EP1032498B1 - Heat-sensitive recording materials and method for authenticity checking - Google Patents

Heat-sensitive recording materials and method for authenticity checking Download PDF

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Publication number
EP1032498B1
EP1032498B1 EP99944434A EP99944434A EP1032498B1 EP 1032498 B1 EP1032498 B1 EP 1032498B1 EP 99944434 A EP99944434 A EP 99944434A EP 99944434 A EP99944434 A EP 99944434A EP 1032498 B1 EP1032498 B1 EP 1032498B1
Authority
EP
European Patent Office
Prior art keywords
heat
recording material
sensitive recording
dye
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.)
Expired - Lifetime
Application number
EP99944434A
Other languages
German (de)
French (fr)
Other versions
EP1032498A1 (en
Inventor
Erich Kranz
Karsten SÜSSENBACH
Gerhard Stork
Michael Reimann
Wolfgang Wagner
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE1998142867 external-priority patent/DE19842867C2/en
Priority claimed from DE1998142866 external-priority patent/DE19842866A1/en
Application filed by Mitsubishi HiTech Paper Flensburg GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Publication of EP1032498A1 publication Critical patent/EP1032498A1/en
Application granted granted Critical
Publication of EP1032498B1 publication Critical patent/EP1032498B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
    • 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
    • B41M5/41—Base layers supports or substrates
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/46—Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
    • 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
    • B41M2205/36—Backcoats; Back 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
    • B41M5/30—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
    • 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
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes

Definitions

  • the invention relates to heat-sensitive recording materials with security features, comprising a carrier paper with a recording layer arranged on one side, the color formers and organic reacting with each other under the influence of heat Contains color acceptors.
  • the invention further relates to methods for checking authenticity of the recording materials according to the invention.
  • Heat-sensitive recording materials have been known for a long time. Usually these materials are used to record femcopies that are public Telephone networks - so-called fax procedures - can be sent. Gradually in importance gain additional areas of application for heat-sensitive recording materials through their use as transfer forms or checks, diplomas, certificates, Package insert for pharmaceutical products, receipts for all kinds of games of chance, stamps, Receipts, parking tickets from parking machines as well as admission tickets and tickets.
  • DE 2518 871 A1 discloses as a security feature for coated papers that two substances of the same type, which contain at least one color former as an azo compound and at least one dye or pigment, are applied in or onto the backing paper.
  • a reagent is applied to the paper by means of a stamp, felt pen or roller device, the substance in or on the carrier paper reacting together with the reagent in the form of color formation.
  • the security feature described in this way can be combined with other security features such as watermarks in accordance with this document.
  • Security features in the manner of added dyes in the paper pulp or on the paper surface are furthermore described in DE 296 17 106 U 1 with regard to the addition of pigments based on anthraquinone and in EP 0 072 481 B1 with respect to an admixture of 2- (4'-amino) -3'-sulfophenyl) -6-methyl-benzothiazole-7-sulfonic acid or its salts are disclosed. All of the last-mentioned proposals do not relate to the field of heat-sensitive recording materials. The use of azine dye as a security feature is not disclosed.
  • DE 27 47 349 C 2 for counterfeit-proof papers which are to be used in particular as payment instructions to be filled in by hand, discloses the use of pyrensulfonic acids or their metal salts, which are either added to the paper pulp or with which the paper web is impregnated, from which full-surface coloring of the paper surface results.
  • EP 0 844 097 A1 discloses a heat-sensitive recording material in which, as a first security feature, a latent image is printed in places on the back by means of a security ink containing a fluorescent reagent.
  • the security ink contains a water-repellent.
  • the security ink containing the fluorescent reagent used as pigment or dye and the water-repellent is contained or dispersed in an aqueous carrier which, in addition to these components, also contains binders, such as thermoplastic resins, which are intended to improve image stability.
  • binders such as thermoplastic resins
  • the present invention now seeks to provide heat sensitive recording materials where multiple, with the help of simple facilities available everywhere Possibilities for examining the authenticity of the paper used are possible are.
  • the invention sees a further object in the development of a security feature, that is far more clearly than a full-surface preparation a test for authenticity of the paper used.
  • the invention wants effective protection before attempting counterfeiting.
  • the invention also sees an object in which Production of a heat-sensitive recording material on those of the pulp components to be dispensed with, such as fluorescent fibers result in the problems within the production process mentioned at the beginning can.
  • the invention sees according to its first and particularly simple Embodiment a heat-sensitive recording material with security feature which comprises a base paper having a recording layer arranged on one side, the color formers and organic reacting with each other under the influence of heat Contains color acceptors.
  • the heat-sensitive recording material is marked in that as a security feature a water-soluble fluorescent under UV radiation Dye without binder in a regular or irregular, in daylight invisible pattern so on the entire surface of the page that of a recording layer opposite side, i.e. the back, is applied that the entire surface has the pattern.
  • An irregular pattern formation in the sense of the present invention preferably corresponds a fine-grained structure that, in other words, is called speckling can be, while a regular pattern is preferably a stripe Structure corresponds.
  • speckling can be, while a regular pattern is preferably a stripe Structure corresponds.
  • the acidic or neutral pH range the one exposed to the dye sees Reverse with the naked eye viewed in daylight slightly colored.
  • the advantage of the water-soluble, without binder applied dye according to the Embodiment above is that the attachment of preprints is not on the problems encountered as in the binder-containing materials known from the prior art or coatings containing water repellents are known.
  • preprints include, for example, flexographic or Offset printing, in particular dry or waterless offset printing, applied prints, How to understand form labels, for example, in the case of which subsequent intended use Use the form fields to be filled in using a thermal printer.
  • those dyes have been found to be suitable with regard to the above-mentioned embodiments of the invention which, as part of a security check by applying an alkaline substance to the back of the recording material according to the invention, lead to a color which is fluorescent even in daylight, in particular also stable.
  • Pyrene sulfonate-based dyes are to be mentioned as a particularly preferred class of dyes.
  • the water-soluble dye which fluoresces under UV radiation is preferably with a weight per unit area of from 0.01 to 40 mg / m 2 , very particularly preferably with a weight per unit area of 0.05 to 7.5 mg / m 2 on the side facing the opposite side provided with a recording layer, applied.
  • the invention sees a heat-sensitive Recording material with security features in front of which is a backing paper with a recording layer arranged on one side, which under the action contains heat-reacting color formers and organic color acceptors and that is characterized in that as a first security feature one with a bare Eye-invisible water-insoluble azine dye is incorporated into the backing paper with surface wetting of the side opposite the recording layer of the recording material with an organic solvent or an acid striking coloration, and that as a second security feature on that of the recording layer opposite side of the backing paper, i.e. one on the back Layer is applied with a weakly visible in the acidic or neutral pH range Pyrene suffonate based dye.
  • the pyrene sulfonate-based dye comes into contact with an alkaline substance a color reaction that leads to a fluorescent in daylight stable color leads.
  • the pyrene sulfonate dye when it comes to avoiding printability problems, without binders applied, however, a joint application with a binder, e.g. possible with a starch line.
  • the azine dye is preferably present in an amount of 0.005 to 0.1% by weight, very particularly preferably incorporated into the backing paper in an amount of 0.01 to 0.03% by weight.
  • azine dyes within the meaning of the present invention are the pyrazine ring (Paradiazine ring) dyes marked with attached aromatic kemen understand.
  • the weight per unit area of the dye in the layer which is applied to the side of the carrier paper opposite the recording layer is between 0.01 and 40 mg / m 2 and particularly preferably between 0.05 and 7.5 mg / m 2 .
  • the invention is particularly preferred as the most tamper-proof embodiment heat-sensitive recording material with security features on the backing paper with a recording layer arranged on one side, which under the action Color reacting with heat and organic color acceptors contains and which is characterized in that as a first security feature one with bioßem Eye-invisible water-insoluble azine dye incorporated into the backing paper is that in the case of surface wetting that opposite the recording layer Side of the recording material with an organic solvent or an acid a striking coloration, and that as a second security feature an under UV radiation fluorescent water-soluble dye without a binder in a regular or irregular patterns that are invisible in daylight on the surface the side opposite to the side provided with a recording layer is that the entire surface has the pattern.
  • the one on the side opposite to the side to be recorded one below Have UV radiation fluorescent water-soluble dye is the implementation a first authenticity check is possible in such a way that the intended for recording Side opposite side is viewed under UV radiation, which at Patterns that are not visible in daylight can be seen.
  • the recording paper according to the invention according to claim 6 the pyrene sulfonate based dye on the side which faces the side to be recorded, in a regular or irregular manner Pattern applied, this pattern can be seen under UV radiation.
  • a particularly preferred method for checking the authenticity of all of the invention Recording papers sees the surface wetting of the page, that of the recording opposite side, especially when using a test pen or a comparable simple device with an alkaline substance, whereby a fluorescent, stable color is visible in daylight. Because in the usual Ink eraser pens contain alkaline substances are also tried in this way Attempts to counterfeit are recognizable.
  • Another method for authenticity checking with regard to the recording papers according to of claims 6 and 11 provides that a surface wetting of the layer that the Recording layer opposite, with a mixture of a primary alcohol, a secondary alcohol and an acid using a test pen, sponge, stamp or a comparable simple technical device in the smallest possible amount is made.
  • a striking coloring of the wetted surface indicates authenticity of the examined heat-sensitive recording material, where possible one of the color reaction of the azine dye with the organic solvent or acid corresponding color reaction in the recording layer should be avoided.
  • Wood-free papers with any area-related are preferably used as backing papers Mass used.
  • the recording layer is optionally applied to a primer.
  • One side of the carrier paper opposite the recording layer applied layer preferably consists of a starch.
  • a commercially available wood-free paper which is intended for the production of security documents, such as travel documents or receipts, and has a mass per unit area of 65 g / m 2 , is essentially made on the back with a starch preparation and on the front with a layer intended for applying the heat-sensitive recording layer Oil-absorbing pigment and binder existing intermediate layer.
  • An irregular pattern in the manner of a fine-grained structure is then applied to the dried starch preparation by means of an aqueous solution of a pyrene sulfonate-based dye.
  • the mass per unit area of the dye applied is 2.8 mg / m 2 .
  • the pattern shows a greenish color
  • UV irradiation of 360 nm the pattern can be seen in a bluish color.
  • the back of the papers has a color that is barely visible to the naked eye.
  • the cellulose entry for a carrier paper to be produced on a Fourdrinier paper machine with a mass per unit area of 80 g / m 2 of azine dye with an amount of 0.015% by weight of commercial goods based on the "atro" weight of the carrier paper is entered.
  • the starch screed to be applied to the back of the backing paper contains a pyrene sulfonate which is present in the back of the starch screed with a mass per unit area of 7 mg / m 2 .
  • a heat-sensitive recording layer is applied to a pigment precoat applied on the front.
  • a starch screed is applied on the back and a pigment precoat on the front.
  • a heat-sensitive recording layer is first applied to the pigment precoat and then dried.
  • a coating with a pyrene sulfonate with a mass per unit area of 2.9 mg / m 2 is applied to the starch screed applied on the back.
  • a felt pen is produced, which is a test substance consisting of a mixture of 70% lactic acid, 15% Contains ethanol and 15% isopropyl alcohol. With the help of this test substance it is possible by surface wetting the opposite side of the recording layer Recording material to cause coloration by dissolving the azine dye. there there is no corresponding color reaction of the recording layer. This would be adjust when using solvents as well as when applying too much the test substance.

