EP0066854A1 - Security paper and method for its manufacture - Google Patents

Security paper and method for its manufacture Download PDF

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Publication number
EP0066854A1
EP0066854A1 EP82104887A EP82104887A EP0066854A1 EP 0066854 A1 EP0066854 A1 EP 0066854A1 EP 82104887 A EP82104887 A EP 82104887A EP 82104887 A EP82104887 A EP 82104887A EP 0066854 A1 EP0066854 A1 EP 0066854A1
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EP
European Patent Office
Prior art keywords
fibers
security
luminescent
security paper
paper 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.)
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EP82104887A
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German (de)
French (fr)
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EP0066854B1 (en
Inventor
Wittich Kaule
Gerhard Stenzel
Gerhard Schwenk
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GAO Gesellschaft fuer Automation und Organisation mbH
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Priority to AT82104887T priority Critical patent/ATE12532T1/en
Publication of EP0066854A1 publication Critical patent/EP0066854A1/en
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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
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/355—Security threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate

Definitions

  • the invention relates to a security paper with luminescent embeddings such as mottled fibers or security. threads.
  • security paper is understood to mean not only banknotes and other monetary documents such as checks, check cards, credit cards, but also other particularly secured documents such as identity cards and the like.
  • Such papers whose commercial or use value far exceeds the material value, must be recognizable as genuine by suitable measures and distinguishable from counterfeiting and counterfeiting.
  • Measures that have proven particularly useful in the past include embedding security threads and luminescent mottled fibers in the paper stock.
  • Such fibers are easy to imitate because commercially available emulsions can be used to produce electrically conductive or magnetizable coatings by immersing the fiber in these emulsions and then drying them in air; for falsification of impressions in many cases a pencil line is sufficient as a replacement for an electrically conductive fiber or a line with a commercially available felt tip pen containing magnetizable ink for a magnetizable fiber.
  • luminescent embeddings can rather be designed in such a way that, although they are easy and simple to detect, the luminescent substances themselves are neither commercially available nor can they be produced using the means available to the counterfeiters.
  • Chelates of the lanthanides are used as luminophores (i.e. the elements with atomic numbers 58-71 in the periodic table of the elements).
  • luminophores are characterized by a particularly narrow-band emission.
  • the line-emitting luminophores are mixed with a printing ink and thus printed on the document. If certain luminophores or their emission lines are present or absent, coded information is recorded which can serve as an authenticity indicator.
  • the emission occurs in the visible range of the optical spectrum; emission lines in the near infrared are also used to expand the usable spectral range.
  • the object of the invention is therefore to propose luminescent mottled fibers and / or security threads for security papers that are clearly identifiable and are difficult to manufacture due to their technology.
  • the concentration of the luminophores in the fibers should therefore be so high that a visual authenticity check is possible even in daylight conditions.
  • security paper is equipped with narrow-band luminescent mottling fibers or security threads made of cellulose acetate; the luminophores used are lanthanide chelates, the luminophore used in each case is dissolved uniformly and with a high concentration in the volume of the cellulose acetate fiber.
  • the luminescent fiber is colorless and detects intensively in the red after excitation with UV light.
  • cellulose acetate is dissolved in acetone and mixed with an acetone solution of a lanthanide chelate.
  • the lanthanide chelates used are soluble in acetone up to high concentrations; Experiments have achieved solubilities of 68% (weight) in acetone.
  • the mixture of the solution mentioned prepared in this way is then spun into a fiber in a manner known per se.
  • the fiber of this invention is preferably colorless and transparent; however, it can also be set to white or colored by additives in a manner known to those skilled in the art.
  • the fiber For use as mottled fiber, the fiber is now generally crimped and cut to a length of 3 to 4 mm.
  • the mottled fibers thus obtained can then be added to the pulp of a paper machine by known methods without further treatment.
  • the spun material is advantageously twisted or woven into a thread; it has proven to be extremely difficult to directly obtain threads of sufficient thickness with the spinning process used.
  • the security thread with information if it is twisted or woven from different luminescent individual fibers.
  • the presence or absence of certain luminophores - recognizable by the presence or absence of certain emission lines or colors - then form the coded information; this can e.g. B. specify the value of banknotes.
  • a particularly striking advantage of these fibers according to the invention is that the luminophore content could be increased by a factor of 20 compared to the prior art.
  • the Lumines has increased accordingly intensity. This surprising effect is caused by the extremely high solubility of the lanthanide chelates in acetone, which has already been mentioned above.
  • a fiber can be dissolved or dissolved with acetone to check the authenticity of the security paper according to the invention; the luminophore also releases and "bleeds" into the paper stock. A correspondingly wide spot can therefore be seen under the UV lamp, which can be used as an authenticity criterion. Because the stain is not visible under room or daylight, security paper tested in this way can then be put back into circulation. Such an authenticity check cannot be carried out with known mottled fibers. Another important advantage results from the narrow-band nature of the luminescence emission of fibers according to the invention. So z. B. preferably a Europium-ß-diketone chelate with a concentration of 5% (weight) is used in a transparent cellulose acetate fiber.
  • this fiber When excited with ultraviolet light, this fiber shows a very intense emission in the red; the corresponding emission line only has a spectral width of 5 nm.
  • the printed image it is therefore only necessary to keep a narrow spectral range free for reliable recognition of the authenticity mark.
  • this invention is the first to produce a colorless fiber that luminesces strongly in red. Mottled fibers with conventional, broadband fluorescence, on the other hand, always have a body color and can therefore already be seen with the naked eye.
  • the invention is in no way limited to fibers and threads with luminescence emission in the visible.
  • Example 2 describes a lanthanide chelate which emits exclusively in the infrared but otherwise has the same properties with regard to the invention as the luminophores emitting in the visible.
  • the use of such mottled fibers or security threads is such.
  • B. advantageous if one does not want to make the authenticity check understandable by everyone for given reasons. In such devices, the emitted light is detected and evaluated by appropriate IR photo detectors or also by IR image converters.
  • a suitable test device for the detection of luminescent mottled fibers is e.g. B. described in DE-AS 20 37 755; it only has to be adapted to the luminophore used by appropriate selection of the filter and the photo receiver.
  • R and R ' can be the same or different or can also be parts of a cyclic product: z. B.
  • a 30% acetone solution is prepared from the synthesized chelate, and this is then added to an acetone solution of cellulose acetate. Then the mixture is pressed through a nozzle into a heated chute and thus spun into an endless thin fiber of cellulose acetate, which contains the luminophore up to a proportion of 10% (weight) in volume. The fiber is then crimped and cut into sections approximately 3 mm in length. The mottled fibers thus produced luminesce intensely at 610 nm when they are irradiated with ultraviolet light; the fibers are lightfast to WS3 and resistant to petrol, benzene, ether and oils.
  • the fibers are added to the pulp of a paper machine in a known manner.
  • the corresponding chelate is prepared as described in Example 1, but using a mole of NdCl 3 .6H 2 O instead of 1 mole of EuCl 3 .6H 2 O.
  • a 30% acetone solution is again produced from the chelate synthesized in this way, this is mixed with an acetone solution of cellulose acetate and spun into a fine fiber. Then several of these fibers are woven into a thread 0.5 mm wide. This thread is colorless and luminescent intensely in the infrared at 1.06 ⁇ m after excitation with visible light; it is lightfast and resistant to petrol, benzene, ether and oils.
  • To produce a corresponding security paper it is guided on a double-round paper machine from a roll between the two layers of the sheet that is formed and is thus enclosed by the paper stock.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)
  • Credit Cards Or The Like (AREA)
  • Inspection Of Paper Currency And Valuable Securities (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)
  • Details Of Garments (AREA)

