spezialpapiere GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Publication of EP0938419A1 publication Critical patent/EP0938419A1/en
Application granted granted Critical
Publication of EP0938419B1 publication Critical patent/EP0938419B1/en
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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
    • 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
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/08—Fastening or securing by means not forming part of the material of the label itself
    • G09F3/10—Fastening or securing by means not forming part of the material of the label itself by an adhesive layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]

Definitions

  • the invention relates to a heat sensitive Recording sheet with a substrate, one on arranged on its front, color formers and Color-sensitive heat-sensitive Recording layer and one on top of it Back trained back coating.
  • a recording sheet of the above Art is known from DE-C-38 36 660.
  • the Back coating can be made from water soluble High polymers such as starch, gelatin, Styrene maleic anhydride copolymer hydrolyzates or polyvinyl alcohol and water-insoluble Polymers such as latices are formed.
  • the Polymers can be used alone or as a mixture be used. With the known Back coating should be prevented that when used as a label, undesirable Influences of plasticizers on a with the Label to be provided, can act.
  • a barrier layer consisting of water-soluble polymers and a water-repellent wax or a wax-like Connection, provided.
  • the desired effect consists in avoiding harmful influences, especially by plasticizers.
  • US-A-4,593,298 discloses one Backside coating containing an alkali salt Styrene maleic acid copolymers and a polymeric Latex. With the known Back coating is said to Water resistance and block resistance be improved. At the same time, the Runnability improves and curl tendency of the paper.
  • EP-B-0 171 810 describes a back coating in which the durability of the recorded image is to be improved by using a polyurethane emulsion with an application weight of 1 to 5 g / m 2 by preventing liquids, such as plasticizers, Oil, water and solvents penetrate the color development layer from the back.
  • EP-A-0 518 552 describes a heat-sensitive recording material in which the substrate either from a thermoplastic Film or synthetic paper.
  • a coating on the back at least 20% from a water-soluble Polymers such as B. polyvinyl alcohol, Cellulose ether or starch.
  • Preferably contains the back coating is also water-insoluble Polymers such as B. copolymers of vinyl acetate-acrylic acid esters, Methacrylic acid esters and Acrylic acid esters, polyurethane resins, Polyvinyl chloride resins and Polyvinylidene chloride resins.
  • the one colored fluorescent dye composition in has its recording layer provided on the back with a barrier layer, which in the essentially from water-soluble Polymer materials, such as polyvinyl alcohol, various cellulose ethers, starch, gelatin, Casein and polyvinyl pyrolidone as well as in water dispersed resins, such as.
  • a barrier layer which in the essentially from water-soluble Polymer materials, such as polyvinyl alcohol, various cellulose ethers, starch, gelatin, Casein and polyvinyl pyrolidone as well as in water dispersed resins, such as.
  • B. Polystyrene emulsions can be produced.
  • the function of the barrier layer is to protect against harmful materials such as oils and Plasticizers used to discolor the in the Record layer developed images can.
  • From DE-A-38 06 201 is a heat sensitive Recording paper known in which the Paper backing has a layer that includes a contains cationic styrene / acrylic copolymer to when calendering or supercalendering the The dust and flakes avoid.
  • Other advantages include: wider contact area with the thermal head when Recording, a high recording density, a excellent point rendering, one low fog and low adhesion as well avoiding pollution or discoloration indicated on the heating head.
  • the order of the cationic styrene / acrylic copolymers may be used in Compound with starch, polyvinyl alcohol, one Latex, pigment or dye using a Size press or a coating device respectively.
  • the suitability of the known heat sensitive recording paper for Manufacture of labels, the back of which against the influence of oils and / or Plasticizers are stable in this document not described.
  • the surface sizing is a coating base paper provided for Manufacturing heat sensitive Recording material is to be used.
  • the surface sizing can save one Styrene / methacrylate is also a water-soluble one Copolymer are used.
  • the object of the present invention is therefore in the development of a heat sensitive Recording material with a Back coating, which compared to the im Substances used in offset and flexographic printing, especially organic solvents and a good one against plasticizers, oils and greases Has blocking effect.
  • the blocking should also the web wound on a roll in the Role can be prevented.
  • acrylate copolymer used is a consisting of acrylate and / or methacrylate To understand copolymer that no styrene or Vinyl acetate components include, and preferably has reactive groups.
  • the copolymer to be used according to the invention can be in the form of an aqueous dispersion or Emulsion present.
  • a alkaline catalyst will crosslink the Guaranteed acrylic copolymers and the Clogging tendency of the paper web counteracted.
  • the invention also contains starch derivatives, how to understand starch ether and starch ester.
  • starch Preferably the starch and that Acrylate copolymers cationic.
  • A mainly serves as the substrate paper made of cellulose fibers, in particular a paper is preferred whose Fibrous material consists of wood-free cellulose fibers.
  • the Back coating based on it Total weight, 40 to 50 parts by weight of starch contains.
  • the Back coating based on it Total weight, 30 to 40 parts by weight Acrylate copolymer included.
  • the Back coating based on it Total weight, 9 to 28 parts by weight, very special preferably 13 to 24 parts by weight of the alkaline Contains catalyst.
  • Suitable alkaline catalysts have been found Metal carbonates have proven to be particularly Calcium carbonate and magnesium carbonate as suitable proven to be a precipitated calcium carbonate entirely is particularly preferred. However, it is unsuitable Sodium carbonate because the sodium ions are one Corrosion of the thermal head can result. Potassium and Chloride compounds.
  • the Backside coating a cross-linking aid, in particular an epichlorohydrin resin.
  • an application weight of 1 to 3 g / m 2 for the backside coating in particular in the range from 1.5 to 2.5 g / m 2 , has proven to be suitable.
  • the heat sensitive according to the invention Recording paper is used as Label on food packaging and is especially for labeling with special Glue-applied labels for frozen foods suitable.
  • the invention Back coating prevents this Application the penetration of plasticizers in the Label so that a discoloration or change of the typeface created on the front in the heat sensitive recording layer is absent.
  • the heat-sensitive recording layer with a Protective layer is covered
  • Another area of application is the production of on the back with additional information printed tickets, but especially those Tickets on the back with solvent-based Magnetic stripes can be printed.
  • An aqueous preparation was prepared from 47 parts by weight of cationic starch, 16 parts by weight of precipitated calcium carbonate and 37 parts by weight of a cationic acrylate copolymer free of styrene or vinyl acetate components.
  • the preparation was adjusted to a solids content of 18% by weight - pH 7.5 - and applied in an amount of 2.2 g / m 2 to a base paper and dried.
  • the other side of the coated web was provided with an intermediate layer for receiving the heat-sensitive recording layer, the essential components of which consisted of an oil-absorbing pigment and binder.
  • the intermediate layer formed was then provided with a conventional heat-sensitive recording layer.

