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EP1925459B1 - Method of producing a heat-sensitive recording material with authentification feature - Google Patents

Method of producing a heat-sensitive recording material with authentification feature Download PDF

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Publication number
EP1925459B1
EP1925459B1 EP07121262.5A EP07121262A EP1925459B1 EP 1925459 B1 EP1925459 B1 EP 1925459B1 EP 07121262 A EP07121262 A EP 07121262A EP 1925459 B1 EP1925459 B1 EP 1925459B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording layer
recording material
methyl
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.)
Not-in-force
Application number
EP07121262.5A
Other languages
German (de)
French (fr)
Other versions
EP1925459A3 (en
EP1925459A2 (en
Inventor
Matthias Neukirch
Matthias Marx
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 HiTec Paper Europe GmbH
Original Assignee
Mitsubishi HiTec Paper Europe 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
Application filed by Mitsubishi HiTec Paper Europe GmbH filed Critical Mitsubishi HiTec Paper Europe GmbH
Publication of EP1925459A2 publication Critical patent/EP1925459A2/en
Publication of EP1925459A3 publication Critical patent/EP1925459A3/en
Application granted granted Critical
Publication of EP1925459B1 publication Critical patent/EP1925459B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • 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
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—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
    • 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
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes

Definitions

  • the present invention relates to a method for producing a heat-sensitive recording material having an authenticating feature, comprising a substrate, optionally a pigmented intermediate layer applied to the substrate, and a heat-sensitive recording layer containing color formers and color acceptors.
  • the present invention also relates to a heat-sensitive recording material produced by this method.
  • Recording materials of this kind determine daily life in society and in professional life.
  • recording materials the authorized use of which is generally to be demonstrated by a specific marking of the material approved for this purpose, various solutions of authenticity-proofing security features have already been proposed in the past.
  • thermosensitive recording material having a security feature in which it is applied in the form of a regular or irregular pattern like a spurious watermark.
  • its security feature is characterized in that it is fluorescent under UV irradiation.
  • the present invention was then based on the object of providing an authentication feature for a recording material which should not be visible at all times and immediately, but only from a desired point in time at which the authenticity of the recording material carrying the feature should be visible.
  • the use of decolorizing substances in heat-sensitive recording materials is known, even if their use was previously associated with completely different objectives.
  • the JP 10 109477 A for a multicolor heat-sensitive recording sheet having at least one less sensitive and more sensitive recording layer incorporation of a preferred encapsulated decolorizing agent as a reaction product of a guanidine component and an isocyanate component in the more sensitive recording layer, thus apparently pursuing similar objects as in U.S. Pat US-A-3,916,068 ,
  • a multicolor heat-sensitive recording material in which the various recording layers generally have different minimum temperatures, above which they then react in a color-forming manner.
  • the known document suggests the incorporation of an organic amine derivative as a deinking agent in one of the recording layers or in one of the adjacent layers.
  • the decolorizing substances are preferably used in multicolor heat-sensitive recording materials to solve typical problems of multicolor of the recording materials.
  • stamping and, in general, all analog printing methods such as, in particular, offset printing have proven to be useful without being limited in any way.
  • application of the solution by means of inkjet printing is suitable.
  • those methods for producing heat-sensitive recording materials according to the embodiments proposed here are particularly preferred, in which the solution is stamped or printed on the heat-sensitive recording layer.
  • the solution can be excellent as an authentication feature on the heat-sensitive recording layer, wherein a layer formed in this way also quickly absorbs and dries.
  • Guanidine carbonate is thus perfectly able to block the color-forming reaction of color former and color acceptors when supplied with heat by the formation of a strongly alkaline environment during the color-forming reaction caused by the heat supply, said blocking being sharply defined in the invention and taking the form of the intended pattern.
  • a disadvantage of Guanidincarbonat is its low stability, which is indicated by a gray to yellowish discoloration. If, however, the recording material according to the invention is used only for a comparatively short period of a few hours up to a few days, guanidine carbonate is very easy to use owing to low procurement prices.
  • Arginine which satisfies the following formula (1) does not have the disadvantages of low stability and at the same time is able to ensure very sharp-edged blockages of the color-forming reaction of color former and color acceptors when heat is applied.
  • a 3 to 5% aqueous arginine solution is preferably used for application to the heat-sensitive recording layer.
  • a wetting agent, in particular olefin, and, based on the arginine solution, to 1 to 3.5%, for example, 12% polyvinylalcohol solution and 4 to 8% ethanol are added.
  • the heat-sensitive recording material according to the invention may comprise as color former at least one substance selected from the group of phthalide, xanthene, fluoran, triarylmethane, diphenylmethane, fluorene, oxazine, thiazine or spiropyran compounds known from the prior art where xanthene compounds are considered preferred.
  • Typical compounds of this type are, for example:
  • the recording layer can also contain, for example, one or more of the following near infrared absorbing compounds:
  • Very particular preferred color formers in the heat-sensitive recording layer in the context of the present invention are those substances selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3 (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N- cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran and 3- (N-ethyl-N-tetrahydrofuryl) -amino-6-methyl -7-anilinofluoran.
  • the recording layer of the heat-sensitive recording material according to the invention may in principle include all the color formers mentioned in particular, and in particular the preferred ones, in particular suitable color acceptors, in particular organic color acceptors.
  • the heat-sensitive recording layer has, as a color acceptor, N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to the formula (2) on.
  • the recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness.
  • Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, Dibenzyl oxalate, benzyl naphthyl ether, diphenyl sulfone, etc., with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 1,2-di (phenoxy) ethane being preferred.
  • Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
  • water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
  • Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, methyl acrylate-butadiene copolymers, etc. are also suitable as binders for incorporation into the heat-sensitive recording layer.
  • thermosensitive recording layer For the purposes of the present invention are polyvinyl alcohol alone and / or in conjunction with acrylate copolymers and / or in conjunction with methyl cellulose as particularly preferred binders which together, based on the total weight (atro) of the recording layer, in a range of 12 to 25 wt % (atro), preferably in a range of 18 to 22% by weight (atro), are incorporated in the thermosensitive recording layer.