Abstract

1. A security paper having threads or fibers embedded in the paper pulp and made of cellulose acetate containing a luminescent substance in even distribution, characterized in that the luminescent substance is a lanthanide chelate showing narrow-band luminescence.

Description

Die Erfindung betrifft ein Sicherheitspapier mit lumineszierenden Einlagerungen wie Melierfasern oder Sicherheits-. fäden.The invention relates to a security paper with luminescent embeddings such as mottled fibers or security. threads.

Unter Sicherheitspapier werden im folgenden neben Banknoten und anderen geldwerten Papieren wie Schecks, Scheckkarten, Kreditkarten auch weitere besonders gesicherte Dokumente wie Ausweise und dergl. verstanden. Derartige Papiere, de- - ren Handels- oder Nutzungswert den Materialwert bei weitem übersteigt, müssen durch geeignete Maßnahmen als echt erkennbar und von Nachahmungen und Fälschungen unterscheidbar sein.In the following, security paper is understood to mean not only banknotes and other monetary documents such as checks, check cards, credit cards, but also other particularly secured documents such as identity cards and the like. Such papers, whose commercial or use value far exceeds the material value, must be recognizable as genuine by suitable measures and distinguishable from counterfeiting and counterfeiting.

Zu den Maßnahmen, die sich zu diesem Zwecke in der Vergangenheit besonders bewährt haben gehört unter anderem auch das Einbetten von Sicherheitsfäden sowie von lumineszierenden Melierfasern in den Papierstoff.Measures that have proven particularly useful in the past include embedding security threads and luminescent mottled fibers in the paper stock.

Der Sicherungswert dieser Echtheitskennzeichen ist darin begründet, daß sie nur während der Papierherstellung in das gerade entstehende Blatt eingebettet werden können. Zur erfolgreichen Nachahmung ist deshalb neben dem Zugriff auf aufwendige Apparaturen handwerkliches Können und Wissen in einem Maße erforderlich, daß dem Fälscher normalerweise nicht verfügbar ist.The security value of these authenticity indicators is based on the fact that they can only be embedded in the sheet just being produced during paper production. Successful imitation therefore requires, in addition to access to complex equipment, manual skills and knowledge to such an extent that the counterfeiter is normally not available.

Trotzdem ist es möglich und auch seit einigen Jahren mit Erfolg versucht worden, den Sicherungswert der vorstehend genannten Echtheitskennzeichen noch weiter zu erhöhen. Dazu stattet man diese mit zusätzlichen Eigenschaften aus, um schon die Nachbildung des Echtheitskennzeichens deutlich zu erschweren. Der Fälscher wird so gezwungen zunächst die Echtheitskennzeichen selbst erfolgreich zu fälschen bzw. nachzuahmen und diese dann in einem zweiten Schritt in das Sicherheitspapier einzubetten.Nevertheless, it is possible, and has been tried for several years with success, to further increase the security value of the above-mentioned authenticity indicators. To do this, they are equipped with additional properties in order to make it difficult to reproduce the authenticity mark. The counterfeiter is thus first forced to successfully counterfeit or imitate the authenticity mark and then in a second step into the Embed security paper.