Abstract

A heat-sensitive recording sheet has A heat-sensitive recording layer containing color formers and color developers formed on one side of a substrate, a backcoat is formed on the side opposite to the recording layer, wherein this backcoat is formed of A mixture containing starch, an acrylate copolymer which does not comprise styrene or vinyl acetate components and has a film-forming temperature of less than 5° C., and an alkaline catalyst.

Description

Die Erfindung betrifft einen wärmeempfindlichen Aufzeichnungsbogen mit einem Substrat, einer auf seiner Vorderseite angeordneten, Farbbildner und Farbakzeptoren enthaltenden wärmeempfindlichen Aufzeichnungsschicht und einer auf seiner Rückseite ausgebildeten Rückseitenbeschichtung.The invention relates to a heat sensitive Recording sheet with a substrate, one on arranged on its front, color formers and Color-sensitive heat-sensitive Recording layer and one on top of it Back trained back coating.

Ein Aufzeichnungsbogen der vorstehend angegebenen Art ist aus der DE-C-38 36 660 bekannt. Die Rückseitenbeschichtung kann aus wasserlöslichen Hochpolymeren, wie Stärke, Gelatine, Styrolmaleinsäureanhydrid-Copolymer-Hydrolysaten oder Polyvinylalkohol sowie aus wasserunlöslichen Polymeren, wie Latices, gebildet werden. Die Polymeren können allein oder als Mischung verwendet werden. Mit der bekannten Rückseitenbeschichtung soll verhindert werden, daß bei der Verwendung als Etikett, unerwünschte Einflüsse von Weichmachern, die auf einem mit dem Etikett zu versehenden Blatt vorhanden sind, einwirken können. A recording sheet of the above Art is known from DE-C-38 36 660. The Back coating can be made from water soluble High polymers such as starch, gelatin, Styrene maleic anhydride copolymer hydrolyzates or polyvinyl alcohol and water-insoluble Polymers such as latices are formed. The Polymers can be used alone or as a mixture be used. With the known Back coating should be prevented that when used as a label, undesirable Influences of plasticizers on a with the Label to be provided, can act.

Bei einer mehrschichtigen, thermisch bedruckbaren Etikettenfolie mit wärmeempfindlicher Farbbildungsschicht auf der Vorderseite des Schichtträgers gemäß der DE-C-32 07 071 ist rückseitig eine Sperrschicht, bestehend aus wasserlöslichen Polymeren und einem wasserabstoßenden Wachs oder einer wachsähnlichen Verbindung, vorgesehen. Die angestrebte Wirkung besteht in der Vermeidung schädlicher Einflüsse, insbesondere durch Kunststoffweichmacher.With a multi-layer, thermally printable Label film with heat sensitive Color formation layer on the front of the Layer support according to DE-C-32 07 071 a barrier layer consisting of water-soluble polymers and a water-repellent wax or a wax-like Connection, provided. The desired effect consists in avoiding harmful influences, especially by plasticizers.

