EP1032498A1 - Materiaux d'impression thermosensibles et procede de verification d'authenticite - Google Patents

Materiaux d'impression thermosensibles et procede de verification d'authenticite

Info

Publication number
EP1032498A1
EP1032498A1 EP99944434A EP99944434A EP1032498A1 EP 1032498 A1 EP1032498 A1 EP 1032498A1 EP 99944434 A EP99944434 A EP 99944434A EP 99944434 A EP99944434 A EP 99944434A EP 1032498 A1 EP1032498 A1 EP 1032498A1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive
material according
dye
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99944434A
Other languages
German (de)
English (en)
Other versions
EP1032498B1 (fr
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 DE1998142866 external-priority patent/DE19842866A1/de
Priority claimed from DE1998142867 external-priority patent/DE19842867C2/de
Application filed by Mitsubishi HiTech Paper Flensburg GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Publication of EP1032498A1 publication Critical patent/EP1032498A1/fr
Application granted granted Critical
Publication of EP1032498B1 publication Critical patent/EP1032498B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/40Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48Elements suited for physical verification, e.g. by irradiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14Security printing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14Security printing
    • B41M3/144Security printing using fluorescent, luminescent or iridescent effects
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; 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
    • B41M5/41Base layers supports or substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; 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
    • B41M5/42Intermediate, backcoat, or covering layers
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/40Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/46Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36Backcoats; Back layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323Organic colour formers, e.g. leuco dyes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; 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
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/423Intermediate, 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 backing paper with a recording layer arranged on one side, which contains color formers and organic color acceptors which react with one another under the action of heat.
  • the invention further relates to methods for checking the authenticity of the recording materials according to the invention.
  • Heat-sensitive recording materials have been known for a long time. These materials are mainly used to record fax copies that are sent over public telephone networks - so-called fax procedures. Additional areas of application for heat-sensitive recording materials are gradually gaining importance through their use as transfer forms or checks, diplomas, certificates, package inserts for pharmaceutical products, receipts for all kinds of games of chance, tokens, receipts, parking tickets from parking machines, as well as entrance tickets and tickets.
  • DE 2518871 A1 discloses as a security feature 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 used with a stamp, felt pen or Roller device applied to the paper, the substance in or on the carrier paper reacts 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 0072481 B1 with respect to an admixture of 2- ⁇ 4'-amino-3 '-sulfophenyl) -6-methyl-benzothiazole-7-sulfonic acid or its salts 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 2747349 C 2 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, for counterfeit-proof papers, which are to be used in particular as payment instructions to be filled in by hand, which results in a full-surface Coloring of the paper surface results.
  • EP 0844097 A1 discloses a heat-sensitive recording material in which, as a first security feature, a latent image in places is printed 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 the image stability.
  • binders such as thermoplastic resins
  • the present invention now intends to provide heat-sensitive recording materials in which, with the aid of simple and widely available devices, several examination options with regard to the authenticity of the paper used are possible.
  • the invention sees a further object in the development of a security feature. times, which enables a check for the authenticity of the paper used far more clearly than a full-surface preparation.
  • the invention aims to provide effective protection against attempts at counterfeiting.
  • the invention also sees an object in the production of a heat-sensitive recording material to dispense with those components to be added to the paper pulp which, for example, fluorescent fibers, can result in the problems mentioned above in the production process.
  • preprints can be easily applied to the back of the heat-sensitive recording materials without the risk of disturbances in the printing process due to components present in a preparation applied on the back, such as binders or water repellents.
  • the invention provides, according to its first and particularly simple embodiment, a heat-sensitive recording material with a security feature, which comprises a carrier paper with a recording layer arranged on one side, which contains color formers and organic color acceptors which react with one another under the action of heat.
  • the heat-sensitive recording material is characterized in that, as a security feature, a water-soluble dye which fluoresces under UV radiation without a binder in a regular or irregular pattern which is invisible in daylight, so on the entire surface of the side which is opposite the side provided with a recording layer, i.e. the back is applied so that the entire surface has the pattern.
  • the heat-sensitive recording paper of the present invention offers a pattern that is more than that of an authenticity test due to the nature of its pattern with a security feature to be demonstrated with an alkaline substance to be applied that goes beyond and cannot easily be imitated security component.
  • An irregular pattern formation in the sense of the present invention preferably corresponds to a fine-grained structure which, in other words, can be referred to as mottling, while a regular pattern preferably corresponds to a strip-like structure.
  • mottling In the acidic or neutral pH range, the reverse side with the dye looks slightly colored when viewed with the naked eye in daylight.
  • the advantage of the water-soluble dye which is applied without a binder according to the above embodiment is that the application of preprints does not encounter the problems which are known in the case of coatings containing binders or hydrophobizing agents known from the prior art.
  • preprints are to be understood, for example, by means of flexographic or offset printing, in particular dry or Wateriess offset printing, such as, for example, form inscriptions, in which the form fields are filled out by means of a thermal printer when subsequently used as intended.