  • the heat-sensitive recording layer may further contain lubricants and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate, etc.; Waxes, for example paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides, castor wax, etc.
  • Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silicic acid and calcium carbonate, in which case calcium carbonate, which is preferred in from 10 to 18% by weight, based on the total weight of the recording layer, of being incorporated in the recording layer is considered preferable.
  • roller coater, knife coater, curtain coater or air brush are particularly suitable as coating apparatus for applying the heat-sensitive recording layer.
  • the coating composition used to form the recording layer is aqueous.
  • the subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.3 to 5.8 g / m 2 .
  • a pigmented intermediate layer is expediently arranged between the recording layer and the substrate of the heat-sensitive recording material according to the invention.
  • the intermediate layer is applied in a preferred embodiment with leveling coating devices, such as, for example, roller coater, doctor blade or doctor blade coaters, the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating compound necessarily to be applied to the substrate heat-sensitive recording layer reduced.
  • leveling coating devices such as, for example, roller coater, doctor blade or doctor blade coaters
  • the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating compound necessarily to be applied to the substrate heat-sensitive recording layer reduced.
  • For the basis weight of the intermediate layer a preferred range between 5 and 20 g / m 2 and even better between 7 and 11 g / m 2 has proven.
  • inorganic oil-absorbing pigments When inorganic oil-absorbing pigments are incorporated in the intermediate layer sandwiched between the recording layer and the substrate, these pigments can absorb the thermoset-liquefied wax components of the thermosensitive recording layer in print image formation, thus favoring still safer and faster operation of the heat-induced recording, thus such an embodiment preferably applies.
  • the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, is having.
  • Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities.
  • the following inorganic pigments are also very well suited as constituents of the intermediate layer: silicon oxide, bentonite, calcium carbonate and aluminum oxide and, in particular, boehmite here. Also mixtures of several different types of inorganic pigments are conceivable.
  • the ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved when the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt .-% consists of inorganic pigment.
  • Pigment mixtures of different organic pigments are conceivable.
  • the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results.
  • a synthetic binder with the admixture of at least one natural polymer, more preferably starch, is a particularly suitable embodiment.
  • the proposed recording material when the solution containing a member of the list comprising guanidine carbonate, lysine and arginine is stamped on the heat-sensitive recording layer, the proposed recording material preferably has a protective layer, including any indication of a possible authentication feature or its shape prevent.
  • a protective layer for example, coating colors, as they are used in the EP-B-0 909 242 and secondly in the EP-B-1 333 991 be proposed.
  • the protective layer combines high environmental resistance with recyclability and good printability in the wet offset process.
  • the protective layers mentioned are both relatively cheap to produce and apply in one layer.
  • inorganic pigments natural or precipitated calcium carbonate, kaolin or titanium oxide are possible for the protective layer.
  • Crosslinking agents for the protective layer are, in particular, cyclic urea, methylolurea, polyamide-epichlorohydrin resin, ammonium zirconium carbonate.
  • the protective layer with a basis weight in a range of 1.5 to 6 g / m 2 and especially between 1.8 and 4 g / m 2 , in particular roller coater, doctor blade or (roll) doctor blade coater, but also curtain coater and air brush application unit offer as coating units for applying the protective layer.
  • a protective layer which are curable by means of actinic radiation.
  • actinic radiation UV or ionizing radiation, such as electron beams to understand.
  • a non-surface treated base paper is to be understood as meaning a base paper which has not been treated in a size press or in a coating device.
  • a non-surface-treated, sized in the mass base paper with an inorganic pigment, in particular calcium carbonate is considered suitable in the mass.
  • films of, for example, polyolefin and polyolefin-coated papers as a substrate are possible to the same extent, without such an embodiment having an exclusive character.
  • a calcined kaolin pigment, styrene-butadiene latex as a binder and, in addition to other aids, starch as cobinder-containing intermediate layer having a basis weight of 9 g / m 2 is applied using a doctor blade.
  • a heat-sensitive recording layer having a basis weight of 5.4 g / m 2 is applied by means of a roller doctor coater.
  • the aqueous coating used for this purpose contains the following components according to the formulation shown in Table 1: ⁇ u> Table 1: ⁇ / u> Data in wt .-% (atro), based on the total weight of the heat-sensitive recording layer color formers 3-dibutylamino-6-methyl-7-anilinofluoran (ODB-2) 9 color acceptor N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxyphenyl) -urea according to formula (2), which is Pergafast ® 201 (CIBA) 22 sensitizer Benzylnaphthyl ether (BNE) 22 binder Polyvinyl alcohol (PVA) 7 co-binder Acrylate copolymers 12 methylcellulose 2 pigment calcium carbonate 16
  • heat-sensitive recording layer which are not stated in percent and based on the total weight in% by weight (atro) include dispersants, defoamers, optical brighteners, thickeners, waxes and crosslinkers.
  • thermosensitive recording layer After drying the thermosensitive recording layer and smoothing the recording material, here a value of 150 Bekk sec is measured, carried out with the aid of a stamp, the application of an aqueous solution to the heat-sensitive recording layer, wherein for the solution, the following components according to the reproduced in Table 2 recipe be used: ⁇ u> Table 2: ⁇ / u> Data in% by weight (atro), based on the total weight of the aqueous arginine solution Solid particles Arginine according to formula (1) 4 wetting agent Olfin 0.5 binder polyvinyl alcohol 1
  • the heat-sensitive recording material is placed for 2 min in a drying oven at 120 ° C heat.
  • the heat causes blackening of the heat-sensitive recording layer as a result of the color-forming reaction of color former and color acceptor, but this blackening does not occur in sharp-edged places where the aqueous arginine solution had previously been applied.

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

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines wärmeempfindlichen Aufzeichnungsmaterials mit Authentifikationsmerkmal, umfassend ein Substrat, optional eine auf das Substrat aufgebrachte pigmentierte Zwischenschicht sowie eine Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht. Die vorliegende Erfindung betrifft auch ein nach diesem Verfahren hergestelltes wärmeempfindliches Aufzeichnungsmaterial.The present invention relates to a method for producing a heat-sensitive recording material having an authenticating feature, comprising a substrate, optionally a pigmented intermediate layer applied to the substrate, and a heat-sensitive recording layer containing color formers and color acceptors. The present invention also relates to a heat-sensitive recording material produced by this method.