Gemäß der DE-A-35 29 781 wurde vorgeschlagen, den Beschichtungsträger zu bedrucken. Um das aufgedruckte Muster erkennen zu können, ist dabei entweder die wärmeempfindliche Aufzeichnungsschicht transparent auszubilden, bzw. muß im Fall der rückseitigen Bedruckung des Schichtträgers die Rückseitenbeschichtung und die zugehörige Klebstoffschicht transparent sein. Abgesehen davon, daß damit der Einsatz von Pigmenten, wie sie z. B. zur Verbesserung der Thermokopfeignung vielfach verwendet werden, ausgeschlossen wird, ist damit in nachteiliger Weise eine komplizierte Folge der einzelnen Verfahrensschritte erforderlich, da sich direkt im Anschluß an die Erzeugung des Streichrohpapiers der Druckvorgang anschließt, dem dann die weiteren Beschichtungs- und Kaschierungsschritte folgen.According to DE-A-35 29 781 it was proposed that To print coating carriers. To do that It is possible to recognize printed patterns either the heat sensitive To make the recording layer transparent, or must be printed on the back of the Backing and the associated adhesive layer be transparent. Apart from the fact that the use of Pigments such as z. B. to improve the Thermo head suitability is widely used, is excluded, is therefore disadvantageous Way a complicated sequence of each Procedural steps required, since directly in the Connection to the production of the coating base paper the printing process follows, followed by the others Coating and lamination steps follow.

Die US-A-4,593,298 offenbart eine Rückseitenbeschichtung, die ein Alkalisalz eines Styrolmaleinsäure-Copolymeren und einen polymeren Latex aufweist. Mit der bekannten Rückseitenbeschichtung soll die Wasserbeständigkeit und die Blockfestigkeit verbessert werden. Gleichzeitig soll auch die Laufeigenschaft verbessert und die Kräuselneigung des Papiers eingeschränkt werden.US-A-4,593,298 discloses one Backside coating containing an alkali salt Styrene maleic acid copolymers and a polymeric Latex. With the known Back coating is said to Water resistance and block resistance be improved. At the same time, the Runnability improves and curl tendency of the paper.

Die EP-B-0 171 810 beschreibt eine Rückseitenbeschichtung, bei der durch Einsatz einer Polyurethan-Emulsion mit einem Auftragsgewicht von 1 bis 5 g/m2 die Haltbarkeit des aufgezeichneten Bildes verbessert werden soll, indem verhindert wird, daß Flüssigkeiten, wie Weichmacher, Öl, Wasser und Lösungsmittel von der Rückseite in die Farbentwicklungsschicht eindringen.EP-B-0 171 810 describes a back coating in which the durability of the recorded image is to be improved by using a polyurethane emulsion with an application weight of 1 to 5 g / m 2 by preventing liquids, such as plasticizers, Oil, water and solvents penetrate the color development layer from the back.

Die EP-A-0 518 552 beschreibt ein wärmeempfindliches Aufzeichnungsmaterial, bei dem das Substrat entweder aus einem thermoplastischen Film oder aus einem synthetischen Papier besteht. Eine rückseitig aufgebrachte Beschichtung besteht zu mindestens 20 % aus einem wasserlöslichen Polymeren, wie z. B. Polyvinylalkohol, Zelluloseether oder Stärke. Vorzugsweise enthält die Rückseitenbeschichtung auch wasserunlösliche Polymere, wie z. B. Copolymere von Vinylacetat-Acrylsäureestern, Methacrylsäureestern und Acrylsäureestern, Polyurethanharze, Polyvinylchloridharze und Polyvinylidenchloridharze. Mit der Rückseitenbeschichtung soll der in der wärmeempfindlichen Aufzeichnungsschicht entstehenden Kräuselung entgegengewirkt werden. Ggf. kann zur Verbesserung der Wasserbeständigkeit der Rückseitenbeschichtung noch ein Vernetzungsmittel zugefügt werden.EP-A-0 518 552 describes a heat-sensitive recording material in which the substrate either from a thermoplastic Film or synthetic paper. There is a coating on the back at least 20% from a water-soluble Polymers such as B. polyvinyl alcohol, Cellulose ether or starch. Preferably contains the back coating is also water-insoluble Polymers such as B. copolymers of vinyl acetate-acrylic acid esters, Methacrylic acid esters and Acrylic acid esters, polyurethane resins, Polyvinyl chloride resins and Polyvinylidene chloride resins. With the Back coating is said to be in the heat sensitive recording layer resulting ripple can be counteracted. Possibly. can improve water resistance the back coating Crosslinking agents are added.