  • the water-soluble dye which fluoresces under UV radiation is preferably with a weight per unit area of 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 that opposite side provided with a recording layer, applied.
  • the invention provides a heat-sensitive recording material with security features, which comprises a carrier paper with a recording layer arranged on one side, which contains color formers and organic color acceptors which react with one another under the action of heat and which is characterized in that the first security feature a water-insoluble azine dye which is invisible to the naked eye is incorporated into the backing paper, which, when the surface of the side of the recording material opposite the recording layer is wetted with an organic solvent or an acid, causes a striking coloration, and as a second security feature on the side of the backing paper opposite the recording layer, So a layer is applied to the back with a dye on Pyre that is only slightly visible in the acidic or neutral pH range sulfonate base.
  • the pyrene sulfonate-based dye undergoes a color reaction in contact with an alkaline substance, which leads to a stable color that fluoresces in daylight.
  • the pyrene sulfonate dye can be applied without a binder when it comes to avoiding printability problems, but a common application with a binder, for example by means of a starch screed, is also possible.
  • the azine dye is preferably incorporated into the backing paper in an amount of 0.005 to 0.1% by weight, very particularly preferably in an amount of 0.01 to 0.03% by weight.
  • Azine dyes for the purposes of the present invention are to be understood as dyes characterized by the pyrazine ring (paradiazine ring) with attached aromatic nuclei.
  • 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 provides a heat-sensitive recording material with security features, which comprises a carrier paper with a recording layer arranged on one side, which contains color formers and organic color acceptors which react with one another under the action of heat and which is characterized in that the first security feature a water-insoluble azine dye which is invisible to the naked eye is incorporated into the backing paper, which causes a striking coloration when the side of the recording material opposite the recording layer is wetted with an organic solvent or an acid, and as a second security feature a water-soluble dye which fluoresces under UV radiation without Binder in a regular or irregular pattern, invisible in daylight, so on the surface of the side that the a recording layer side is applied, that the entire surface has the pattern.
  • the first security feature a water-insoluble azine dye which is invisible to the naked eye is incorporated into the backing paper, which causes a striking coloration when the side of the recording material opposite the recording layer is wetted with an organic solvent or an acid
  • a second security feature a water-soluble dye which
  • the advantage of the water-soluble dye applied without a binder is that the application of preprints does not encounter the printability problems explained above.
  • the recording papers according to the invention as claimed in claims 1 and 11 which have a water-soluble dye which fluoresces under UV radiation on the side opposite the side intended for recording, it is possible to carry out a first authenticity check in such a way that the side intended for recording opposite side is viewed under UV radiation, whereby the pattern that is not visible in daylight can be seen. If, in the recording paper according to the invention, the pyrene sulfonate-based dye is applied to the side opposite the side to be recorded in a regular or irregular pattern, this pattern can be seen under UV radiation.
  • a particularly preferred method for checking the authenticity of all of the recording papers according to the invention provides for the surface wetting of the side opposite the side to be recorded, in particular using a test pen or a comparable simple device with an alkaline substance, as a result of which a fluorescent, stable color visible in daylight is produced. Since the usual ink eraser pens contain alkaline substances, attempts at counterfeiting can also be identified in this way.
  • Another method for checking the authenticity of the recording papers according to claims 6 and 11 provides that a surface wetting of the layer opposite the recording layer with a mixture of a primary alcohol, a secondary alcohol and an acid by means of a test pen, sponge, stamp or a comparable simple technical device is made in the smallest possible amount.
  • a conspicuous coloration of the wetted surface indicates the authenticity of the heat-sensitive recording material under investigation, wherein a color reaction in the recording layer corresponding to the color reaction of the azine dye with the organic solvent or the acid should be avoided if possible.
  • Wood-free papers with any mass per unit area are preferably used as backing papers.
  • the recording layer is optionally applied to a primer.
  • a layer applied to the side of the carrier paper opposite the recording 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 using 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.
  • Example 2 as part of a production test, the pulp 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 handicraft based on the "atro" weight of the
  • 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 primer 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 which contains a mixture of 70% lactic acid, 15% ethanol and 15% isopropyl alcohol as the test substance.
  • this test substance it is possible to bring about a coloration by dissolving the azine dye by surface-wetting the side of the recording material opposite the recording layer. There is no corresponding color reaction of the recording layer. This would occur if solvents were used as if the test substance were applied too heavily.
  • an alkaline substance is applied to the opposite side of the recording material from the recording layer.
  • the reaction of the pyrene sulfonate-based dyes with the alkaline substance immediately leads to a stable color that fluoresces in daylight.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Credit Cards Or The Like (AREA)
  • Paper (AREA)
  • Accessory Devices And Overall Control Thereof (AREA)
EP99944434A 1998-09-19 1999-08-19 Materiaux d'impression thermosensibles et procede de verification d'authenticite Expired - Lifetime EP1032498B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19842867 1998-09-19
DE1998142866 DE19842866A1 (de) 1998-09-19 1998-09-19 Wärmeempfindliches Aufzeichnungsmaterial mit Sicherheitsmerkmal
DE19842866 1998-09-19
DE1998142867 DE19842867C2 (de) 1998-09-19 1998-09-19 Wärmeempfindliches Aufzeichnungsmaterial und ein Verfahren zur Authentizitätsprüfung
PCT/EP1999/006060 WO2000016986A1 (fr) 1998-09-19 1999-08-19 Materiaux d'impression thermosensibles et procede de verification d'authenticite