In diesem-Zusammenhang sind bereits Sicherheitsfäden mit magnetischen und /oder elektrisch leitenden Beschichtungen bekannt geworden. Einbettungen mit solchen Eigenschaften sind aber einerseits vergleichsweise leicht nachzubilden und erfordern andererseits zu ihrer überprüfung vergleichsweise komplizierte Vorrichtungen.In this context, security threads with magnetic and / or electrically conductive coatings have already become known. Embedding with such properties is, on the one hand, comparatively easy to reproduce and, on the other hand, requires comparatively complicated devices to be checked.

Leicht nachzuahmen sind solche Fasern, weil man mit handelsüblichen Emulsionen elektrisch leitende bzw. magnetisierbare Beschichtungen durch Eintauchen der Faser in diese Emulsionen und anschließende Lufttrocknung herstellen kann; für Eindrucksfälschungen genügt in vielen Fällen schon ein Bleistiftstrich als Ersatz für eine elektrisch leitende Faser bzw. ein Strich mit einem im Handel erhältlichen Filzschreiber, der magnetisierbare Tinte enthält, für eine magnetisierbare Faser.Such fibers are easy to imitate because commercially available emulsions can be used to produce electrically conductive or magnetizable coatings by immersing the fiber in these emulsions and then drying them in air; for falsification of impressions in many cases a pencil line is sufficient as a replacement for an electrically conductive fiber or a line with a commercially available felt tip pen containing magnetizable ink for a magnetizable fiber.

Vergleichsweise aufwendig zu prüfen sind solche Fasern, weil die Detektoren zum Nachweis der elektrischen bzw. der magnetischen Eigenschaften in 'der Regel sehr nahe und dabei mit definiertem Abstand an die Fasern herangebracht werden müssen; außerdem muß das Echtheitssignal bei diesen Merkmalen in jedem Falle durch nachgeschaltete Auswertevorrichtungen in ein visuell erkennbares umgewandelt werden. Bei visuell lumineszierenden Kennzeichen wird diese Auswertung vom Auge des Beobachters erledigt. Deshalb treten die o. g. Nachteile bei der Verwendung lumineszierender Einbettungen nicht auf. Zur Verwendung in Sicherheitspapieren kann man lumineszierende Einbettungen vielmehr so ausbilden, daß sie zwar leicht und einfach nachzuweisen sind, die Lumineszenzstoffe selbst dabei aber weder im Handel erhältlich noch ihre Herstellung mit den dem Fälscher verfügbaren Mitteln durchführbar ist.Such fibers are comparatively difficult to test because the detectors for detecting the electrical or magnetic properties generally have to be brought very close to the fibers and at a defined distance; in addition, the authenticity signal for these features must in any case be converted into a visually recognizable one by downstream evaluation devices. In the case of visually luminescent characteristics, this evaluation is carried out by the eye of the observer. Therefore, the above-mentioned Disadvantages of using luminescent embeddings do not arise. For use in security papers, luminescent embeddings can rather be designed in such a way that, although they are easy and simple to detect, the luminescent substances themselves are neither commercially available nor can they be produced using the means available to the counterfeiters.

In diesem Sinne geeignete Luminophore und ihre Herstellung werden für die Anwendung auch bei Sicherheitspapieren in der CH-PS 516 196 beschrieben.In this sense, suitable luminophores and their production are described for use also in security papers in CH-PS 516 196.

Als Luminophore werden Chelate der Lanthanide verwendet (d. h. die Elemente mit den Ordnungszahlen 58 - 71 im Periodensystem der Elemente).Chelates of the lanthanides are used as luminophores (i.e. the elements with atomic numbers 58-71 in the periodic table of the elements).

Diese Luminophore zeichnen sich durch eine besonders schmalbandige Emission aus. In der o. g. Patentschrift werden die linienhaft emittierenden Luminophore einer Druckfarbe beigemischt und so auf das Dokument gedruckt. Durch Anwesenheit bzw. Abwesenheit bestimmter Luminophore bzw. ihrer Emissionslinien wird eine kodierte Information aufgezeichnet, welche als Echtheitskennzeichen dienen kann. Die Emission erfolgt dabei im sichtbaren Bereich des optischen Spektrums; zur Erweiterung des verwendbaren Spektralbereichs werden ferner Emissionslinien im nahen Infrarot herangezogen.These luminophores are characterized by a particularly narrow-band emission. In the above Patent specification, the line-emitting luminophores are mixed with a printing ink and thus printed on the document. If certain luminophores or their emission lines are present or absent, coded information is recorded which can serve as an authenticity indicator. The emission occurs in the visible range of the optical spectrum; emission lines in the near infrared are also used to expand the usable spectral range.

Sicherheitspapiere mit fluoreszierenden Fasern und fluoreszierenden Sicherheitsfäden sind aus der GB-PS 417 488 bekannt. Diese Patentschrift lehrt Sicherheitsfäden bzw. Melierfasern mit fluoreszierenden Stoffen zu imprägnieren, welche im Ultravioletten anregbar sind und im Sichtbaren emittieren. Als entsprechende Luminophore wird u. a. ein Zink-Komplex von 8-Hydroxy-Chinolin genannt; die dort aufgeführten Luminophore haben ein sehr breitbandiges Emissionsspektrum. Sie sind deshalb einerseits einfach nachahmbar und andererseits nicht sicher identifizierbar.Security papers with fluorescent fibers and fluorescent security threads are known from GB-PS 417 488. This patent teaches impregnating security threads or mottled fibers with fluorescent substances which are excitable in the ultraviolet and emit in the visible. As a corresponding luminophore u. a. called a zinc complex of 8-hydroxy-quinoline; the luminophores listed there have a very broad-band emission spectrum. On the one hand, they are therefore easy to imitate and, on the other hand, they cannot be identified with certainty.