Abstract

A method of checking the authenticity of a heat-sensitive recording material having a carrier paper with a recording layer which is arranged on one face and which contains colorant formers and organic colorant acceptors that react with one another when heated; and a security feature provided as a water-soluble dye which fluoresces under UV radiation, the dye being applied without binder in a pattern, invisible under daylight, to a surface of a face of the carrier paper opposite the face provided with the recording layer, so that the entire surface has the pattern, the water-soluble dye being applied at a mass per unit area between 0.01 and 40 mg/m<HIL><2</SP><PDAT>, the method comprising the step of wetting the surface of the layer opposite the recording layer with an alkaline substance.</PTEXT>

Description

Die Erfindung betrifft wärmeempfindliche Aufzeichnungsmaterialien mit Sicherheitsmerkmalen, aufweisend ein Trägerpapier mit einer auf einer Seite angeordneten Aufzeichnungsschicht, die unter Einwirkung von Wärme miteinander reagierende Farbbildner und organische Farbakzeptoren enthält. Femer betrifft die Erfindung Verfahren zur Authentizitätsprüfung der erfindungsgemäßen Aufzeichnungsmaterialien.The invention relates to heat-sensitive recording materials with security features, comprising a carrier paper with a recording layer arranged on one side, the color formers and organic reacting with each other under the influence of heat Contains color acceptors. The invention further relates to methods for checking authenticity of the recording materials according to the invention.

Wärmeempfindliche Aufzeichnungsmaterialien sind seit längerer Zeit bekannt. Überwiegend werden diese Materialien zur Aufzeichnung von Femkopien verwendet, die über öffentliche Femsprechnetze - sogenanntes Telefaxverfahren - versandt werden. Sukzessive an Bedeutung gewinnen zusätzliche Einsatzgebiete für wärmeempfindliche Aufzeichnungsmaterialien durch ihre Verwendung als Überweisungsformulare oder Schecks, Diploma, Zertifikate, Beipackzettel für pharmazeutische Produkte, Belege für Glücksspiele aller Art, Wertzeichen, Kassenbons, Parkzettel von Parkautomaten sowie Eintritts- und Fahrkarten.Heat-sensitive recording materials have been known for a long time. Mostly these materials are used to record femcopies that are public Telephone networks - so-called fax procedures - can be sent. Gradually in importance gain additional areas of application for heat-sensitive recording materials through their use as transfer forms or checks, diplomas, certificates, Package insert for pharmaceutical products, receipts for all kinds of games of chance, stamps, Receipts, parking tickets from parking machines as well as admission tickets and tickets.