Ein in der DE-A-37 20 171 beschriebenes wärmeempfindliches Aufzeichnungsmaterial, das eine gefärbte Fluorezenzfarbstoffzusammensetzung in seiner Aufzeichnungsschicht aufweist, ist rückseitig mit einer Sperrschicht versehen, die im wesentlichen aus wasserlöslichen Polymermaterialien, wie Polyvinylalkohol, verschiedenen Zelluloseethern, Stärke, Gelatine, Kasein und Polyvinylpyrolidon sowie in Wasser dispergierten Harzen, wie z. B. Polystyrolemulsionen, hergestellt werden kann. Die Funktion der Sperrschicht besteht im Schutz vor schädlichen Materialien, wie Ölen und Weichmachern, die zur Verfärbung der in der Aufzeichnungsschicht entwickelten Bilder führen können.One described in DE-A-37 20 171 heat-sensitive recording material, the one colored fluorescent dye composition in has its recording layer provided on the back with a barrier layer, which in the essentially from water-soluble Polymer materials, such as polyvinyl alcohol, various cellulose ethers, starch, gelatin, Casein and polyvinyl pyrolidone as well as in water dispersed resins, such as. B. Polystyrene emulsions can be produced. The The function of the barrier layer is to protect against harmful materials such as oils and Plasticizers used to discolor the in the Record layer developed images can.

Aus der DE-A-38 06 201 ist ein wärmeempfindliches Aufzeichnungspapier bekannt, bei dem der Papierträger eine Schicht aufweist, die ein kationisches Styrol/Acryl-Copolymer enthält, um beim Kalandrieren oder Superkalandrieren des Papiers die Staub- und Flockenbildung zu vermeiden. Als weitere Vorteile werden eine breitere Kontaktfläche mit dem Wärmekopf beim Aufzeichnen, eine hohe Aufzeichnungsdichte, ein ausgezeichnetes Punktwiedergabevermögen, eine geringe Schleierbildung und geringe Haftung sowie die Vermeidung der Verschmutzung bzw. Verfärbung am Wärmekopf angegeben. Der Auftrag des kationischen Styrol/Acryl-Copolymeren kann ggf. in Verbindung mit Stärke, Polyvinylalkohol, einem Latex, Pigment oder Farbstoff mittels einer Leimpresse oder einer Beschichtungseinrichtung erfolgen. Die Eignung des bekannten wärmeempfindlichen Aufzeichnungspapiers zur Herstellung von Etiketten, deren Rückseite gegenüber dem Einfluß von Ölen und/oder Weichmachern stabil ist, wird in dieser Schrift nicht beschrieben.From DE-A-38 06 201 is a heat sensitive Recording paper known in which the Paper backing has a layer that includes a contains cationic styrene / acrylic copolymer to when calendering or supercalendering the The dust and flakes avoid. Other advantages include: wider contact area with the thermal head when Recording, a high recording density, a excellent point rendering, one low fog and low adhesion as well avoiding pollution or discoloration indicated on the heating head. The order of the cationic styrene / acrylic copolymers may be used in Compound with starch, polyvinyl alcohol, one Latex, pigment or dye using a Size press or a coating device respectively. The suitability of the known heat sensitive recording paper for Manufacture of labels, the back of which against the influence of oils and / or Plasticizers are stable in this document not described.

Gemäß der JP-A-60-2397 ist die Oberflächenleimung eines Streichrohpapiers vorgesehen, das zur Herstellung wärmeempfindlichen Aufzeichnungsmaterials eingesetzt werden soll. Alternativ wird dort vorgeschlagen, einen Vorstrich - unterhalb der wärmeempfindlichen Aufzeichnungsschicht - vorzusehen. Im Fall der Oberflächenleimung kann außer einem Styrol/Methacrylat auch noch ein wasserlösliches Copolymer zum Einsatz kommen.According to JP-A-60-2397, the surface sizing is a coating base paper provided for Manufacturing heat sensitive Recording material is to be used. Alternatively, one is proposed there Primer - below the heat sensitive Recording layer - to be provided. In the case of Surface sizing can save one Styrene / methacrylate is also a water-soluble one Copolymer are used.

In der Vergangenheit hat sich gezeigt, daß die bekannten Maßnahmen zur Ausbildung eines ausreichenden Widerstandes gegenüber Ölen, Fetten, Weichmachern und organischen Lösungsmitteln nicht ausreichend sind. In the past it has been shown that the known measures for training a sufficient resistance to oils, greases, Plasticizers and organic solvents are not are sufficient.