Bei einer Prüfung resultiert daraus ferner der Nachteil, daß man zur sicheren Erkennung der Lumineszenz, welche sich vom Druckbild farblich abheben muß, einen relativ großen Spektralbereich für dieses Echtheitskennzeichen freizuhalten hat; die zu verwendeten Druckfarben dürfen diesen Spektralbereich deshalb nicht tangieren. Ein weiterer Nachteil ist darin zu sehen, daß die genannten Fluoreszenzstoffe leicht erhältlich sind und ihre Verfügbarkeit das Nachbilden entsprechender Fasern bzw. Fäden naturgemäß erleichtert.In the case of a test, this also results in the disadvantage that a relatively large spectral range must be kept free for this authenticity mark in order to reliably detect the luminescence, which must be different in color from the printed image; the printing inks to be used must therefore not affect this spectral range. Another disadvantage is the fact that the fluorescent substances mentioned are readily available and their availability naturally facilitates the replication of appropriate fibers or threads.

Durch die US-PS 22 55 696 wird die o. g. Sicherungsmethode weiter ausgebildet. Der schon erwähnte Zink-Komplex wird dazu in Aceton gelöst und einer acetonischen Lösung von Celluloseacetat zugemischt. Aus dieser Lösung wird dann eine Celluloseacetatfaser gesponnen, die den Luminophor mit einer Konzentration von maximal 0,5 % (Gewicht) enthält. Die so hergestellte Faser fluoresziert nach Anregung mit ultraviolettem Licht. Infolge der geringen Konzentration des Luminophors in der Faser muß eine visuelle überprüfung bei abgedunkeltem Raumlicht stattfinden. Darüberhinaus sind auch hier die schon bei der GB-PS 417 488 genannten Nachteile wirksam.By the US-PS 22 55 696 the above. Security method further trained. The zinc complex mentioned above is dissolved in acetone and mixed with an acetone solution of cellulose acetate. A cellulose acetate fiber is then spun from this solution, which contains the luminophore with a concentration of at most 0.5% (weight). The fiber produced in this way fluoresces after excitation with ultraviolet light. As a result of the low concentration of the luminophore in the fiber, a visual check must be carried out in the darkened room light. In addition, the disadvantages already mentioned in GB-PS 417 488 are also effective here.

Aufgabe der Erfindung ist es deshalb, lumineszierende Melierfasern und/oder Sicherheitsfäden für Sicherheitspapiere vorzuschlagen, die eindeutig identifizierbar sind und aufgrund ihrer Technologie schwer herstellbar sind. Die Konzentration der Luminophore in den Fasern soll daher so hoch sein, daß eine visuelle Echtheitsprüfung auch bei Tageslichtbedingungen möglich ist.The object of the invention is therefore to propose luminescent mottled fibers and / or security threads for security papers that are clearly identifiable and are difficult to manufacture due to their technology. The concentration of the luminophores in the fibers should therefore be so high that a visual authenticity check is possible even in daylight conditions.

Die Lösung dieser Aufgabe gelingt mit den im Kennzeichen des Hauptanspruchs genannten Mitteln. Weitere Ausbildungen der Erfindung sind den Unteransprüchen zu entnehmen.This problem is solved with the means mentioned in the characterizing part of the main claim. Further developments of the invention can be found in the subclaims.

Erfindungsgemäß wird Sicherheitspapier mit schmalbandig lumineszierenden Melierfasern bzw. Sicherheitsfäden aus Celluloseacetat ausgestattet; die dabei verwendeten Luminophore sind Lanthanid-Chelate, der jeweils verwendete Luminophor ist gleichmäßig und mit hoher Konzentration im Volumen der Celluloseacetatfaser gelöst.According to the invention, security paper is equipped with narrow-band luminescent mottling fibers or security threads made of cellulose acetate; the luminophores used are lanthanide chelates, the luminophore used in each case is dissolved uniformly and with a high concentration in the volume of the cellulose acetate fiber.

In der bevorzugten Ausführung der Verbindung ist die lumineszierende Faser farblos und ermittiert nach Anregung mit UV-Licht intensiv im Roten.In the preferred embodiment of the compound, the luminescent fiber is colorless and detects intensively in the red after excitation with UV light.

Zur Herstellung von lumineszierenden Fasern gemäß dieser Erfindung wird Celluloseacetat in Aceton gelöst und mit einer acetonischen Lösung eines Lanthanid-Chelates vermischt. Die verwendeten Lanthanid-Chelate sind in Aceton bis zu hohen Konzentrationen löslich; bei Versuchen wurden Löslichkeiten von 68 % (Gewicht) in Aceton erreicht. Die derart hergestellte Mischung der genannten Lösung wird nun in an sich bekannter Weise zu einer Faser versponnen.To produce luminescent fibers in accordance with this invention, cellulose acetate is dissolved in acetone and mixed with an acetone solution of a lanthanide chelate. The lanthanide chelates used are soluble in acetone up to high concentrations; Experiments have achieved solubilities of 68% (weight) in acetone. The mixture of the solution mentioned prepared in this way is then spun into a fiber in a manner known per se.