Aufzeichnungsmaterialien der genannten Art bestimmen das tägliche Leben in der Gesellschaft und innerhalb des Berufslebens. Für den Einsatz von Aufzeichnungsmaterialien, deren berechtigte Verwendung allgemein durch eine spezifische Markierung des für diesen Zweck zugelassenen Materials nachzuweisen ist, wurden in der Vergangenheit bereits verschiedene Lösungen authentizitätsnachweisender Sicherheitsmerkmale vorgeschlagen.Recording materials of this kind determine daily life in society and in professional life. For the use of recording materials, the authorized use of which is generally to be demonstrated by a specific marking of the material approved for this purpose, various solutions of authenticity-proofing security features have already been proposed in the past.

Authentizitätsnachweise für Dokumente in Form passiver Untersuchungen werden beispielsweise ermöglicht durch sich größter Beliebtheit erfreuender Wasserzeichen, das sind Zeichnungen im Papier, die in der Regel durch unterschiedliche Papierdicke hervorgerufen wird. Es wird unterschieden zwischen

  • echten Wasserzeichen, die durch Verdrängung (so genannte Licht-Wasserzeichen) oder durch Anreicherung (so genannte Schatten-Wasserzeichen) der Fasermasse beispielsweise unter Verwendung eines Egoutteurs in der Siebpartie einer Papiermaschine hergestellt werden,
  • halbechten, so genannten Moletten-Wasserzeichen, die durch die Prägung des noch nassen Papiers in der Pressenpartie einer Papiermaschine erzeugt werden, wobei die Ausbildung solcher wie auch echter Wasserzeichen in den Substraten wärmeempfindlicher Aufzeichnungsmaterialien unter anderem in der EP 0 611 664 B1 beschrieben wird,
  • und schließlich unechten Wasserzeichen, wobei letztere gewöhnlich außerhalb der Papiermaschine entweder durch das Prägen oder durch das Bedrucken des fertig gestellten Papiers mit einem farblosen, gerne auch unter UV-Licht fluoreszierenden Lack erstellt werden, wie es unter anderem in der EP-A-0 844 097 beschrieben wird. Im zuletzt beschriebenen Beispiel für ein unechtes Wasserzeichen wird selbstverständlich keine unterschiedliche Papierdicke mehr durch die Zeichnung im Papier hervorgerufen.
Authenticates for documents in the form of passive examinations, for example, are made possible by the greatest popularity of pleasing watermarks, ie drawings in the paper, which are usually caused by different paper thickness. It is differentiated between
  • genuine watermarks produced by displacement (so-called light watermarks) or by enrichment (so-called shadow watermarks) of the fiber mass, for example using a dandy cutter in the wire section of a paper machine,
  • Halbchten, so-called Moletten watermark, which are produced by the embossing of the still wet paper in the press section of a paper machine, the formation of such as real watermarks in the substrates of heat-sensitive recording materials, inter alia in the EP 0 611 664 B1 is described
  • and finally spurious watermarks, the latter usually being produced outside the paper machine either by embossing or by printing the finished paper with a colorless, often UV-fluorescent, varnish, as described, inter alia, in US Pat EP-A-0 844 097 is described. Of course, in the example of a fake watermark described last, no different paper thickness is caused by the drawing in the paper.

Gleichzeitig ist aus der gattungsgemäßen EP-B-1 032 498 ein wärmeempfindliches Aufzeichnungsmaterial mit einem Sicherheitsmerkmal bekannt, bei dem dieses wie bei einem unechten Wasserzeichen in der Form eines regelmäßigen oder unregelmäßigen Musters aufgebracht ist. Bei dem derart bekannten Aufzeichnungsmaterial wird sein Sicherheitsmerkmal dadurch gekennzeichnet, dass es unter UV-Bestrahlung fluoreszierend ist.At the same time is from the generic EP-B-1 032 498 a thermosensitive recording material having a security feature in which it is applied in the form of a regular or irregular pattern like a spurious watermark. In the recording material thus known, its security feature is characterized in that it is fluorescent under UV irradiation.

Ausgehend von den bekannten unechten Wasserzeichen wurde es als ein Nachteil für bestimmte Anwendungen erkannt, dass dieses authentizitätsnachweisende Sicherheitsmerkmal jederzeit erkennbar ist. Der vorliegenden Erfindung lag dann die Aufgabe zugrunde, ein Authentifikationsmerkmal für ein Aufzeichnungsmaterial zur Verfügung zu stellen, das nicht jederzeit und unmittelbar, sondern nur ab einem gewünschten Zeitpunkt, in dem die Echtheit des das Merkmal tragenden Aufzeichnungsmaterials nachgewiesen werden soll, sichtbar sein soll.Based on the known spurious watermarks, it has been recognized as a disadvantage for certain applications that this authenticity-proofing security feature is recognizable at all times. The present invention was then based on the object of providing an authentication feature for a recording material which should not be visible at all times and immediately, but only from a desired point in time at which the authenticity of the recording material carrying the feature should be visible.

Die vorgegebene Aufgabe wird gelöst durch ein Verfahren zur Herstellung eines wärmeempfindlichen Aufzeichnungsmaterials mit einem Authentifikationsmerkmal, umfassend ein Substrat sowie eine Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht, wobei Farbbildner und Farbakzeptoren unter Einwirkung von Wärme farbbildend miteinander reagieren. Das vorgeschlagene Verfahren wird dadurch gekennzeichnet, dass die Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht mittels einer Lösung, enthaltend einen Vertreter aus der Liste, umfassend:

  • Guanidincarbonat,
  • Lysin und
  • Arginin,
beaufschlagt oder unterlegt wird. Nachfolgend erfolgt schließlich die Trocknung der Lösung in beliebiger Art und Weise.The object is achieved by a method for producing a heat-sensitive recording material having an authentication feature, comprising a substrate and a thermosensitive recording layer containing color formers and color acceptors, color formers and color acceptors reacting with each other in a color-forming manner under the action of heat. The proposed method is characterized in that the thermosensitive recording layer containing color formers and color acceptors by means of a solution containing a member of the list comprising:
  • guanidine carbonate,
  • Lysine and
  • arginine,
charged or underlaid. Subsequently, finally, the drying of the solution takes place in any manner.

Die vorgegebene Aufgabe wird auch durch ein wärmeempfindliches Aufzeichnungsmaterial, umfassend ein Substrat sowie eine Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht, gelöst, wobei das Aufzeichnungsmaterial dadurch gekennzeichnet wird, dass die Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht mittels einer Lösung, enthaltend einen Vertreter aus der Liste, umfassend:

  • Guanidincarbonat,
  • Lysin und
  • Arginin,
beaufschlagt oder unterlegt ist und nach einem Verfahren gemäß obiger Ausführungen hergestellt ist.The object is also achieved by a heat-sensitive recording material comprising a substrate and a heat-sensitive recording layer containing a color former and color acceptors, the recording material being characterized in that the heat-sensitive recording layer containing the color formers and color acceptors is prepared by means of a solution containing a representative from the list. full:
  • guanidine carbonate,
  • Lysine and
  • arginine,
loaded or underlaid and is prepared by a method according to the above statements.