Die Aufgabe der vorliegenden Erfindung besteht daher in der Entwicklung eines wärmeempfindlichen Aufzeichnungsmaterials mit einer Rückseitenbeschichtung, die gegenüber den im Offset- und Flexodruck verwendeten Substanzen, insbesondere organischen Lösungsmitteln sowie gegenüber Weichmachern, Ölen und Fetten eine gute Sperrwirkung aufweist. Ferner soll das Verblocken der auf eine Rolle aufgewickelten Bahn in der Rolle verhindert werden.The object of the present invention is therefore in the development of a heat sensitive Recording material with a Back coating, which compared to the im Substances used in offset and flexographic printing, especially organic solvents and a good one against plasticizers, oils and greases Has blocking effect. The blocking should also the web wound on a roll in the Role can be prevented.

Die Lösung der Aufgabe gelingt bei einem wärmeempfindlichen Aufzeichnungsbogen mit einem Substrat, einer auf seiner Vorderseite angeordneten, Farbbildner und Farbakzeptoren enthaltenden wärmeepfindlichen Aufzeichnungsschicht und einer auf seiner Rückseite ausgebildeten Rückseitenbeschichtung dadurch, daß die Rückseitenbeschichtung aus einer Mischung gebildet ist, die

  • Stärke,
  • ein keine Styrol- oder Vinylacetatkomponenten umfassendes Acrylatcopolymeres mit einer Filmbildungstemperatur < 5 °C und
  • einen alkalischen Katalysator
enthält.
Vorzugsweise liegt die Mindestfilmbildungstemperatur bei < 2 °C.The object is achieved with a heat-sensitive recording sheet having a substrate, a heat-sensitive recording layer arranged on its front side, containing color formers and color acceptors, and a rear-side coating formed on its rear side in that the rear-side coating is formed from a mixture which
  • Strength,
  • an acrylate copolymer comprising no styrene or vinyl acetate components and having a film-forming temperature of <5 ° C. and
  • an alkaline catalyst
contains.
The minimum film formation temperature is preferably <2 ° C.

Unter dem in Beschreibung und Ansprüchen verwendeten Begriff Acrylatcopolymerisat ist ein aus Acrylat und/oder Methacrylat bestehendes Copolymerisat zu verstehen, das keine Styrol- oder Vinylacetatcomponenten umfaßt und vorzugsweise reaktionsfähige Gruppen aufweist.Under the in description and claims The term acrylate copolymer used is a consisting of acrylate and / or methacrylate To understand copolymer that no styrene or Vinyl acetate components include, and preferably has reactive groups.

Das erfindungsgemäß einzusetzende Copolymerisat kann in Form einer wässrigen Dispersion oder Emulsion vorliegen. Durch den Einsatz eines alkalischen Katalysators wird die Vernetzung des Acrylatcopolymeren gewährleistet und der Verblockungsneigung der Papierbahn entgegengewirkt.The copolymer to be used according to the invention can be in the form of an aqueous dispersion or Emulsion present. By using a alkaline catalyst will crosslink the Guaranteed acrylic copolymers and the Clogging tendency of the paper web counteracted.

Unter Stärke sind im Rahmen der vorliegenden Erfindung außer Stärke selbst auch Stärkederivate, wie Stärkeether und Stärkeester zu verstehen.Among strengths are within the scope of the present In addition to starch itself, the invention also contains starch derivatives, how to understand starch ether and starch ester.

Vorzugsweise sind die Stärke und das Acrylatcopolymere kationisch.Preferably the starch and that Acrylate copolymers cationic.

Als Substrat dient vorzugsweise ein hauptsächlich aus Zellulosefasern bestehendes Papier, insbesondere wird ein Papier bevorzugt, dessen Faserstoff aus holzfreien Zellulosefasern besteht.A mainly serves as the substrate paper made of cellulose fibers, in particular a paper is preferred whose Fibrous material consists of wood-free cellulose fibers.

Vermutlich erklärt sich die hervorragende Sperrwirkung durch die Filmbildungseigenschaften des Acrylatcopolymeren, das ohne den erfindungsgemäßen Zusatz von Stärke einen relativ weichen und leicht klebrigen Film bildet.The excellent is probably explained Barrier effect due to the film formation properties of the acrylate copolymer, which without the addition of starch according to the invention a relative forms a soft and slightly sticky film.

Es wird weiterhin bevorzugt, daß die Rückseitenbeschichtung, bezogen auf ihr Gesamtgewicht, 40 bis 50 Gew.-Teile Stärke enthält.It is further preferred that the Back coating, based on it Total weight, 40 to 50 parts by weight of starch contains.

Weiterhin wird bevorzugt, daß die Rückseitenbeschichtung, bezogen auf ihr Gesamtgewicht, 30 bis 40 Gew.-Teile Acrylatcopolymeres enthälu.It is further preferred that the Back coating, based on it Total weight, 30 to 40 parts by weight Acrylate copolymer included.