Die Faser nach dieser Erfindung ist vorzugsweise farblos und transparent; sie kann aber in einer dem Fachmann bekannten Weise durch Zusätze auch weiß oder farbig eingestellt werden.The fiber of this invention is preferably colorless and transparent; however, it can also be set to white or colored by additives in a manner known to those skilled in the art.

Zum Einsatz als Melierfaser wird die Faser nun im allgemeinen gekräuselt und auf 3 bis 4 mm Länge geschnitten. Die so erhaltenen Melierfasern können dann ohne weitere Behandlung nach bekannten Verfahren der Pulpe einer Papiermaschine zugefügt werden.For use as mottled fiber, the fiber is now generally crimped and cut to a length of 3 to 4 mm. The mottled fibers thus obtained can then be added to the pulp of a paper machine by known methods without further treatment.

Für den Einsatz als Sicherheitsfaden wird das Spinngut vorteilhafterweise zu einem Faden verdrillt oder verwoben; es hat sich nämlich als äußerst schwierig erwiesen, mit dem angewendeten Spinnverfahren- direkt Fäden von ausreichender Dicke zu erzielen.For use as a security thread, the spun material is advantageously twisted or woven into a thread; it has proven to be extremely difficult to directly obtain threads of sufficient thickness with the spinning process used.

Dabei ist es möglich, den Sicherheitsfaden mit einer Information zu versehen, wenn man ihn aus unterschiedlich lumineszierenden Einzelfasern verdrillt bzw. verwebt. An- bzw. Abwesenheit bestimmter Luminophore - erkennbar durch An- bzw. Abwesenheit bestimmter Emissionslinien- bzw. Farben - bilden dann die codierte Information; diese kann z. B. den Wert von Banknoten angeben.It is possible to provide the security thread with information if it is twisted or woven from different luminescent individual fibers. The presence or absence of certain luminophores - recognizable by the presence or absence of certain emission lines or colors - then form the coded information; this can e.g. B. specify the value of banknotes.

Ein besonders augenfälliger Vorteil dieser erfindungsgemäßen Fasern ist, daß der Luminophoregehalt gegenüber dem Stand der Technik um einen Faktor 20 gesteigert werden konnte. Dementsprechend gesteigert ist auch die Lumineszenzintensität. Dieser überraschende Effekt wird verursacht durch die außerordentlich große Löslichkeit der Lanthanid-Chelate in Aceton, auf die bereits weiter oben hingewiesen wurde.A particularly striking advantage of these fibers according to the invention is that the luminophore content could be increased by a factor of 20 compared to the prior art. The Lumines has increased accordingly intensity. This surprising effect is caused by the extremely high solubility of the lanthanide chelates in acetone, which has already been mentioned above.

Wegen der starken Lumineszenzintensität kann man zur Prüfung der Echtheit des erfindungsgemäßen Sicherheitspapiers eine Faser mit Aceton an- oder auflösen; dabei löst sich auch der Luminophor und "blutet" in den Papierstoff aus. Unter der UV-Lampe wird deshalb ein entsprechend breiter Fleck erkennbar, der als Echtheitskriterium verwendet werden kann. Weil der Fleck unter Raum- bzw. Tageslicht nicht sichtbar ist, kann ein so geprüftes Sicherheitspapier anschließend wieder in den Umlauf gegeben werden. Eine derartige Echtheitsprüfung läßt sich mit bekannten Melierfasern nicht durchführen. Ein weiterer wichtiger Vorteil resultiert aus der Schmalbandigkeit der Lumineszenzemission erfindungsgemäßer Fasern. So wird z. B. bevorzugt ein Europium-ß-Diketonchelat mit einer Konzentration von 5 % (Gewicht) in einer transparenten Celluloseacetatfaser verwendet. Bei Anregung mit ultraviolettem Licht zeigt diese Faser eine sehr intensive Emission im Roten; die entsprechende Emissionslinie hat dabei nur eine spektrale Breite von 5nm. Bei der Gestaltung des Druckbildes muß man deshalb nur einen schmalen Spektralbereich für ein sicheres Erkennen des Echtheitskennzeichens freihalten.Because of the strong luminescence intensity, a fiber can be dissolved or dissolved with acetone to check the authenticity of the security paper according to the invention; the luminophore also releases and "bleeds" into the paper stock. A correspondingly wide spot can therefore be seen under the UV lamp, which can be used as an authenticity criterion. Because the stain is not visible under room or daylight, security paper tested in this way can then be put back into circulation. Such an authenticity check cannot be carried out with known mottled fibers. Another important advantage results from the narrow-band nature of the luminescence emission of fibers according to the invention. So z. B. preferably a Europium-ß-diketone chelate with a concentration of 5% (weight) is used in a transparent cellulose acetate fiber. When excited with ultraviolet light, this fiber shows a very intense emission in the red; the corresponding emission line only has a spectral width of 5 nm. When designing the printed image, it is therefore only necessary to keep a narrow spectral range free for reliable recognition of the authenticity mark.