Grundsätzlich ist die Verwendung von entfärbend reagierenden Substanzen in wärmeempfindlichen Aufzeichnungsmaterialien bekannt, auch wenn ihre Verwendung bisher mit vollkommen anderen Zielsetzungen verbunden war. So schlägt beispielsweise die JP 10 109477 A für ein mehrfarbiges wärmeempfindliches Aufzeichnungsblatt mit mindestens einer unempfindlicheren und einer empfindlicheren Aufzeichnungsschicht die Einbindung eines bevorzugt eingekapselten Entfärbungsmittels als Reaktionsprodukt aus einer Guanidinkomponente und einer Isocyanatkomponente in der empfindlicheren Aufzeichnungsschicht vor, womit offensichtlich ähnliche Ziele verfolgt werden wie in der US-A-3,916,068 .Basically, the use of decolorizing substances in heat-sensitive recording materials is known, even if their use was previously associated with completely different objectives. For example, the JP 10 109477 A for a multicolor heat-sensitive recording sheet having at least one less sensitive and more sensitive recording layer, incorporation of a preferred encapsulated decolorizing agent as a reaction product of a guanidine component and an isocyanate component in the more sensitive recording layer, thus apparently pursuing similar objects as in U.S. Pat US-A-3,916,068 ,

Auch hier wird ein mehrfarbiges wärmeempfindliches Aufzeichnungsmaterial vorgeschlagen, bei dem die verschiedenen Aufzeichnungsschichten in üblicherweise verschieden hohe Mindesttemperaturen aufweisen, oberhalb derer sie dann farbbildend reagieren. Um in einem solchen Fall einfarbige Schriftbilder statt Schriftbilder aus einer Kombination unterschiedlicher Farben zu erhalten, schlägt die bekannte Schrift die Einbindung eines organischen Aminderivats als Entfär-bungsmittel in eine der Aufzeichnungsschichten oder in einer der angrenzenden Schichten vor.Here, too, a multicolor heat-sensitive recording material is proposed in which the various recording layers generally have different minimum temperatures, above which they then react in a color-forming manner. In order to obtain monochrome typefaces instead of typefaces from a combination of different colors in such a case, the known document suggests the incorporation of an organic amine derivative as a deinking agent in one of the recording layers or in one of the adjacent layers.

Entsprechend den zuvor gewürdigten Schriften werden die entfärbend reagierenden Substanzen also bevorzugt in mehrfarbigen wärmeempfindlichen Aufzeichnungsmaterialien benutzt, um typische Probleme aus der Mehrfarbigkeit der Aufzeichnungsmaterialien zu lösen.Thus, according to the above-mentioned documents, the decolorizing substances are preferably used in multicolor heat-sensitive recording materials to solve typical problems of multicolor of the recording materials.

Für Wärmetransfermaterialien schlägt die EP-A-1 041 448 schließlich ein entfärbbares Material aus Farbstoffvorläufer, Entwickler, Matrixmaterial und Entfärber vor, bei dem der Entfärber den Farbstoffvorläufer physikalisch oder chemisch absorbieren soll. Ziel einer solchen Entfärbung soll es sein, das bekannte Wärmetransfermaterial besser dem Recycling wieder zuführen zu können.For heat transfer materials beats the EP-A-1 041 448 Finally, a decolorizable material of dye precursor, developer, matrix material and decolorizer, in which the decolorizer physically or chemically absorb the dye precursor. The aim of such a decolorization should be to be able to better recycle the known heat transfer material recycling.

Keine der somit als Stand der Technik zu berücksichtigenden Schriften legen die Verwendung von Guanidincarbonat, Lysin und/oder Arginin in einer zusätzlichen Schicht eines wärmeempfindlichen Aufzeichnungsmaterials nahe, keine dieser Schriften erwähnt deren Einsatzmöglichkeit als Authentifikationsmerkmal.None of the documents thus considered as prior art suggest the use of guanidine carbonate, lysine and / or arginine in an additional layer of a thermosensitive recording material, none of these documents mention their use as an authentication feature.

Die Lösung zur Beaufschlagung oder Unterlegung der wärmeempfindlichen Aufzeichnungsschicht wird bevorzugt in Form

  • eines Musters,
  • von Logos bzw. von fortlaufenden Nummerierungen
  • eines diagonalen Streifengittermusters
und/oder in Formen, wie sie aus zyklisch wiederkehrenden Wasserzeichen bekannt sind, aufgebracht. Es ist somit möglich, die wärmeempfindliche Aufzeichnungsschicht mit der Lösung zu unterlegen, so dass sie zwischen Substrat und Aufzeichnungsschicht bzw., sofern im Rahmen einer bevorzugten Ausführungsform gegeben, zwischen pigmentierter Zwischenschicht und Aufzeichnungsschicht ausgebildet wird. Als besonders bevorzugt gilt eine Ausführungsvariante, bei der die Lösung direkt auf die wärmeempfindliche Aufzeichnungsschicht aufgebracht wird.The solution for charging or underlaying the heat-sensitive recording layer is preferably in the form
  • a pattern,
  • logos or consecutive numbering
  • a diagonal stripe grid pattern
and / or in forms known from cyclically recurring watermarks. It is thus possible to underlay the heat-sensitive recording layer with the solution so that it is formed between the substrate and the recording layer or, if in a preferred embodiment, between the pigmented intermediate layer and the recording layer. Particularly preferred is a variant in which the solution is applied directly to the heat-sensitive recording layer.