Publications (2)

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

Family

ID=26048936

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99944434A Expired - Lifetime EP1032498B1 (fr) 1998-09-19 1999-08-19 Materiaux d'impression thermosensibles et procede de verification d'authenticite

Country Status (7)

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

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP5253802B2 (ja) * 2004-04-02 2013-07-31 カーウッド・インコーポレイテッド 精肉の好ましい赤色を生じさせ且つ維持する改良された包装方法
ES2317253T3 (es) * 2004-06-11 2009-04-16 Ahlstrom Kauttua Oy Material de seguridad multicapa y su procedimiento de fabricacion.
DE102006056003B4 (de) * 2006-11-24 2008-08-14 Mitsubishi Hitec Paper Flensburg Gmbh Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal
US8330122B2 (en) * 2007-11-30 2012-12-11 Honeywell International Inc Authenticatable mark, systems for preparing and authenticating the mark
DE102009017444A1 (de) 2009-04-15 2010-10-21 Sension, Biologische Detektions- Und Schnelltestsysteme Gmbh Wärmeempfindliches Aufzeichnungsmaterial mit Sicherheitsmerkmal
ES2391928T3 (es) * 2009-12-01 2012-12-03 Mitsubishi Hitec Paper Europe Gmbh Material de registro termosensible con una característica de autenticidad

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT37053B (de) 1908-04-24 1909-04-26 Ignatz Dr Palocz Inhaliervorrichtung.
DE2518871A1 (de) * 1974-04-26 1975-11-13 Portals Ltd Sicherheitsdokumente
FR2365656A1 (fr) 1976-05-25 1978-04-21 Arjomari Prioux Papier de securite
DE3132146A1 (de) 1981-08-14 1983-03-03 Bayer Ag, 5090 Leverkusen Faelschungssicheres papier
FR2566440B1 (fr) 1984-06-22 1988-07-22 Jalon Michel Fibres de securite et autres matieres rendues luminescentes par un procede de teinture, leurs procedes de realisation et leurs applications
US5630869A (en) 1988-01-12 1997-05-20 Sicipa Holding S.A. Reversibly photochromic printing inks
US5308824A (en) 1990-09-28 1994-05-03 Mitsubishi Paper Mills Limited Recording material
DE19501289A1 (de) 1995-01-18 1996-07-25 Feldmuehle Ag Stora Wärmeempfindliches Aufzeichnungsmaterial und seine Verwendung
DE29617106U1 (de) 1996-10-01 1997-02-27 Papierfabrik Schoeller & Hoesch GmbH, 76593 Gernsbach Papier
EP0844097B1 (fr) 1996-11-21 2001-07-18 Ncr International Inc. Papier thermique avec des caractéristiques de sécurité et encre de sécurité à cet effet

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0016986A1 *

Also Published As

Publication number Publication date
JP4372353B2 (ja) 2009-11-25
WO2000016986A1 (fr) 2000-03-30
ATE220997T1 (de) 2002-08-15
DE59902110D1 (de) 2002-08-29
JP2002526302A (ja) 2002-08-20
US6632773B1 (en) 2003-10-14
ES2181470T3 (es) 2003-02-16
EP1032498B1 (fr) 2002-07-24

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