Zur Vermeidung bzw. Erkennung von Fälschungen wurden in der Vergangenheit bereits verschiedene Lösungen vorgeschlagen. Neben der Verwendung von Wasserzeichen wurde insbesondere der Einsatz von unter ultravioletter Bestrahlung fluoreszierenden Fasem vorgeschlagen, die dem Papierfaserstoff vor der Blattbildung in geringer Menge zugemischt werden. Entsprechende Vorschläge finden sich für nicht dem Gebiet der wärmeempfindlichen Aufzeichnungsmaterialien zuzurechnende Papiere in der AT E 37053 B und gemäß der DE 195 01 289 A 1 für ein wärmeempfindliches Aufzeichnungspapier. Die Einarbeitung fluoreszierender Fasern in den Papierfaserstoff wirkt sich jedoch nachteilig in produktionstechnischer Hinsicht beispielsweise durch verlängerte Reinigungsstillstände an der Papiermaschine aus. Gleichzeitig kann der Ausschuß von so hergestelltem Papier nur sehr eingeschränkt recycelt werden aufgrund der mit bloßem Auge auffälligen Synthesefasern.Various solutions have already been proposed in the past for avoiding or detecting counterfeits. In addition to the use of watermarks, the use of fibers which fluoresce under ultraviolet radiation and which are admixed in a small amount with the paper pulp before sheet formation has been proposed in particular. Corresponding proposals can be found in AT E 37053 B for papers not belonging to the field of heat-sensitive recording materials and according to DE 195 01 289 A1 for a heat-sensitive recording paper. The incorporation of fluorescent fibers in the paper pulp, however, has a disadvantage in terms of production technology, for example due to extended cleaning downtimes on the paper machine. At the same time, the reject of paper produced in this way can only be recycled to a very limited extent due to the synthetic fibers which are noticeable to the naked eye.

In der DE 2518 871 A 1 wird für beschichtete Papiere als Sicherheitsmerkmal offenbart, daß zwei gleichgeartete Substanzen, die wenigstens einen Farbbildner als Azo-Verbindung und wenigstens einen Farbstoff oder ein Pigment enthalten, in bzw. auf das Trägerpapier aufgebracht sind. Zur Authentizitätsprüfung wird ein Reagenz mittels Stempel, Filzstift oder Walzeneinrichtung auf das Papier aufgebracht, wobei die Substanz in bzw. auf dem Trägerpapier zusammen mit dem Reagenz in Form von Farbbildung reagiert. Das so beschriebene Sicherheitsmerkmal kann entsprechend dieser Schrift mit anderen Sicherheitsmerkmalen, wie Wasserzeichen, kombiniert werden. DE 2518 871 A1 discloses as a security feature for coated papers that two substances of the same type, which contain at least one color former as an azo compound and at least one dye or pigment, are applied in or onto the backing paper. For the authenticity check, a reagent is applied to the paper by means of a stamp, felt pen or roller device, the substance in or on the carrier paper reacting together with the reagent in the form of color formation. The security feature described in this way can be combined with other security features such as watermarks in accordance with this document.

Sicherheitsmerkmale in der Art zugegebener Farbstoffe in der Papiermasse oder auf der Papieroberfläche werden femer in der DE 296 17 106 U 1 hinsichtlich der Zugabe von Pigmenten auf Anthrachinonbasis sowie in der EP 0 072 481 B 1 hinsichtlich einer Beimischung von 2-(4'-Amino-3'-sulfophenyl)-6-methyl-benzthiazol-7-sulfonsäure oder deren Salzen offenbart. Die zuletzt genannten Vorschläge beziehen sich allesamt nicht auf das Gebiet der wärmeempfindlichen Aufzeichnungsmaterialien. Die Verwendung von Azinfarbstoff als Sicherheitsmerkmal wird nicht offenbart.Security features in the manner of added dyes in the paper pulp or on the paper surface are furthermore described in DE 296 17 106 U 1 with regard to the addition of pigments based on anthraquinone and in EP 0 072 481 B1 with respect to an admixture of 2- (4'-amino) -3'-sulfophenyl) -6-methyl-benzothiazole-7-sulfonic acid or its salts are disclosed. All of the last-mentioned proposals do not relate to the field of heat-sensitive recording materials. The use of azine dye as a security feature is not disclosed.

Als alleiniges Sicherheitsmerkmal offenbart die DE 27 47 349 C 2 für fälschungssichere Papiere, die insbesondere als für von Hand auszufüllende Zahlungsanweisungen eingesetzt werden sollen, die Verwendung von Pyrensulfonsäuren oder deren Metallsalzen, die entweder der Papiermasse zugegeben werden oder mit denen die Papierbahn imprägniert wird, woraus eine vollflächige Einfärbung der Papieroberfläche resultiert.As the only security feature, DE 27 47 349 C 2 for counterfeit-proof papers, which are to be used in particular as payment instructions to be filled in by hand, discloses the use of pyrensulfonic acids or their metal salts, which are either added to the paper pulp or with which the paper web is impregnated, from which full-surface coloring of the paper surface results.

Aus der EP 0 844 097 A 1 ist ein wärmeempfindliches Aufzeichnungsmaterial bekannt, bei dem als ein erstes Sicherheitsmerkmal stellenweise ein latentes Bild mittels einer ein fluoreszierendes Reagenz enthaltenden Sicherheitstinte auf die Rückseite aufgedruckt ist. Zur Ausbildung eines zweiten Sicherheitsmerkmals in Form eines wasserdichten Bildes auf der Rückseite des wärmeempfindlichen Aufzeichnungsmaterials enthält die Sicherheitstinte ein wasserabweisendes Mittel. Die das als Pigment oder Farbstoff verwendete fluoreszierende Reagenz und das wasserabweisende Mittel enthaltende Sicherheitstinte ist in einem wässrigen Träger enthalten bzw. dispergiert, der außer diesen Komponenten noch Bindemittel, wie thermoplastische Harze, enthält, die zur Verbesserung der Bildbeständigkeit dienen sollen. Nachteilig bei diesem Vorschlag ist die kostenaufwendige Herstellung mittels Drucktechnik und die Tatsache, daß durch den wasserabweisenden Charakter der Sicherheitstinte die Anordnung von Preprints mittels der üblichen Druckverfahren erschwert wird. EP 0 844 097 A1 discloses a heat-sensitive recording material in which, as a first security feature, a latent image is printed in places on the back by means of a security ink containing a fluorescent reagent. To form a second security feature in the form of a waterproof image on the back of the heat-sensitive recording material, the security ink contains a water-repellent. The security ink containing the fluorescent reagent used as pigment or dye and the water-repellent is contained or dispersed in an aqueous carrier which, in addition to these components, also contains binders, such as thermoplastic resins, which are intended to improve image stability. Disadvantages of this proposal are the costly production by means of printing technology and the fact that the arrangement of preprints by means of the usual printing methods is made more difficult by the water-repellent nature of the security ink.