Als mögliche Verfahren zur Aufbringung der Lösung auf die wärmeempfindliche Aufzeichnungsschicht haben sich Stempeln sowie generell alle analogen Druckverfahren wie insbesondere Offset-Drucken bewährt, ohne darauf in irgendeiner Art und Weise beschränkt zu sein. Auch ist die Aufbringung der Lösung mittels Tintenstrahldruck geeignet. Es gelten auf jeden Fall solche Verfahren zur Herstellung von wärmeempfindlichen Aufzeichnungsmaterialien entsprechend der hier vorgeschlagenen Ausführungsformen als besonders bevorzugt, bei denen die Lösung auf die wärmeempfindliche Aufzeichnungsschicht gestempelt bzw. gedruckt wird.As a possible method of applying the solution to the heat-sensitive recording layer, stamping and, in general, all analog printing methods such as, in particular, offset printing have proven to be useful without being limited in any way. Also, the application of the solution by means of inkjet printing is suitable. In any case, those methods for producing heat-sensitive recording materials according to the embodiments proposed here are particularly preferred, in which the solution is stamped or printed on the heat-sensitive recording layer.

Ist beispielsweise eine 15%-tige wässerige Guanidincarbonat-Lösung mit einem pH-Wert von 11,5, in einer bevorzugten Ausführungsform mit einem Zusatz von, bezogen auf die wässerige Guanidincarbonat-Lösung, 5 % Ethanol versehen, lässt sich die Lösung als Authentifikationsmerkmal hervorragend auf die wärmeempfindliche Aufzeichnungsschicht aufbringen, wobei eine derart ausgebildete Schicht zudem schnell einzieht und trocknet.For example, if a 15% aqueous Guanidincarbonat solution with a pH of 11.5, provided in a preferred embodiment with an addition of, based on the aqueous guanidine carbonate solution, 5% ethanol, the solution can be excellent as an authentication feature on the heat-sensitive recording layer, wherein a layer formed in this way also quickly absorbs and dries.

Guanidincarbonat ist somit hervorragend in der Lage, die farbbildende Reaktion von Farbbildner und Farbakzeptoren bei Wärmezufuhr durch die Ausbildung einer stark alkalischen Umgebung während der durch die Wärmezufuhr hervorgerufenen farbbildenden Reaktion zu blockieren, wobei diese Blockierung erfindungswesentlich scharf begrenzt und in Form des beabsichtigten Musters erfolgt. Nachteilig an Guanidincarbonat ist dessen geringe Stabilität, was sich durch eine graue bis gelbliche Verfärbung zeigt. Wird das erfindungsgemäße Aufzeichnungsmaterial hingegen nur für einen vergleichsweise kurzen Zeitraum von wenigen Stunden bis hin zu wenigen Tagen genutzt, ist Guanidincarbonat aufgrund niedriger Beschaffungspreise sehr gut zu nutzen.Guanidine carbonate is thus perfectly able to block the color-forming reaction of color former and color acceptors when supplied with heat by the formation of a strongly alkaline environment during the color-forming reaction caused by the heat supply, said blocking being sharply defined in the invention and taking the form of the intended pattern. A disadvantage of Guanidincarbonat is its low stability, which is indicated by a gray to yellowish discoloration. If, however, the recording material according to the invention is used only for a comparatively short period of a few hours up to a few days, guanidine carbonate is very easy to use owing to low procurement prices.

Arginin, welches der folgenden Formel (1) genügt,

Figure imgb0001
weist nicht die Nachteile einer geringen Stabilität auf und ist gleichzeitig in der Lage, sehr scharfkantige Blockierungen der farbbildenden Reaktion von Farbbildner und Farbakzeptoren bei Wärmezufuhr zu gewährleisten. Dazu wird bevorzugt eine 3 bis 5%tige wässerige Argininlösung zur Aufbringung auf die wärmeempfindliche Aufzeichnungsschicht benutzt. In diese Lösung kann zusätzlich ein Netzmittel, insbesondere Olfin, und, bezogen auf die Argininlösung, zu 1 bis 3,5 % eine beispielsweise 12%tige Polyvinylalkohollösung und zu 4 bis 8 % Ethanol zugegeben werden.Arginine which satisfies the following formula (1)
Figure imgb0001
 does not have the disadvantages of low stability and at the same time is able to ensure very sharp-edged blockages of the color-forming reaction of color former and color acceptors when heat is applied. For this purpose, a 3 to 5% aqueous arginine solution is preferably used for application to the heat-sensitive recording layer. In this solution, in addition, a wetting agent, in particular olefin, and, based on the arginine solution, to 1 to 3.5%, for example, 12% polyvinylalcohol solution and 4 to 8% ethanol are added.

Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial kann als Farbbildner mindestens eine Substanz enthalten, ausgewählt aus der Gruppe der aus dem Stand der Technik bekannten Phthalid-, Xanthen-, Fluoran-, Triarylmethan-, Diphenylmethan-, Fluoren-, Oxazin-, Thiazin- oder Spiropyran-Verbindungen, wobei Xanthen-Verbindungen als bevorzugt gelten.The heat-sensitive recording material according to the invention may comprise as color former at least one substance selected from the group of phthalide, xanthene, fluoran, triarylmethane, diphenylmethane, fluorene, oxazine, thiazine or spiropyran compounds known from the prior art where xanthene compounds are considered preferred.

Typische Verbindungen dieser Art sind beispielsweise:Typical compounds of this type are, for example:

Xanthen-Verbindungen:Xanthene compounds:

Rhodamine-B-anilinolactam, Rhodamine-B-p-chloroanilinolactam, 3-Diethylamino-7-dibenzylaminofluoran, 3-Diethylamino-7-octylaminofluoran, 3-Diethylamino-7-phenylfluoran, 3-Diethylamino-7-chlorofluoran, 3-Diethylamino-6-chloro-7-methylfluoran, 3-Diethylamino-7-(3,4-dichloroanilino)fluoran, 3-Diethylamino-7-(2-chloroanilino)fluoran, 3-Diethylamino-6-methyl-7-anilinofluoran, 3-(N-Ethyl, N-tolyl)amino-6-methyl-7-anilinofluoran, 3-Piperidino-6-methyl-7-anilino-fluoran, 3-(N-Ethyl, N-tolyl)amino-6-methyl-7-phenylethylfluoran, 3-Diethylamino-7-(4-nitroanilino)fluoran, 3-(N-Methyl, N-propyl)amino-6-methyl-7-anilinofluoran, 3-(N-Methyl, N-cyclohexyl)amino-6-methyl-7-anilino-fluoran, 3-(N-Ethyl, N-tetra-hydrofuryl)amino-6-methyl-7-anilinofluoran, etc.Rhodamine-B-anilinolactam, rhodamine-Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3-diethylamino-7-phenylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6- chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3-diethylamino-7- (2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N Ethyl, N-tolyl) amino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilino-fluoran, 3- (N-ethyl, N-tolyl) amino-6-methyl-7- phenylethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3- (N -methyl, N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl, N-cyclohexyl) amino-6-methyl-7-anilino-fluoran, 3- (N-ethyl, N-tetrahydrofuryl) amino-6-methyl-7-anilinofluoran, etc.