Vorteilhaft ist ferner, daß mit dieser Erfindung erstmals eine farblose Faser herstellbar ist, die stark rot luminesziert. Melierfasern mit herkömmlicher, breitbandiger Fluoreszenz weisen dagegen stets eine Körperfarbe auf und sind dadurch bereits mit bloßem Auge auszumachen.It is also advantageous that this invention is the first to produce a colorless fiber that luminesces strongly in red. Mottled fibers with conventional, broadband fluorescence, on the other hand, always have a body color and can therefore already be seen with the naked eye.

Offensichtliche Vorteile ergeben sich auch für die Konstruktion von automatisch arbeitenden Vorrichtungen zum Prüfen der Echtheit von erfindungsgemäßem Sicherheitspapier. Weil man dem Fotodetektor nur Licht aus einem kleinen Spektralbereich zuführen muß und die anderen Bereiche des Spektrums durch geeignete Filter abdeckbar sind, kann das Signalrauschverhältnis sehr günstig gehalten werden; dies gestattet eine einfache und kostengünstige Konstruktion des Prüfgerätes. Dabei ist das günstige Signalrauschverhältnis insbesondere auch durch die gegenüber dem Stand der Technik beträchtlich gesteigerte Lumineszenzintensität, d. h. den Signalpegel verursacht.Obvious advantages also result for the construction of automatically operating devices for checking the authenticity of security paper according to the invention. Because you only have to feed light from a small spectral range to the photodetector and the other areas of the spectrum can be covered by suitable filters, the signal-to-noise ratio can be kept very favorable; this allows a simple and inexpensive construction of the test device. The favorable signal-to-noise ratio is in particular also caused by the luminescence intensity, that is to say the signal level, which is considerably higher than in the prior art.

Auch wenn bevorzugte Ausführungen der Erfindung eine sichtbare Lumineszenz verwenden, ist deshalb die Erfindung keineswegs auf Fasern und Fäden mit Lumineszenzemission im Sichtbaren beschränkt. Im nachstehenden Beispiel 2 ist ein Lanthanid-Chelat beschrieben, der ausschließlich im Infraroten emittiert aber sonst im Hinblick auf die Erfindung die gleichen Eigenschaften aufweist, wie die im Sichtbaren emittierenden Luminophore. Die Anwendung solcher Melierfasern bzw. Sicherheitsfäden ist z. B. vorteilhaft, wenn man aus gegebenen Gründen die Echtheitskontrolle nicht von jedermann nachvollziehbar gestalten will. In solchen Vorrichtungen wird das emittierte Licht durch entsprechende IR-Fotodetektoren oder auch durch IR-Bildwandler nachgewiesen und ausgewertet. Eine geeignete Prüfvorrichtung zum Nachweis lumineszierender Melierfasern ist z. B. in der DE-AS 20 37 755 beschrieben; sie muß lediglich durch entsprechende Wahl der Filter und des Fotoempfängers an den verwendeten Luminophor angepaßt werden.Therefore, even if preferred embodiments of the invention use visible luminescence, the invention is in no way limited to fibers and threads with luminescence emission in the visible. Example 2 below describes a lanthanide chelate which emits exclusively in the infrared but otherwise has the same properties with regard to the invention as the luminophores emitting in the visible. The use of such mottled fibers or security threads is such. B. advantageous if one does not want to make the authenticity check understandable by everyone for given reasons. In such devices, the emitted light is detected and evaluated by appropriate IR photo detectors or also by IR image converters. A suitable test device for the detection of luminescent mottled fibers is e.g. B. described in DE-AS 20 37 755; it only has to be adapted to the luminophore used by appropriate selection of the filter and the photo receiver.

Die Erfindung wird nachstehend anhand von zwei Beispielen näher erläutert:The invention is explained in more detail below using two examples:

Beispiel 1example 1

Herstellung einer farblosen Melierfaser, die im Sichtbaren bei 610 nm luminesziert.Production of a colorless mottled fiber that luminesces in the visible at 610 nm.

1 Mol Europiumchlorid (EuCl3· 6H20) wird in Methanol gelöst und mit einer methanolischen Lösung von 4 Mol 1-Phenyl-1,3-butandion vermischt. Dazu gibt man unter Rühren eine Lösung von 4,2 Mol Piperidin in Methanol zu, wobei sich das Reaktionsgemisch unter Erwärmung gelb färbt. Nach dem Abkühlen gießt man das Gemisch unter starkem Rühren in 20 1 Wasser, wobei der Chelat als weiße Flocke ausgeschieden wird, die abfiltriert, gewaschen und an Luft bei 80° C getrocknet werden.1 mol of europium chloride (EuCl 3 .6H 2 0) is dissolved in methanol and mixed with a methanolic solution of 4 mol of 1-phenyl-1,3-butanedione. A solution of 4.2 mol of piperidine in methanol is added with stirring, the The reaction mixture turns yellow when heated. After cooling, the mixture is poured into 20 l of water with vigorous stirring, the chelate being separated out as a white flake, which is filtered off, washed and dried in air at 80.degree.

Statt 1-Phenyl-1,3 butandion können auch alle Derivate von β-Diketonen bzw. Verbindungen mit 1-Hydroxy-3-Oxo-Gruppierungen der allgemeinen Formel als chelatbildende Liganden eingesetzt werden, sofern damit eine Energieübertragung auf das Zentralatom - das hier immer ein Lanthanid (Ordnungszahl 58 - 71) ist - ermöglicht wird.Instead of 1-phenyl-1,3-butanedione, it is also possible to use all derivatives of β-diketones or compounds having 1-hydroxy-3-oxo groups of the general formula can be used as chelating ligands, provided this enables energy transfer to the central atom - which is always a lanthanide (atomic number 58 - 71).