Die vorliegende Erfindung will nun wärmeempfindliche Aufzeichnungsmaterialien zur Verfügung stellen, bei denen mit Hilfe einfacher und überall verfügbarer Einrichtungen mehrere Untersuchungsmöglichkeiten hinsichtlich der Authentizität des eingesetzten Papiers möglich sind. Eine weitere Aufgabe sieht die Erfindung in der Entwicklung eines Sicherheitsmerkmals, das weitaus deutlicher als eine vollflächige Präparation eine Prüfung auf Authentizität des eingesetzten Papiers ermöglicht. Gleichzeitig will die Erfindung einen wirksamen Schutz vor Fälschungsversuchen schaffen. Die Erfindung sieht auch eine Aufgabe darin, bei der Herstellung eines wärmeempfindlichen Aufzeichnungsmaterials auf solche der Papiermasse zuzugebende Komponenten zu verzichten, die wie beispielsweise fluoreszierende Fasem die eingangs erwähnten Probleme innerhalb des Produktionsprozesses zur Folge haben können. Ein weiterer wichtiger Aufgabenaspekt besteht schließlich darin, daß im Bedarsfall sogenannte Preprints problemlos auf die Rückseite der wärmeempfindlichen Aufzeichnungsmaterialien aufgebracht werden können, ohne daß durch in einer rückseitig aufgetragenen Präparation vorliegende Komponenten, wie z.B. Binde - oder Hydrophobierungsmittel, Störungen des Druckprozesses zu befürchten sind.The present invention now seeks to provide heat sensitive recording materials where multiple, with the help of simple facilities available everywhere Possibilities for examining the authenticity of the paper used are possible are. The invention sees a further object in the development of a security feature, that is far more clearly than a full-surface preparation a test for authenticity of the paper used. At the same time, the invention wants effective protection before attempting counterfeiting. The invention also sees an object in which Production of a heat-sensitive recording material on those of the pulp components to be dispensed with, such as fluorescent fibers result in the problems within the production process mentioned at the beginning can. Finally, another important aspect of the task is that in case of need so-called preprints easily on the back of the heat-sensitive recording materials can be applied without having to be applied on the back Preparation components, e.g. Binders or water repellents, Problems with the printing process are to be feared.

Zur Lösung der Aufgabe sieht die Erfindung gemäß ihrer ersten und besonders einfachen Ausführungsform ein wärmeempfindliches Aufzeichnungsmaterial mit Sicherheitsmerkmal vor, das ein Trägerpapier mit einer auf einer Seite angeordneten Aufzeichnungsschicht umfaßt, die unter Einwirkung von Wärme miteinander reagierende Farbbildner und organische Farbakzeptoren enthält. Gekennzeichnet ist das wärmeempfindliche Aufzeichnungsmaterial dadurch, daß als Sicherheitsmerkmal ein unter UV-Bestrahlung fluoreszierender wasserlöslicher Farbstoff ohne Bindemittel in einem regelmäßigen oder unregelmäßigen, bei Tageslicht unsichtbaren Muster so auf die gesamte Oberfläche der Seite, die der mit einer Aufzeichnungsschicht versehenen Seite gegenüberliegt, i.e. die Rückseite, aufgebracht ist, daß die gesamte Oberfläche das Muster aufweist.To achieve the object, the invention sees according to its first and particularly simple Embodiment a heat-sensitive recording material with security feature which comprises a base paper having a recording layer arranged on one side, the color formers and organic reacting with each other under the influence of heat Contains color acceptors. The heat-sensitive recording material is marked in that as a security feature a water-soluble fluorescent under UV radiation Dye without binder in a regular or irregular, in daylight invisible pattern so on the entire surface of the page that of a recording layer opposite side, i.e. the back, is applied that the entire surface has the pattern.

Im Gegensatz zu den bisher bekannten Ausführungsformen von Sicherheitspapieren, bei denen entweder durch den Eintrag entsprechender Farbstoffe in die Faserstoffmasse oder durch Präparation eine vollflächig wirksame Fluoreszenz erreicht wurde, bietet das wärmeempfindliche Aufzeichnungspapier der vorliegenden Erfindung durch die Art seiner Musterung eine über das im Rahmen einer Authentizitätsprüfung mit einer aufzubringenden alkalischen Substanz nachzuweisende Sicherheitsmerkmal hinausgehende und nicht ohne weiteres nachzuahmende Sicherheitskomponente.In contrast to the previously known embodiments of security papers, at which either through the entry of appropriate dyes in the pulp or preparation has achieved full-surface fluorescence, which offers heat-sensitive Recording paper of the present invention by the way it is patterned one about the one to be brought up as part of an authenticity check alkaline substance to be proven safety feature and not without further security component to be imitated.

Eine unregelmäßige Musterbildung im Sinne der vorliegenden Erfindung entspricht vorzugsweise einer feinkörnigen Struktur, die, anders ausgedrückt, als Sprenkelung bezeichnet werden kann, während ein regelmäßiges Muster vorzugsweise einer streifenförmigen Struktur entspricht. Im sauren oder neutralen pH-Bereich sieht die mit dem Farbstoff beaufschlagte Rückseite mit bloßem Auge bei Tageslicht betrachtet leicht gefärbt aus. An irregular pattern formation in the sense of the present invention preferably corresponds a fine-grained structure that, in other words, is called speckling can be, while a regular pattern is preferably a stripe Structure corresponds. In the acidic or neutral pH range, the one exposed to the dye sees Reverse with the naked eye viewed in daylight slightly colored.

Der Vorteil des wasserlöslichen, ohne Bindemittel aufgebrachten Farbstoffes gemäß der vorstehenden Ausführungsform besteht darin, daß die Anbringung von Preprints nicht auf die Probleme stößt, wie sie bei den aus dem Stand der Technik bekannten bindemittelhaltigen oder Hydrophobierungsmittel enthaltenden Beschichtungen bekannt sind.The advantage of the water-soluble, without binder applied dye according to the Embodiment above is that the attachment of preprints is not on the problems encountered as in the binder-containing materials known from the prior art or coatings containing water repellents are known.

Unter Preprints sind in der vorliegenden Beschreibung beispielsweise mittels Flexo- oder Offsetdruck, - insbesondere Trocken- oder Waterless-Offsetdruck - aufgebrachte Aufdrucke, wie zum Beispiel Formularbeschriftungen zu verstehen, bei denen bei der späteren bestimmungsgemäßen Verwendung die Ausfüllung der Formularfelder mittels Thermodrucker erfolgt.In the present description, preprints include, for example, flexographic or Offset printing, in particular dry or waterless offset printing, applied prints, How to understand form labels, for example, in the case of which subsequent intended use Use the form fields to be filled in using a thermal printer.