Triarylmethan-Verbindungen:Triarylmethane compounds:

3,3-Bis(p-dimethylaminophenyl)-6-dimethylaminophthalid (Kristall Violett Lacton), 3,3-Bis(p-dimethylaminophenyl)phthalid, 3-(p-Dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalid, 3-(p-Dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalid, 3-(p-Dimethylaminophenyl)-3-(2-phenylindol-3-yl)phthalid, 3,3-Bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalid, 3,3-Bis(1,2-dimethylindol-3-yl)-6-dimethylamino-phthalid, 3,3-Bis(9-ethylcarbazol-3-yl)-5-dimethylaminophthalid, 3,3-Bis(2-phenyl-indol-3-yl)-5-dimethylaminophthalid, 3-p-Dimethylaminophenyl-3(1-methylpyrrol-2-yl)-6-dimethylaminophthalid, etc.3,3-Bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (Crystal Violet Lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindole-3 -yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3.3 Bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylamino-phthalide, 3,3-bis (9-ethylcarbazole 3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenyl-indol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3 (1-methylpyrrol-2-yl) -6- dimethylaminophthalide, etc.

Diphenylmethan-Verbindungen:Diphenylmethane compounds:

4,4'-Bis-dimethylaminophenyl-benzhydrylbenzylether, N-Halophenylleucoauramine, N-2,4,5-Trichlorophenyl-leucoauramin, und dergleichen.4,4'-bis-dimethylaminophenyl benzhydryl benzyl ether, N-halophenyl leucoauramines, N-2,4,5-trichlorophenyl leucoauramine, and the like.

Thiazine-Verbindungen:Thiazine compounds:

Benzoylleucomethylenblau, p-Nitrobenzoylleucomethylenblau, etc.Benzoylleucomethylene blue, p-nitrobenzoylleucomethylene blue, etc.

Spiropyran-Verbindungen:Spiropyran compounds:

3-methylspiro-dinaphthopyran, 3-ethylspiro-dinaphthopyran, 3,3-dichlorospiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)spiropyran, 3-propyl-spiro-benzopyran, etc.3-methylspiro-dinaphthopyran, 3-ethylspiro-dinaphthopyran, 3,3-dichlorospiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho (3-methoxy-benzo) spiropyran, 3-propyl-spiro-benzopyran, etc ,

Weiterhin kann die Aufzeichnungsschicht beispielsweise auch eine oder mehrere der folgenden, im nahen Infrarot-Bereich absorbierenden Verbindungen enthalten:Furthermore, the recording layer can also contain, for example, one or more of the following near infrared absorbing compounds:

3,6-Bis(dimethylamino)fluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3,6-Bis(diethylamino)-fluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Dibutylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Dibutylamino-6-diethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3,6-Bis(dimethylamino)fluoren-9-spiro-3'-(6'-diethylamino-phthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3-Dibutylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3,6-Bis-(diethylamino)fluoren-9-spiro-3'-(6'-diethylaminophthalid), 3,6-Bis-(dimethylamino)-fluoren-9-spiro-3'-(6'-dibutylaminophthalid), 3-Dibutylamino-6-di-ethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dibutylaminophthalid), 3,3-Bis[2-(4-dimethylamino-phenyl)-2-(4-methoxyphenyl)-ethenyl]-4,5,6,7-tetrachlorophthalid, etc.3,6-Bis (dimethylamino) fluorene-9-spiro-3 '- (6'-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-dimethylaminophthalide), 3.6- Bis (diethylamino) -fluorene-9-spiro-3 '- (6'-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene -9-spiro-3 '- (6'-dimethylaminophthalide) 3,6-bis (dimethylamino) fluorene-9-spiro-3 '- (6'-diethylamino-phthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-diethylaminophthalide), 3 Dibutylamino-6-dimethylaminofluorene-9-spiro-3 '- (6'-diethylaminophthalide), 3,6-bis- (diethylamino) -fluorene-9-spiro-3' - (6'-diethylaminophthalide), 3,6-bis - (dimethylamino) -fluorene-9-spiro-3 '- (6'-dibutylaminophthalide), 3-dibutylamino-6-di-ethylaminofluorene-9-spiro-3' - (6'-diethylaminophthalide), 3-diethylamino-6 -dimethylaminofluorene-9-spiro-3 '- (6'-dibutylaminophthalide), 3,3-bis [2- (4-dimethylamino-phenyl) -2- (4-methoxyphenyl) -ethenyl] -4,5,6, 7-tetrachlorophthalide, etc.

Als ganz besonders bevorzugte Farbbildner in der wärmeempfindlichen Aufzeichnungsschicht gelten im Rahmen der vorliegenden Erfindung solche Substanzen, ausgesucht aus der Liste, umfassend: 3-diethylamino-6-methyl-7-Anilinofluoran, 3-dibutylamino-6-methyl-7-Anilinofluoran, 3-(N-methyl-N-propyl)amino-6-methyl-7-Anilinofluoran, 3-(N-ethyl-N-isoamyl)amino-6-methyl-7-Anilinofluoran, 3-(N-methyl-N-cyclohexyl)amino-6-methyl-7-Anilinofluoran, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-Anilinofluoran und 3-(N-ethyl-N-tetrahydrofuryl)-amino-6-methyl-7-Anilinofluoran.Very particular preferred color formers in the heat-sensitive recording layer in the context of the present invention are those substances selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3 (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N- cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran and 3- (N-ethyl-N-tetrahydrofuryl) -amino-6-methyl -7-anilinofluoran.

Die Aufzeichnungsschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials kann grundsätzlich alle zu den genannten und insbesondere zu den bevorzugt aufgeführten Farbbildner im einzelnen passenden Farbakzeptoren, insbesondere organische Farbakzeptoren beinhalten. Bevorzugt weist die wärmeempfindliche Aufzeichnungsschicht als Farbakzeptor N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß der Formel (2),

Figure imgb0002
auf.The recording layer of the heat-sensitive recording material according to the invention may in principle include all the color formers mentioned in particular, and in particular the preferred ones, in particular suitable color acceptors, in particular organic color acceptors. Preferably, the heat-sensitive recording layer has, as a color acceptor, N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to the formula (2)
Figure imgb0002
 on.