Als besonders geeignet hat sich erwiesen, daß die Rückseitenbeschichtung, bezogen auf ihr Gesamtgewicht, 9 bis 28 Gew.-Teile, ganz besonders bevorzugt 13 bis 24 Gew.-Teile, des alkalischen Katalysators enthält.It has proven particularly suitable that the Back coating, based on it Total weight, 9 to 28 parts by weight, very special preferably 13 to 24 parts by weight of the alkaline Contains catalyst.

Als geeignete alkalische Katalysatoren haben sich Metallcarbonate erwiesen, insbesondere haben sich Calciumcarbonat und Magnesiumcarbonat als geeignet erwiesen, wobei ein gefälltes Calciumcarbonat ganz besonders bevorzugt ist. Ungeeignet ist dagegen Natriumcarbonat, da die Natriumionen eine Korrosion des Thermokopfes zur Folge haben können. Ebenfalls ungeeignet sind Kalium- und Chloridverbindungen.Suitable alkaline catalysts have been found Metal carbonates have proven to be particularly Calcium carbonate and magnesium carbonate as suitable proven to be a precipitated calcium carbonate entirely is particularly preferred. However, it is unsuitable Sodium carbonate because the sodium ions are one Corrosion of the thermal head can result. Potassium and Chloride compounds.

Gemäß einer weiteren Ausführungsform kann die Rückseitenbeschichtung ein Vernetzungshilfsmittel, insbesondere ein Epichlorhydrinharz, enthalten.According to a further embodiment, the Backside coating a cross-linking aid, in particular an epichlorohydrin resin.

Insbesondere hat sich ein Auftragsgewicht für die Rückseitenbeschichtung von 1 bis 3 g/m2, insbesondere im Bereich von 1,5 bis 2,5 g/m2, als geeignet erwiesen. In particular, an application weight of 1 to 3 g / m 2 for the backside coating, in particular in the range from 1.5 to 2.5 g / m 2 , has proven to be suitable.

Der Einsatz von kationischen Komponenten zum Erhalt einer erfindungsgemäßen Rückseitenbeschichtung ist nicht zu verwechseln mit der seit langem bekannten Verwendung kationischer Leimungsmittel, wie sie zur Masseleimung dem Faserstoff zugesetzt werden oder ggf. auch als Oberflächenleimungsmittel mittels einer Leimpresse oder ähnlichen Vorrichtungen aufgetragen werden. Diese bekannten Auftragsmethoden führen nicht zu einem geschlossenen Film, wie er mit der erfindungsgemäß vorgesehenen Rückseitenbeschichtung auf einer Seite einer Papierbahn erzeugt wird.The use of cationic components for Obtaining an inventive Reverse coating is not to be confused with the long-known use cationic sizing agents, such as Bulk sizing can be added to the fiber or if necessary also as a surface sizing agent a size press or similar devices be applied. These well-known Application methods do not lead to one closed film, as with the invention provided back coating on a Side of a paper web is generated.

Alle in Beschreibung und Patentansprüchen der vorliegenden Anmeldung angegebenen Gew.-Teile sind als otro-Gew.-Teile, d. h. ofentrocken, zu verstehen.All in description and claims of the parts by weight given in the present application as otro parts by weight, d. H. oven dry, too understand.

Das erfindungsgemäße wärmeempfindliche Aufzeichnungspapier findet seine Verwendung als Etikett bei der Lebensmittelverpackung und ist insbesondere zur Etikettierung von mit speziellen Leimen aufzubringenden Etiketten für Tiefkühlkost geeignet. Die erfindungsgemäße Rückseitenbeschichtung verhindert bei dieser Anwendung das Eindringen von Weichmachern in das Etikett, so daß eine Verfärbung oder Veränderung des auf der Vorderseite erzeugten Schriftbildes in der wärmeempfindlichen Aufzeichnungsschicht ausbleibt. The heat sensitive according to the invention Recording paper is used as Label on food packaging and is especially for labeling with special Glue-applied labels for frozen foods suitable. The invention Back coating prevents this Application the penetration of plasticizers in the Label so that a discoloration or change of the typeface created on the front in the heat sensitive recording layer is absent.

Desweiteren wird noch bevorzugt, daß die wärmeempfindliche Aufzeichnungsschicht mit einer Schutzschicht abgedeckt istFurthermore, it is preferred that the heat-sensitive recording layer with a Protective layer is covered

Ein weiteres Einsatzgebiet ist die Herstellung von rückseitig mit zusätzlichen Informationen bedruckten Tickets, insbesondere aber von solchen Tickets, die rückseitig mit lösungsmittelhaltigen Magnetstreifen bedruckt werden.Another area of application is the production of on the back with additional information printed tickets, but especially those Tickets on the back with solvent-based Magnetic stripes can be printed.