R und R' können dabei gleich oder verschieden oder auch Teile eines cyclischen Produktes sein: z. B. R'=R=CH3-oder C2H5 - oder C3H2- (allgemein CnH2n+1) oder CF3- oder C 2 F 5- (allgemein CnF2n+1) oder Phenyl- oder Naphthyl-oder Thienyl- oder Piperidyl.R and R 'can be the same or different or can also be parts of a cyclic product: z. B. R '= R = CH 3 - or C 2 H 5 - or C 3 H 2 - (generally C n H 2n + 1 ) or CF 3 - or C 2 F 5 - (generally C n F 2n + 1 ) or phenyl or naphthyl or thienyl or piperidyl.

Aus dem synthetisierten Chelat wird eine 30%ige acetonische Lösung hergestellt, und diese anschließend einer acetonischen Lösung von Celluloseacetat zugesetzt. Danach wird das Gemisch durch eine Düse in einen beheizten Fällschacht gedrückt und so zu einer endlosen dünnen Faser aus Celluloseacetat versponnen, welche den Luminophor bis zu einem Anteil von 10 % (Gewicht) im Volumen enthält. Die Faser wird dann gekräuselt und in Abschnitte von ungefähr 3 mm Länge geschnitten. Die so hergestellten Melierfasern lumineszieren intensiv bei 610 nm, wenn sie mit ultraviolettem Licht bestrahlt werden; die Fasern sind lichtecht bis WS3 und beständig gegenüber Benzin, Benzol, Äther und ölen.A 30% acetone solution is prepared from the synthesized chelate, and this is then added to an acetone solution of cellulose acetate. Then the mixture is pressed through a nozzle into a heated chute and thus spun into an endless thin fiber of cellulose acetate, which contains the luminophore up to a proportion of 10% (weight) in volume. The fiber is then crimped and cut into sections approximately 3 mm in length. The mottled fibers thus produced luminesce intensely at 610 nm when they are irradiated with ultraviolet light; the fibers are lightfast to WS3 and resistant to petrol, benzene, ether and oils.

Zur Herstellung von Sicherheitspapier werden die Fasern in bekannter Weise der Pulpe einer Papiermaschine beigegeben.To produce security paper, the fibers are added to the pulp of a paper machine in a known manner.

Beispiel 2 /Example 2 /

Herstellung des farblosen Sicherheitsfadens der im Infraroten bei 1,06 µm luminesziert.Production of the colorless security thread which luminesces in the infrared at 1.06 µm.

Der entsprechende Chelat wird wie in Beispiel 1 beschrieben hergestellt, wobei jedoch statt 1 Mol EuCl3·6H2O ein Mol NdCl3·6H2O verwendet wird. Aus dem so synthetisierten Chelat wird wieder eine 30%ige acetonische Lösung hergestellt, diese mit einer acetonischen Lösung von Celluloseacetat vermischt und zu einer feinen Faser versponnen. Anschließend werden mehrere dieser Fasern zu einem Faden von 0,5 mm Breite verwoben. Dieser Faden ist farblos und luminesziert intensiv im Infraroten bei 1,06 µm nach Anregung mit sichtbarem Licht; er ist lichtecht und beständig gegenüber Benzin, Benzol, Äther und ölen. Zur Herstellung eines entsprechenden Sicherheitspapiers wird er auf einer Doppel-Rundsieb-Papiermaschine von Rolle zwischen die beiden Lagen des sich bildenden Blattes geführt und so vom Papierstoff umschlossen.The corresponding chelate is prepared as described in Example 1, but using a mole of NdCl 3 .6H 2 O instead of 1 mole of EuCl 3 .6H 2 O. A 30% acetone solution is again produced from the chelate synthesized in this way, this is mixed with an acetone solution of cellulose acetate and spun into a fine fiber. Then several of these fibers are woven into a thread 0.5 mm wide. This thread is colorless and luminescent intensely in the infrared at 1.06 µm after excitation with visible light; it is lightfast and resistant to petrol, benzene, ether and oils. To produce a corresponding security paper, it is guided on a double-round paper machine from a roll between the two layers of the sheet that is formed and is thus enclosed by the paper stock.

Claims (15)