Als geeignet hinsichtlich der o.a. Ausführungsformen der Erfindung haben sich insbesondere solche Farbstoffe gezeigt, die im Rahmen einer Sicherheitsprüfung durch Aufbringung einer alkalischen Substanz auf die Rückseite des erfindungsgemäßen Aufzeichnungsmaterials zu einer auch bei Tageslicht fluoreszierenden, insbesondere auch beständigen Farbe führen. Als besonders bevorzugte Farbstoffklasse sind dabei Farbstoffe auf Pyrensulfonatbasis anzuführen.
Vorzugsweise ist der unter UV-Bestrahlung fluoreszierende wasserlösliche Farbstoff mit einer flächenbezogenen Masse von 0,01 bis 40 mg/m2, ganz besonders bevorzugt mit einer flächenbezogenen Masse von 0,05 bis 7,5 mg/m2 auf die Seite, die der mit einer Aufzeichnungsschicht versehenen Seite gegenüberliegt, aufgebracht.In particular, those dyes have been found to be suitable with regard to the above-mentioned embodiments of the invention which, as part of a security check by applying an alkaline substance to the back of the recording material according to the invention, lead to a color which is fluorescent even in daylight, in particular also stable. Pyrene sulfonate-based dyes are to be mentioned as a particularly preferred class of dyes.
The water-soluble dye which fluoresces under UV radiation is preferably with a weight per unit area of from 0.01 to 40 mg / m 2 , very particularly preferably with a weight per unit area of 0.05 to 7.5 mg / m 2 on the side facing the opposite side provided with a recording layer, applied.

Als weitere und besonders fälschungssichere Ausführungsform sieht die Erfindung ein wärmeempfindliches Aufzeichnungsmaterial mit Sicherheitsmerkmalen vor, das ein Trägerpapier mit einer auf einer Seite angeordneten Aufzeichnungsschicht umfaßt, die unter Einwirkung von Wärme miteinander reagierende Farbbildner und organische Farbakzeptoren enthält und das dadurch gekennzeichnet ist, daß als erstes Sicherheitsmerkmal ein mit bloßem Auge unsichtbarer wasserunlöslicher Azinfarbstoff in das Trägerpapier eingearbeitet ist, der bei einer Oberflächenbenetzung der der Aufzeichnungsschicht gegenüberliegenden Seite des Aufzeichnungsmaterials mit einem organischen Lösungsmittel oder einer Säure eine auffällige Färbung bewirkt, und daß als zweites Sicherheitsmerkmal auf die der Aufzeichnungsschicht gegenüberliegende Seite des Trägerpapiers, also auf die Rückseite eine Schicht aufgebracht ist mit einem im sauren oder neutralen pH-Bereich nur schwach sichtbaren Farbstoff auf Pyrensuffonatbasis. Der Farbstoff auf Pyrensulfonatbasis geht im Kontakt mit einer alkalischen Substanz eine Farbreaktion ein, die zu einer bei Tageslicht fluoreszierenden beständigen Farbe führt. As a further and particularly forgery-proof embodiment, the invention sees a heat-sensitive Recording material with security features in front of which is a backing paper with a recording layer arranged on one side, which under the action contains heat-reacting color formers and organic color acceptors and that is characterized in that as a first security feature one with a bare Eye-invisible water-insoluble azine dye is incorporated into the backing paper with surface wetting of the side opposite the recording layer of the recording material with an organic solvent or an acid striking coloration, and that as a second security feature on that of the recording layer opposite side of the backing paper, i.e. one on the back Layer is applied with a weakly visible in the acidic or neutral pH range Pyrene suffonate based dye. The pyrene sulfonate-based dye comes into contact with an alkaline substance a color reaction that leads to a fluorescent in daylight stable color leads.

Bei der vorstehend beschriebenen Ausführungsform der Erfindung kann der Pyrensulfonatfarbstoff, wenn es um die Vermeidung von Bedruckbarkeitsproblemen geht, ohne Bindemittel aufgebracht werden, jedoch ist auch ein gemeinsamer Auftrag mit einem Bindemittel, z.B. mittels eines Stärkestriches möglich.In the embodiment of the invention described above, the pyrene sulfonate dye, when it comes to avoiding printability problems, without binders applied, however, a joint application with a binder, e.g. possible with a starch line.

Vorzugsweise ist der Azinfarbstoff in einer Menge von 0,005 bis 0,1 Gew.-%, ganz besonders bevorzugt in einer Menge von 0,01 bis 0,03 Gew.-% in das Trägerpapier eingearbeitet.The azine dye is preferably present in an amount of 0.005 to 0.1% by weight, very particularly preferably incorporated into the backing paper in an amount of 0.01 to 0.03% by weight.

Unter den Azinfarbstoffen im Sinne der vorliegenden Erfindung sind durch den Pyrazin-Ring (Paradiazin-Ring) mit angelagerten aromatischen Kemen gekennzeichnete Farbstoffe zu verstehen.Among the azine dyes within the meaning of the present invention are the pyrazine ring (Paradiazine ring) dyes marked with attached aromatic kemen understand.

Hinsichtlich der sowohl in den vorstehenden Absätzen wie auch im nachfolgenden Absatz als besonders fälschungssicher beschriebenen Ausführungsformen der Erfindung wird weiterhin bevorzugt, daß die flächenbezogene Masse des Farbstoffes in der Schicht, die auf die der Aufzeichnungsschicht gegenüberliegende Seite des Trägerpapiers aufgebracht ist, zwischen 0,01 und 40 mg/m2 und besonders bevorzugt zwischen 0,05 und 7,5 mg/m2 liegt.With regard to the embodiments of the invention described in the preceding paragraphs as well as in the following paragraph as particularly forgery-proof, it is further preferred that the weight per unit area of the dye in the layer which is applied to the side of the carrier paper opposite the recording layer is between 0.01 and 40 mg / m 2 and particularly preferably between 0.05 and 7.5 mg / m 2 .

Ganz besonders bevorzugt als fälschungssicherste Ausführungsform sieht die Erfindung ein wärmeempfindliches Aufzeichnungsmaterial mit Sicherheitsmerkmalen vor, das ein Trägerpapier mit einer auf einer Seite angeordneten Aufzeichnungsschicht umfaßt, die unter Einwirkung von Wärme miteinander reagierende Farbbildner und organische Farbakzeptoren enthält und das dadurch gekennzeichnet ist, daß als erstes Sicherheitsmerkmal ein mit bioßem Auge unsichtbarer wasserunlöslicher Azinfarbstoff in das Trägerpapier eingearbeitet ist, der bei einer Oberflächenbenetzung der der Aufzeichnungsschicht gegenüberliegenden Seite des Aufzeichnungsmaterials mit einem organischen Lösungsmittel oder einer Säure eine auffällige Färbung bewirkt, und daß als zweites Sicherheitsmerkmal ein unter UV-Bestrahlung fluoreszierender wasserlöslicher Farbstoff ohne Bindemittel in einem regelmäßigen oder unregelmäßigen, bei Tageslicht unsichtbaren Muster so auf die Oberfläche der Seite, die der mit einer Aufzeichnungsschicht versehenen Seite gegenüberliegt, aufgebracht ist, daß die gesamte Oberfläche das Muster aufweist.The invention is particularly preferred as the most tamper-proof embodiment heat-sensitive recording material with security features on the backing paper with a recording layer arranged on one side, which under the action Color reacting with heat and organic color acceptors contains and which is characterized in that as a first security feature one with bioßem Eye-invisible water-insoluble azine dye incorporated into the backing paper is that in the case of surface wetting that opposite the recording layer Side of the recording material with an organic solvent or an acid a striking coloration, and that as a second security feature an under UV radiation fluorescent water-soluble dye without a binder in a regular or irregular patterns that are invisible in daylight on the surface the side opposite to the side provided with a recording layer is that the entire surface has the pattern.