Die nachfolgenden Beispiele erläutern die Erfindung.The following examples explain the Invention.

Beispiel 1:Example 1:

Es wurde eine wässrige Präparation aus 47 Gew.-Teilen kationischer Stärke, 16 Gew.-Teilen gefälltem Calciumcarbonat und 37 Gew.-Teilen eines von Styrol- oder Vinylacetatkomponenten freien kationischen Acrylatcopolymeren vorbereitet. Die Präparation wurde auf einen Feststoffgehalt von 18 Gew.% eingestellt - pH-Wert 7,5 - und in einer Menge von 2,2 g/m2 auf ein Streichrohpapier aufgetragen und getrocknet. Die andere Seite der gestrichenen Warenbahn wurde mit einer zur Aufnahme der wärmeempfindlichen Aufzeichnungsschicht dienenden Zwischenschicht versehen, deren wesentliche Komponenten aus einem ölabsorbierenden Pigment und Bindemittel bestanden. Die gebildete Zwischenschicht wurde anschließend mit einer üblichen wärmeempfindlichen Aufzeichnungsschicht versehen. An aqueous preparation was prepared from 47 parts by weight of cationic starch, 16 parts by weight of precipitated calcium carbonate and 37 parts by weight of a cationic acrylate copolymer free of styrene or vinyl acetate components. The preparation was adjusted to a solids content of 18% by weight - pH 7.5 - and applied in an amount of 2.2 g / m 2 to a base paper and dried. The other side of the coated web was provided with an intermediate layer for receiving the heat-sensitive recording layer, the essential components of which consisted of an oil-absorbing pigment and binder. The intermediate layer formed was then provided with a conventional heat-sensitive recording layer.

Beispiel 2:Example 2:

Aus den gleichen Komponenten wurde eine weitere Präparation mit 18 Gew.-% Feststoffgehalt vorbereitet, wobei jedoch 44 Gew.-Teile kationische Stärke, 34 Gew.-Teile eines wäßrigen kationischen Acrylatpolymeren und 22 Gew.-Teile gefälltes Calciumcarbonat eingesetzt wurden.Another became from the same components Preparation with 18% solids content prepared, however, 44 parts by weight of cationic starch, 34 Parts by weight of an aqueous cationic Acrylate polymers and 22 parts by weight of precipitated Calcium carbonate were used.

Claims (12)

  1. Heat-sensitive recording sheet have a substrate, a heat-sensitive recording layer comprising colour formers and colour acceptors that is arranged on its face, and a reverse-side coating arranged on its reverse side, characterised in that the reverse-side coating is formed from a mixture that comprises
    starch,
    an acrylate copolymer having a film-formation temperature <5°C that does not contain any styrene or vinyl acetate components, and
    an alkaline catalyst.
  2. Heat-sensitive recording sheet according to claim 1, characterised in that the starch and the acrylate copolymer are cationic.
  3. Heat-sensitive recording sheet according to either claim 1 or claim 2, characterised in that the reverse-side coating comprises from 40 to 50 parts by weight of starch based on its total weight.
  4. Heat-sensitive recording sheet according to any one of claims 1 to 3, characterised in that the reverse-side coating comprises from 30 to 40 parts by weight of acrylate copolymer based on its total weight.
  5. Heat-sensitive recording sheet according to any one of claims 1 to 4, characterised in that the reverse-side coating comprises from 9 to 28 parts by weight of the alkaline catalyst based on its total weight.
  6. Heat-sensitive recording sheet according to any one of claims 1 to 5, characterised in that the reverse-side coating comprises from 13 to 24 parts by weight of the alkaline catalyst based on its total weight.
  7. Heat-sensitive recording sheet according to any one of claims 1 to 6, characterised in that the alkaline catalyst is a metal carbonate.
  8. Heat-sensitive recording sheet according to any one of claims 1 to 7, characterised in that the alkaline catalyst is calcium carbonate.
  9. Heat-sensitive recording sheet according to any one of claims 1 to 8, characterised in that the alkaline catalyst is a precipitated calcium carbonate.
  10. Heat-sensitive recording sheet according to any one of claims 1 to 9, characterised in that the reverse-side coating is applied at an application weight of from 1 to 3 g/m2.
  11. Heat-sensitive recording sheet according to any one of claims 1 to 10,
    characterised in that the substrate consists of paper.
  12. Heat-sensitive recording sheet according to any one of claims 1 to 11,
    characterised in that the heat-sensitive recording layer is covered with a protective layer.
EP98946412A 1997-09-12 1998-08-22 Thermo-sensitive printing sheet comprising a back coating containing starch, an acrylate copolymer and an alkaline catalyst Expired - Lifetime EP0938419B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE1997140072 DE19740072A1 (en) 1997-09-12 1997-09-12 Heat-sensitive recording sheet
DE19740072 1997-09-12
DE19748258 1997-10-31
DE1997148258 DE19748258A1 (en) 1997-10-31 1997-10-31 Thermographic material, used in labels, e.g. for frozen food
PCT/EP1998/005347 WO1999014056A1 (en) 1997-09-12 1998-08-22 Thermo-sensitive printing sheet comprising a back coating containing starch, an acrylate copolymer and an alkaline catalyst