1. Sicherheitspapier mit eingebettetem lumineszierenden Fäden oder Fasern aus Celluloseacetat, dadurch gekennzeichnet, daß das Celluloseacetat. mit schmalbandig lumineszierenden Lanthanid-Chelaten im Volumen durchgefärbt ist.1. Security paper with embedded luminescent threads or fibers made of cellulose acetate, characterized in that the cellulose acetate. is colored through in volume with narrow-band luminescent lanthanide chelates. 2. Sicherheitspapier nach Anspruch 1, dadurch gekennzeichnet, daß die Lanthanid-Chelate mit Konzentrationen bis zu 10% (Gewicht) im Celluloseacetat vorhanden sind.2. Security paper according to claim 1, characterized in that the lanthanide chelates are present in concentrations of up to 10% (weight) in the cellulose acetate. 3. Sicherheitspapier nach Anspruch 2, dadurch gekennzeichnet, daß die lumineszierenden Fäden oder Fasern nach Anregung mit ultraviolettem Licht im Sichtbaren schmalbandig emittieren.3. Security paper according to claim 2, characterized in that the luminescent threads or fibers emit narrow band in the visible after excitation with ultraviolet light. 4. Sicherheitspapier nach Anspruch 3, dadurch gekennzeichnet, daß die lumineszierenden Fäden oder Fasern farblos sind und nach Anregung mit ultraviolettem Licht schmalbandig rot lumineszieren.4. Security paper according to claim 3, characterized in that the luminescent threads or fibers are colorless and luminesce red narrow band after excitation with ultraviolet light. 5. Sicherheitspapier nach Anspruch 3, dadurch gekennzeichnet, daß die eingebetteten lumineszierenden Fäden oder Fasern mit Infraroten schmalbandig emittieren.5. Security paper according to claim 3, characterized in that the embedded luminescent threads or fibers emit narrowband with infrared. 6. Sicherheitspapier nach Anspruch 2, dadurch gekennzeichnet, daß die Einbettung in der Form eines Sicherheitsfadens aus gewobenen oder verdrillten Fäden vorliegt.6. Security paper according to claim 2, characterized in that the embedding is in the form of a security thread made of woven or twisted threads. 7. Sicherheitspapier nach Anspruch 2, dadurch gekennzeichnet, daß die lumineszierenden Fäden oder Fasern farblos sind.7. Security paper according to claim 2, characterized in that the luminescent threads or fibers are colorless. 8. Sicherheitspapier nach Anspruch 4, dadurch gekennzeichnet, daß der Luminophor ein Europium-Chelat ist.8. Security paper according to claim 4, characterized in that the luminophore is a europium chelate. 9. Sicherheitspapier nach Anspruch 5, dadurch gekennzeichnet, daß der Luminophor ein Neodym-Chelat ist.9. Security paper according to claim 5, characterized in that the luminophore is a neodymium chelate. 10. Sicherheitspapier nach Anspruch 2, dadurch gekennzeichnet, daß der chelatbildende Ligand zur Gruppe der -Diketone gehört.10. Security paper according to claim 2, characterized in that the chelating ligand belongs to the group of diketones. 11. Sicherheitspapier nach Anspruch 7, dadurch gekennzeichnet, daß es einen Sicherheitsfaden enthält, der aus Fasern mit unterschiedlichen Luminophoren gezwirnt bzw. gewebt ist, wobei dem Sicherheitsfaden durch die Verwendung bzw. Nichtverwendung bestimmter Lumiophore eine kodierte Information aufgeprägt ist.11. Security paper according to claim 7, characterized in that it is a security thread contains, which is twisted or woven from fibers with different luminophores, wherein the security thread through the use or non-use of certain Lumiophore a coded information is imprinted. 12. Verfahren zur Herstellung von lumineszierenden Fasern in Sicherheitspapieren gemäß Anspruch 2, dadurch gekennzeichnet, daß zur Herstellung der Fasern eine acetonische Lösung von Celluloseacetat mit einer acetonischen Lösung des Lanthanid-Chelats gemischt wird und die Lösung anschließend zu einer feinen Faser versponnen wird.12. A process for the production of luminescent fibers in security papers according to claim 2, characterized in that for the production of the fibers an acetone solution of cellulose acetate is mixed with an acetone solution of the lanthanide chelate and the solution is then spun into a fine fiber. 13. Verfahren zur Herstellung von lumineszierenden Melierfasern in Sicherheitspapieren nach Anspruch 12, dadurch gekennzeichnet, daß die fein gesponnenen Fasern zunächst gekräuselt und dann geschnitten werden.13. A method for producing luminescent mottled fibers in security papers according to claim 12, characterized in that the finely spun fibers are first crimped and then cut. 14. Verfahren zur Herstellung von lumineszierenden Sicherheitsfäden in Sicherheitspapieren nach Anspruch 12, dadurch gekennzeichnet, daß die fein gesponnenen Fasern zu einem Faden verzwirnt oder verwoben werden.14. A method for producing luminescent security threads in security papers according to claim 12, characterized in that the finely spun fibers are twisted or woven into a thread. 15. Verfahren zur Echtheitsprüfung eines Sicherheitspapiers nach Anspruch 2, dadurch gekennzeichnet, daß zunächst eine lumineszierende Faser bzw. ein aus solchen Fasern gewebter Faden mit Aceton an- oder aufgelöst wird und sodann die Lumineszenz der Restfaser sowie des im benachbarten Papierstoff dispergierten Fasermaterials als Kriterium für die Echtheit des Sicherheitspapiers herangezogen wird.15. A method for checking the authenticity of a security paper according to claim 2, characterized in that first a luminescent fiber or a thread woven from such fibers is dissolved or dissolved with acetone and then the luminescence of the residual fiber and of the fiber material dispersed in the adjacent paper stock as a criterion for the authenticity of the security paper is used.
EP82104887A 1981-06-05 1982-06-03 Security paper and method for its manufacture Expired EP0066854B1 (en)

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ATE12532T1 (en) 1985-04-15
ES8400524A1 (en) 1983-10-16
DE3122470C2 (en) 1985-09-05
JPS5854099A (en) 1983-03-30
EP0066854B1 (en) 1985-04-03
DE3122470A1 (en) 1983-01-05
ES514027A0 (en) 1983-10-16

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