Auch hier besteht der Vorteil des wasserlöslichen, ohne Bindemittel aufgebrachten Farbstoffes darin, daß die Anbringung von Preprints nicht auf die vorstehend erläuterten Bedruckbarkeitsprobleme stößt. Here too there is the advantage of the water-soluble dye which is applied without a binder in that the application of preprints does not address the printability problems discussed above encounters.

Hinsichtlich der erfindungsgemäßen Aufzeichnungspapiere gemäß der Ansprüche 1 und 11, die auf der Seite, die der zur Aufzeichnung vorgesehenen Seite gegenüberliegt, einen unter UV-Bestrahlung fluoreszierenden wasserlöslichen Farbstoff aufweisen, ist die Durchführung einer ersten Authentizitätsprüfung derart möglich, indem die der zur Aufzeichnung vorgesehenen Seite gegenüberliegende Seite unter UV-Bestrahlung betrachtet wird, wobei das bei Tageslicht nicht sichtbare Muster zu erkennen ist. Wird bei dem erfindungsgemäßen Aufzeichnungspapier gemäß Anspruch 6 der Farbstoff auf Pyrensulfonatbasis auf die Seite, die der zur Aufzeichnung vorgesehenen Seite gegenüberliegt, in einem regelmäßigen oder unregelmäßigen Muster aufgebracht, so ist dieses Muster unter UV-Bestrahlung zu erkennen.With regard to the recording papers according to the invention according to claims 1 and 11, the one on the side opposite to the side to be recorded, one below Have UV radiation fluorescent water-soluble dye is the implementation a first authenticity check is possible in such a way that the intended for recording Side opposite side is viewed under UV radiation, which at Patterns that are not visible in daylight can be seen. Will with the recording paper according to the invention according to claim 6, the pyrene sulfonate based dye on the side which faces the side to be recorded, in a regular or irregular manner Pattern applied, this pattern can be seen under UV radiation.

Ein besonders bevorzugtes Verfahren zur Authentizitätsprüfung aller erfindungsgemäßen Aufzeichnungspapiere sieht die Oberflächenbenetzung der Seite, die der zur Aufzeichnung vorgesehenen Seite gegenüberliegt, insbesondere unter Benutzung eines Teststiftes oder einer vergleichbaren einfachen Vorrichtung mit einer alkalischen Substanz vor, wodurch eine bei Tageslicht sichtbare fluoreszierende beständige Farbe entsteht. Da in den üblichen Tintenlöschstiften alkalische Substanzen enthalten sind, werden auf diese Weise auch versuchte Fälschungsversuche erkennbar.A particularly preferred method for checking the authenticity of all of the invention Recording papers sees the surface wetting of the page, that of the recording opposite side, especially when using a test pen or a comparable simple device with an alkaline substance, whereby a fluorescent, stable color is visible in daylight. Because in the usual Ink eraser pens contain alkaline substances are also tried in this way Attempts to counterfeit are recognizable.

Ein weiteres Verfahren zur Authentizitätsprüfung hinsichtlich der Aufzeichnungspapiere gemäß der Ansprüche 6 und 11 sieht vor, daß eine Oberflächenbenetzung der Schicht, die der Aufzeichnungsschicht gegenüberliegt, mit einer Mischung aus einem primären Alkohol, einem sekundären Alkohol und einer Säure mittels eines Teststiftes, Schwammes, Stempels oder einer vergleichbaren einfachen technischen Vorrichtung in möglichst geringer Menge vorgenommen wird. Eine auffällige Färbung der benetzten Oberfläche läßt auf die Echtheit des untersuchten wärmeempfindlichen Aufzeichnungsmaterials schließen, wobei möglichst eine der Farbreaktion des Azinfarbstoffes mit dem organischen Lösungsmittel oder der Säure entsprechende Farbreaktion in der Aufzeichnungsschicht zu vermeiden ist.Another method for authenticity checking with regard to the recording papers according to of claims 6 and 11 provides that a surface wetting of the layer that the Recording layer opposite, with a mixture of a primary alcohol, a secondary alcohol and an acid using a test pen, sponge, stamp or a comparable simple technical device in the smallest possible amount is made. A striking coloring of the wetted surface indicates authenticity of the examined heat-sensitive recording material, where possible one of the color reaction of the azine dye with the organic solvent or acid corresponding color reaction in the recording layer should be avoided.

Die in Beschreibung und Patentansprüchen gemachten Angaben zur flächenbezogenen Masse und zu Gew.-% beziehen sich auf das "atro"-Gewicht, d. h. absolut trockene Gewichtsanteile.The information given in the description and claims for area-related Mass and wt .-% refer to the "atro" weight, i. H. absolutely dry parts by weight.

Als Trägerpapiere werden vorzugsweise holzfreie Papiere mit beliebiger flächenbezogener Masse eingesetzt. Die Aufzeichnungsschicht wird gegebenenfalls auf einen Vorstrich aufgebracht. Eine auf die der Aufzeichnungsschicht gegenüberliegende Seite des Trägerpapieres aufgebrachte Schicht besteht vorzugsweise aus einer Stärke. Wood-free papers with any area-related are preferably used as backing papers Mass used. The recording layer is optionally applied to a primer. One side of the carrier paper opposite the recording layer applied layer preferably consists of a starch.

Die nachfolgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.