Publications (2)

Publication Number Publication Date
EP0938419A1 EP0938419A1 (en) 1999-09-01
EP0938419B1 true EP0938419B1 (en) 2000-11-15

Family

ID=26039914

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98946412A Expired - Lifetime EP0938419B1 (en) 1997-09-12 1998-08-22 Thermo-sensitive printing sheet comprising a back coating containing starch, an acrylate copolymer and an alkaline catalyst

Country Status (7)

Country Link
US (1) US6326330B1 (en)
EP (1) EP0938419B1 (en)
JP (1) JP2001505150A (en)
AT (1) ATE197574T1 (en)
DE (1) DE59800342D1 (en)
ES (1) ES2153707T3 (en)
WO (1) WO1999014056A1 (en)

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Publication number Priority date Publication date Assignee Title
EP2329959A1 (en) 2009-12-01 2011-06-08 Mitsubishi HiTec Paper Flensburg GmbH Heat-sensitive recording material with barrier coating

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DE10108982A1 (en) * 2001-02-23 2002-09-12 Mitsubishi Hitec Paper Flensbu Heat sensitive recording material and its use
US6833913B1 (en) 2002-02-26 2004-12-21 Kla-Tencor Technologies Corporation Apparatus and methods for optically inspecting a sample for anomalies
ES2339168T3 (en) * 2007-09-10 2010-05-17 Mitsubishi Hitec Paper Flensburg Gmbh HEAT SENSITIVE REGISTRATION MATERIAL WITH COVER OF THE REVERSE FACE.
WO2011032738A1 (en) * 2009-09-21 2011-03-24 Mitsubishi Hitec Paper Flensburg Gmbh Heat-sensitive recording material with reverse face coating
EP2329958B1 (en) 2009-12-01 2012-10-03 Mitsubishi HiTec Paper Europe GmbH Heat sensitive recording material with reverse coating

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JPS57146686A (en) 1981-03-05 1982-09-10 Ricoh Co Ltd Thermal recording type label sheet
JPS58199189A (en) 1982-05-17 1983-11-19 Toppan Printing Co Ltd Heat sensitive recording material
JPS602397A (en) 1983-06-21 1985-01-08 Ricoh Co Ltd Thermal recording material
JPS6147292A (en) 1984-08-15 1986-03-07 Jujo Paper Co Ltd Thermal recording paper
GB2163562B (en) 1984-08-20 1988-08-03 Ricoh Kk Adhesive thermosensitive recording sheet
GB2166558B (en) 1984-08-30 1988-09-21 Fuji Photo Film Co Ltd Heat-sensitive recording paper
SE500916C2 (en) * 1986-06-16 1994-10-03 Ricoh Kk Thermosensitive recording material with recording layer containing fluorescence dye composition
US4855277A (en) 1986-06-16 1989-08-08 Hobart Corporation Thermosensitive recording material having recording layer containing fluorescent dye
JPS63209990A (en) * 1987-02-27 1988-08-31 Fuji Photo Film Co Ltd Thermal recording paper
JP2528905B2 (en) 1987-10-27 1996-08-28 三菱製紙株式会社 Method for manufacturing thermosensitive recording medium
JPH04364983A (en) 1991-06-12 1992-12-17 Oji Paper Co Ltd Thermal recording body
EP0602494B1 (en) 1992-12-10 1996-10-09 Mitsubishi Paper Mills, Ltd. Ink jet recording sheet

Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP2329959A1 (en) 2009-12-01 2011-06-08 Mitsubishi HiTec Paper Flensburg GmbH Heat-sensitive recording material with barrier coating
WO2011067004A1 (en) 2009-12-01 2011-06-09 Mitsubishi Hitec Paper Europe Gmbh Heat-sensitive recording material with barrier coating

Also Published As

Publication number Publication date
DE59800342D1 (en) 2000-12-21
WO1999014056A1 (en) 1999-03-25
US6326330B1 (en) 2001-12-04
JP2001505150A (en) 2001-04-17
ATE197574T1 (en) 2000-12-15
ES2153707T3 (en) 2001-03-01
EP0938419A1 (en) 1999-09-01

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