Die Aufzeichnungsschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials kann zur Erhöhung der thermischen Ansprechempfindlichkeit bevorzugt auch Sensibilisatoren mit einem Schmelzpunkt idealerweise von 60°C bis 180°C, besonders bevorzugt mit einem Schmelzpunkt von 80°C bis 140°C, enthalten. Derartige Sensibilisatoren sind beispielsweise: Benzyl-p-benzyloxy-benzoat, Stearamid, N-Methylolstearamid, p-Benzylbiphenyl, 1,2-Di(phenoxy)-ethan, 1,2-Di(m-methylphenoxy)ethan, m-Terphenyl, Dibenzyloxalat, Benzyl-naphthylether, Diphenylsulfon, etc., wobei Benzylnaphthylether, Diphenylsulfon, 1,2-Di(m-methylphenoxy)ethan und 1,2-Di(phenoxy)-ethan als bevorzugt gelten.The recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness. Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, Dibenzyl oxalate, benzyl naphthyl ether, diphenyl sulfone, etc., with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 1,2-di (phenoxy) ethane being preferred.

Geeignete Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht sind beispielsweise wasserlösliche Bindemittel wie Stärke, Hydroxyethylzellulose, Methylzellulose, Carboxymethylzellulose, Gelatine, Kasein, Polyvinylalkohole, modifizierte Polyvinylalkohole, Natriumpolyacrylate, Acrylamid-Acrylat-Copolymere, Acrylamid-Acrylat-Methacrylat-Terpolymere, Alkalisalze von Styrol-Maleinsäure-anhydrid-Copolymeren oder Ethylen-Maleinsäureanhydrid-Copolymeren, etc., die allein oder in Kombination untereinander eingesetzt werden können; auch wasserunlösliche Latexbinder wie Styrol-Butadiene-Copolymere, Acrylnitril-Butadien-Copolymere, Methyl-Acrylat-Butadien-Copolymere, etc. bieten sich als Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht an. Im Sinne der vorliegenden Erfindung gelten Polyvinylalkohol allein und/oder in Verbindung mit Acrylat-Copolymere und/oder in Verbindung mit Methylcellulose als besonders bevorzugte Bindemittel, die zusammen, bezogen auf das Gesamtgewicht (atro) der Aufzeichnungsschicht, in einem Bereich von 12 bis 25 Gew.-% (atro), bevorzugt in einem Bereich von 18 bis 22 Gew.-% (atro) in die wärmeempfindliche Aufzeichnungsschicht eingebunden sind.Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene. Maleic anhydride copolymers or ethylene-maleic anhydride copolymers, etc., which may be used alone or in combination with each other; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, methyl acrylate-butadiene copolymers, etc. are also suitable as binders for incorporation into the heat-sensitive recording layer. For the purposes of the present invention are polyvinyl alcohol alone and / or in conjunction with acrylate copolymers and / or in conjunction with methyl cellulose as particularly preferred binders which together, based on the total weight (atro) of the recording layer, in a range of 12 to 25 wt % (atro), preferably in a range of 18 to 22% by weight (atro), are incorporated in the thermosensitive recording layer.

Zur Vermeidung des Klebens an einem Thermokopf und zur Vermeidung einer übermäßigen Abnutzung des Thermokopfes kann die wärmeempfindliche Aufzeichnungsschicht weiterhin Gleit- und Trennmittel enthalten wie Metallsalze höherer Fettsäuren, zum Beispiel Zinkstearat, Kalziumstearat, usw.; Wachse, zum Beispiel Paraffin, oxidiertes Paraffin, Polyethylen, Polyethylenoxid, Stearamide, Kastorwachs, usw. Weitere Bestandteile der Aufzeichnungsschicht sind beispielsweise Pigmente, bevorzugt anorganische Pigmente wie beispielsweise Aluminium(hydr)oxid, Kieselsäure und Kalziumkarbonat, wobei hier insbesondere Kalziumkarbonat, das bevorzugt in einer Menge von 10 bis 18 Gew.-%, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in die Aufzeichnungsschicht eingebunden sein soll, als bevorzugt gilt.In order to prevent sticking to a thermal head and to avoid excessive wear of the thermal head, the heat-sensitive recording layer may further contain lubricants and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate, etc.; Waxes, for example paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides, castor wax, etc. Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silicic acid and calcium carbonate, in which case calcium carbonate, which is preferred in from 10 to 18% by weight, based on the total weight of the recording layer, of being incorporated in the recording layer is considered preferable.

Als Beschichtungsvorrichtung zum Auftrag der wärmeempfindlichen Aufzeichnungsschicht bieten sich insbesondere Rollrakelstreichwerk, Messerstreichwerk, Vorhangbeschichter oder Luftbürste an. Entsprechend einer bevorzugten Ausführungsform ist die zur Ausbildung der Aufzeichnungsschicht genutzte Beschichtungsmasse wässerig. Die anschließende Trocknung der Beschichtungsmasse geschieht üblicherweise durch ein Verfahren, bei dem Wärme zugeführt wird, wie es durch Heißluft-Schwebetrockner oder auch Kontakttrockner geschieht. Bewährt ist auch eine Kombination aus den aufgeführten Trockenverfahren. Die flächenbezogene Masse der wärmeempfindlichen Aufzeichnungsschicht liegt bevorzugt zwischen 2 und 6 g/m2 und noch besser zwischen 2,3 und 5,8 g/m2.Roller coater, knife coater, curtain coater or air brush are particularly suitable as coating apparatus for applying the heat-sensitive recording layer. According to a preferred embodiment, the coating composition used to form the recording layer is aqueous. The subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes. The basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.3 to 5.8 g / m 2 .