Beispiel 1:Example 1:

Ein handelsübliches holzfreies Papier, das zur Herstellung von Sicherheitsbelegen, wie Fahrtausweisen oder Quittungsbelegen, vorgesehen ist, und eine flächenbezogene Masse von 65 g/m2 aufweist, wird rückseitig mit einer Stärkepräparation und vorderseitig mit einer zum Auftrag der wärmeempfindlichen Aufzeichnungsschicht vorgesehenen, im wesentlichen aus ölabsorbierendem Pigment und Bindemittel bestehenden Zwischenschicht versehen. Auf die getrocknete Stärkepräparation wird anschließend mittels einer wässerigen Lösung eines Farbstoffes auf Pyrensulfonatbasis ein unregelmäßiges Muster in der Art einer feinkörnigen Struktur aufgebracht. Die flächenbezogene Masse des aufgebrachten Farbstoffes beträgt 2,8 mg/m2. Unter UV-Bestrahlung von 254 nm zeigt das Muster eine grünliche Farbe, unter UV-Bestrahlung von 360 nm ist das Muster in bläulicher Farbe zu erkennen. Bei Tageslicht weisen die Papiere rückseitig eine mit bloßem Auge schwach sichtbare Färbung auf.A commercially available wood-free paper, which is intended for the production of security documents, such as travel documents or receipts, and has a mass per unit area of 65 g / m 2 , is essentially made on the back with a starch preparation and on the front with a layer intended for applying the heat-sensitive recording layer Oil-absorbing pigment and binder existing intermediate layer. An irregular pattern in the manner of a fine-grained structure is then applied to the dried starch preparation by means of an aqueous solution of a pyrene sulfonate-based dye. The mass per unit area of the dye applied is 2.8 mg / m 2 . Under UV irradiation of 254 nm the pattern shows a greenish color, under UV irradiation of 360 nm the pattern can be seen in a bluish color. In daylight, the back of the papers has a color that is barely visible to the naked eye.

Beispiel 2:Example 2:

Im Rahmen eines Produktionsversuchs wird in den Zellstoffeintrag für ein auf einer Langsieb - Papiermaschine herzustellendes Trägerpapier mit einer flächenbezogenen Masse von 80 g/m2 Azinfarbstoff mit einer Menge von 0,015 Gew.-% Handelsware bezogen auf das "atro"-Gewicht des Trägerpapiers eingegeben. Der auf die Rückseite des Trägerpapiers aufzubringende Stärkestrich enthält ein Pyrensulfonat, das im rückseitigen Stärkestrich mit einer flächenbezogenen Masse von 7 mg/m2 vorliegt. Auf einen vorderseitig aufgebrachten Pigmentvorstrich wird eine wämeempfindliche Aufzeichnungsschicht aufgetragen.In the course of a production test, the cellulose entry for a carrier paper to be produced on a Fourdrinier paper machine with a mass per unit area of 80 g / m 2 of azine dye with an amount of 0.015% by weight of commercial goods based on the "atro" weight of the carrier paper is entered. The starch screed to be applied to the back of the backing paper contains a pyrene sulfonate which is present in the back of the starch screed with a mass per unit area of 7 mg / m 2 . A heat-sensitive recording layer is applied to a pigment precoat applied on the front.

Beispiel 3:Example 3:

Auf ein für ein handelsübliches Ticketpapier vorgesehenes Trägerpapier, das dem vorstehend beschriebenen Trägerpapier entspricht, jedoch eine flächenbezogene Masse von 67 g/m2 aufweist, wird rückseitig ein Stärkestrich und vorderseitig ein Pigment-Vorstrich aufgebracht. Auf den Pigment-Vorstrich wird zunächst eine wärmeempfindliche Aufzeichnungsschicht aufgetragen und anschließend getrocknet. Auf dem rückseitig aufgetragen Stärkestrich wird abschließend eine Beschichtung mit einem Pyrensulfonat mit einer flächenbezogenen Masse von 2,9 mg/m2 aufgebracht. On a backing paper intended for a commercially available ticket paper, which corresponds to the backing paper described above, but has a mass per unit area of 67 g / m 2 , a starch screed is applied on the back and a pigment precoat on the front. A heat-sensitive recording layer is first applied to the pigment precoat and then dried. Finally, a coating with a pyrene sulfonate with a mass per unit area of 2.9 mg / m 2 is applied to the starch screed applied on the back.

Beispiel 4:Example 4:

Zwecks Authentizitätsprüfung der Aufzeichnungsmaterialien nach den Beispielen 2 und 3 wird ein Filzstift hergestellt, der als Prüfsubstanz eine Mischung aus 70% Milchsäure, 15% Ethanol und 15% Isopropylalkohol enthält. Mit Hilfe dieser Prüfsubstanz ist es möglich, durch Oberflächenbenetzung der der Aufzeichnungsschicht gegenüberliegenden Seite des Aufzeichnungsmaterials eine Färbung durch Anlösen des Azinfarbstoffes zu bewirken. Dabei bleibt eine entsprechende Farbreaktion der Aufzeichnungsschicht aus. Diese würde sich bei der Verwendung von Lösungsmittel genauso einstellen wie bei einem zu starkem Auftrag der Prüfsubstänz.To check the authenticity of the recording materials according to Examples 2 and 3 a felt pen is produced, which is a test substance consisting of a mixture of 70% lactic acid, 15% Contains ethanol and 15% isopropyl alcohol. With the help of this test substance it is possible by surface wetting the opposite side of the recording layer Recording material to cause coloration by dissolving the azine dye. there there is no corresponding color reaction of the recording layer. This would be adjust when using solvents as well as when applying too much the test substance.

Unter Benutzung eines handelsüblichen Tintenkillers wird anschließend eine alkalische Substanz auf die der Aufzeichnungsschicht gegenüberliegenden Seite des Aufzeichnungsmaterials aufgebracht. Die Reaktion der Farbstoffe auf Pyrensulfonat-Basis mit der alkalischen Substanz führt augenblicklich zu einer bei Tageslicht fluoreszierenden beständigen Farbe.Then, using a commercially available ink killer, make an alkaline one Substance on the side of the recording material opposite the recording layer applied. The reaction of the pyrene sulfonate-based dyes with the alkaline Substance instantly leads to a constant fluorescence in daylight Colour.

Claims (15)

  1. Heat-sensitive recording material having a security feature, having a support paper with a recording layer arranged on one side, the recording layer containing colour formers and organic colour acceptors that react with one another under the action of heat, characterised in that as security feature a water-soluble dye that fluoresces under UV radiation, without binder, is applied to the surface of the side opposite the side provided with a recording layer, in a regular or non-regular pattern that is invisible in daylight, in such a manner that the entire surface has the pattern.
  2. Heat-sensitive recording material according to claim 1, characterised in that the water-soluble dye forms, in contact with an alkaline substance, a colour that fluoresces in daylight.
  3. Heat-sensitive recording material according to either one of claims 1 and 2, characterised in that the water-soluble dye is applied in a mass per unit area of from 0.01 to 40 mg/m2.
  4. Heat-sensitive recording material according to any one of claims 1 to 3, characterised in that the water-soluble dye is applied in a mass per unit area of from 0.05 to 7.5 mg/m2.
  5. Heat-sensitive recording material according to any one of claims 1 to 4, characterised in that the water-soluble dye is a pyrenesulfonate-based dye.
  6. Heat-sensitive recording material having security features, having a support paper with a recording layer arranged on one side, the recording layer containing colour formers and organic colour acceptors that react with one another under the action of heat, characterised in that as first security feature there is incorporated into the support paper a water-insoluble azine dye invisible to the naked eye, which dye produces a conspicuous colouration when the surface of the side of the recording material opposite the recording layer is wetted with an organic solvent or with an acid, and as second security feature there is applied to the side of the support paper opposite the recording layer a layer having a pyrenesulfonate-based dye which is only faintly visible in an acidic or neutral pH range but which in contact with an alkaline substance enters into a colour reaction that results in a lasting colour that fluoresces in daylight.
  7. Heat-sensitive recording material according to claim 6, characterised in that azine dye is incorporated into the support paper in an amount of from 0.005 to 0.1 % by weight.
  8. Heat-sensitive recording material according to either one of claims 6 and 7, characterised in that azine dye is incorporated into the support paper in an amount of from 0.01 to 0.03 % by weight.
  9. Heat-sensitive recording material according to any one of claims 6 to 8, characterised in that the pyrenesulfonate-based dye is applied in a mass per unit area of from 0.01 to 40 mg/m2.
  10. Heat-sensitive recording material according to any one of claims 6 to 9, characterised in that the pyrenesulfonate-based dye is applied in a mass per unit area of from 0.05 to 7.5 mg/m2.
  11. Heat-sensitive recording material according to any one of claims 1 to 10, characterised in that as first security feature there is incorporated into the support paper a water-insoluble azine dye invisible to the naked eye, which dye produces a conspicuous colouration when the surface of the side of the recording material opposite the recording layer is wetted with an organic solvent or with an acid, and as second security feature a water-soluble dye that fluoresces under UV radiation, without binder, is applied to the surface of the side opposite the side provided with a recording layer, in a regular or non-regular pattern that is invisible in daylight, in such a manner that the entire surface has the pattern.
  12. Method of testing the authenticity of the heat-sensitive recording material according to any one of claims 6 to 11, characterised in that the surface of the layer opposite the recording layer is wetted with a mixture of a primary alcohol, a secondary alcohol and an acid.
  13. Method of testing the authenticity of the heat-sensitive recording material according to claim 12, characterised in that the wetting is effected using a test pen, a sponge, a stamp or a comparably simple device.
  14. Method of testing the authenticity of the heat-sensitive recording material according to any one of claims 2 and 6 to 11 and also 3 to 5 in part insofar as claims 3 to 5 are dependent on claim 2, characterised in that the surface of the layer opposite the recording layer is wetted with an alkaline substance.
  15. Method of testing the authenticity of the heat-sensitive recording material according to claim 14, characterised in that the wetting is effected using a test pen or a comparably simple device.
EP99944434A 1998-09-19 1999-08-19 Heat-sensitive recording materials and method for authenticity checking Expired - Lifetime EP1032498B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19842867 1998-09-19
DE1998142867 DE19842867C2 (en) 1998-09-19 1998-09-19 Heat-sensitive recording material and a method for checking authenticity
DE19842866 1998-09-19
DE1998142866 DE19842866A1 (en) 1998-09-19 1998-09-19 Thermographic material useful e.g. for travel ticket or receipt has (ir)regular pattern of reagent fluorescing in ultraviolet light and invisible in daylight as security mark on back
PCT/EP1999/006060 WO2000016986A1 (en) 1998-09-19 1999-08-19 Heat-sensitive recording materials and method for authenticity checking

Publications (2)

Publication Number Publication Date
EP1032498A1 EP1032498A1 (en) 2000-09-06
EP1032498B1 true EP1032498B1 (en) 2002-07-24

Family

ID=26048936

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99944434A Expired - Lifetime EP1032498B1 (en) 1998-09-19 1999-08-19 Heat-sensitive recording materials and method for authenticity checking

Country Status (7)

Country Link
US (1) US6632773B1 (en)
EP (1) EP1032498B1 (en)
JP (1) JP4372353B2 (en)
AT (1) ATE220997T1 (en)
DE (1) DE59902110D1 (en)
ES (1) ES2181470T3 (en)
WO (1) WO2000016986A1 (en)

Cited By (1)

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EP1925459B1 (en) * 2006-11-24 2014-03-12 Mitsubishi HiTec Paper Europe GmbH Method of producing a heat-sensitive recording material with authentification feature

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US6803344B2 (en) 2001-12-21 2004-10-12 Ncr Corporation Thermal paper with preprinted indicia
US7166154B2 (en) * 2003-11-06 2007-01-23 Hewlett-Packard Development Company, L.P. System and a method for an edible, optically invisible ink
NZ550224A (en) * 2004-04-02 2010-08-27 Curwood Inc A film that uses an oxide of nitrogen to create nitroxymyoglobin and maintain the red colour of fresh meat
ATE413286T1 (en) * 2004-06-11 2008-11-15 Ahlstrom Kauttua Oy LAYERED SAFETY MATERIAL AND PRODUCTION PROCESS THEREOF
US8330122B2 (en) * 2007-11-30 2012-12-11 Honeywell International Inc Authenticatable mark, systems for preparing and authenticating the mark
DE102009017444A1 (en) 2009-04-15 2010-10-21 Sension, Biologische Detektions- Und Schnelltestsysteme Gmbh Heat-sensitive recording material with security feature
EP2329955B1 (en) * 2009-12-01 2012-07-25 Mitsubishi HiTec Paper Europe GmbH Heat-sensitive recording material with authenticity characteristic

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AT37053B (en) 1908-04-24 1909-04-26 Ignatz Dr Palocz Inhalation device.
DE2518871A1 (en) 1974-04-26 1975-11-13 Portals Ltd SECURITY DOCUMENTS
FR2365656A1 (en) * 1976-05-25 1978-04-21 Arjomari Prioux SECURITY PAPER
DE3132146A1 (en) 1981-08-14 1983-03-03 Bayer Ag, 5090 Leverkusen COUNTERFEIT-PROOF PAPER
FR2566440B1 (en) 1984-06-22 1988-07-22 Jalon Michel SECURITY FIBERS AND OTHER MATERIALS MADE LUMINESCENT BY A DYEING PROCESS, THEIR PROCESSES AND THEIR APPLICATIONS
GB2214191B (en) 1988-01-12 1990-10-31 Sicpa Holding Sa Reversibly photochromic printing inks
US5308824A (en) * 1990-09-28 1994-05-03 Mitsubishi Paper Mills Limited Recording material
DE19501289A1 (en) 1995-01-18 1996-07-25 Feldmuehle Ag Stora Heat sensitive paper for thermal printing
DE29617106U1 (en) 1996-10-01 1997-02-27 Schoeller & Hoesch Papierfab paper
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Publication number Priority date Publication date Assignee Title
EP1925459B1 (en) * 2006-11-24 2014-03-12 Mitsubishi HiTec Paper Europe GmbH Method of producing a heat-sensitive recording material with authentification feature

Also Published As

Publication number Publication date
ATE220997T1 (en) 2002-08-15
JP2002526302A (en) 2002-08-20
US6632773B1 (en) 2003-10-14
JP4372353B2 (en) 2009-11-25
EP1032498A1 (en) 2000-09-06
ES2181470T3 (en) 2003-02-16
DE59902110D1 (en) 2002-08-29
WO2000016986A1 (en) 2000-03-30

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