Zwischen der Aufzeichnungsschicht und dem Substrat des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials ist zweckmäßigerweise eine pigmentierte Zwischenschicht angeordnet. Ist die Zwischenschicht in einer bevorzugten Ausführungsform mit egalisierenden Beschichtungsvorrichtungen aufgetragen, wie sie beispielsweise Walzenstreichwerke, Streichmesser- oder (Roll-) Rakelstreichwerke darstellen, kann die Zwischenschicht ferner einen positiven Beitrag zur Egalisierung der Substratoberfläche leisten, womit sich die Menge an notwendigerweise aufzubringender Beschichtungsmasse für die wärmeempfindliche Aufzeichnungsschicht reduziert. Für die flächenbezogene Masse der Zwischenschicht hat sich ein bevorzugter Bereich zwischen 5 und 20 g/m2 und noch besser zwischen 7 und 11 g/m2 bewährt.Between the recording layer and the substrate of the heat-sensitive recording material according to the invention, a pigmented intermediate layer is expediently arranged. If the intermediate layer is applied in a preferred embodiment with leveling coating devices, such as, for example, roller coater, doctor blade or doctor blade coaters, the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating compound necessarily to be applied to the substrate heat-sensitive recording layer reduced. For the basis weight of the intermediate layer, a preferred range between 5 and 20 g / m 2 and even better between 7 and 11 g / m 2 has proven.

Werden in die zwischen der Aufzeichnungsschicht und Substrat gelegene Zwischenschicht anorganische ölabsorbierende Pigmente eingebunden, können diese Pigmente die durch Hitzeeinwirkung des Thermokopfes verflüssigten Wachsbestandteile der wärmeempfindlichen Aufzeichnungsschicht bei der Druckbildausbildung aufnehmen und begünstigen damit eine noch sichere und schnellere Funktionsweise der wärmeinduzierten Aufzeichnung, weshalb eine solche Ausführungsform als bevorzugt gilt.When inorganic oil-absorbing pigments are incorporated in the intermediate layer sandwiched between the recording layer and the substrate, these pigments can absorb the thermoset-liquefied wax components of the thermosensitive recording layer in print image formation, thus favoring still safer and faster operation of the heat-induced recording, thus such an embodiment preferably applies.

Besonders vorteilhaft ist es, wenn die Pigmente der Zwischenschicht eine Ölabsorption von mindestens 80 cm3/100 g und noch besser von 100 cm3/100 g, bestimmt nach der japanischen Norm JIS K 5101, aufweisen. Kalziniertes Kaolin hat sich aufgrund seines großen Absorptionsreservoirs in den Hohlräumen besonders bewährt. Jedoch auch folgende anorganische Pigmente sind als Bestandteile der Zwischenschicht sehr gut geeignet: Siliziumoxid, Bentonit, Kalziumkarbonat sowie Aluminiumoxid und hier besonders Böhmit. Auch Mischungen aus mehreren verschiedenartigen anorganischen Pigmenten sind vorstellbar.It is particularly advantageous if the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, is having. Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities. However, the following inorganic pigments are also very well suited as constituents of the intermediate layer: silicon oxide, bentonite, calcium carbonate and aluminum oxide and, in particular, boehmite here. Also mixtures of several different types of inorganic pigments are conceivable.

In Versuchen zeigte sich, dass auch die Einbindung von organischen Pigmenten in die pigmentierte Zwischenschicht sehr vorteilhaft sein kann, was damit begründet wird, dass solche organischen Pigmente in einem besonderen Maße einem hohen Wärmereflexionsvermögen der Zwischenschicht zuträglich sind. Die in einer Zwischenschicht eines wärmeempfindlichen Aufzeichnungsmaterials angeordneten organischen, so genannten Hohlkörperpigmente weisen in ihrem Inneren Luft auf, die einen guten Wärmeisolator darstellt. Die so als Wärmereflexionsschicht optimierte Zwischenschicht erhöht das Ansprechverhalten der Aufzeichnungsschicht gegenüber Wärme, was das Auflösungsvermögen des wärmeempfindlichen Aufzeichnungsmaterials deutlich erhöht und ferner die Druckgeschwindigkeit im Thermodrucker nach oben zu setzen vermag.Experiments have shown that the incorporation of organic pigments into the pigmented intermediate layer can also be very advantageous, which is justified by the fact that such organic pigments are to a particular extent conducive to a high heat reflectivity of the intermediate layer. The arranged in an intermediate layer of a heat-sensitive recording material organic, so-called hollow body pigments have in their interior air, which is a good heat insulator. The intermediate layer thus optimized as the heat reflection layer increases the response of the recording layer to heat, which remarkably increases the resolving power of the thermosensitive recording material and further raises the printing speed in the thermal printer.

Das Mengenverhältnis zwischen organischem und anorganischem Pigment ist ein Kompromiss der von den beiden Pigmentarten bewirkten Effekte, der besonders vorteilhaft gelöst wird, wenn die Pigmentmischung zu 5 bis 30 Gew.-% bzw. besser zu 8 bis 20 Gew.-% aus organischem und zu 95 bis 70 Gew.-% bzw. besser zu 92 bis 80 Gew.-% aus anorganischem Pigment besteht. Pigmentmischungen aus unterschiedlichen organischen Pigmenten sind vorstellbar.The ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved when the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt .-% consists of inorganic pigment. Pigment mixtures of different organic pigments are conceivable.

Neben den anorganischen und gegebenenfalls auch organischen Pigmenten enthält die pigmentierte Zwischenschicht mindestens ein Bindemittel bevorzugt auf Basis eines synthetischen Polymers, wobei beispielsweise Styrol-Butadien-Latex besonders gute Ergebnisse liefert. Die Verwendung eines synthetischen Bindemittels unter Beimischung mindestens eines natürlichen Polymers, wie besonders bevorzugt Stärke, stellt eine besonders geeignete Ausführungsform dar. Im Rahmen von Versuchen mit anorganischen Pigmenten wurde ferner festgestellt, dass mit einem Bindemittel-Pigment-Verhältnis innerhalb der pigmentierten Zwischenschicht zwischen 3:7 und 1:9, jeweils bezogen auf Gew.-%, eine besonders geeignete Ausführungsform vorliegt.In addition to the inorganic and optionally also organic pigments, the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results. The use of a synthetic binder with the admixture of at least one natural polymer, more preferably starch, is a particularly suitable embodiment. In the context of inorganic pigment tests, it has further been found that with a binder to pigment ratio within the pigmented interlayer between 3: 7 and 1: 9, in each case based on wt .-%, a particularly suitable embodiment is present.

Insbesondere, wenn die Lösung mit einem Vertreter aus der Liste, umfassend Guanidincarbonat, Lysin und Arginin, auf die wärmeempfindliche Aufzeichnungsschicht aufgestempelt bzw. aufgedruckt ist, weist das vorgeschlagene Aufzeichnungsmaterial bevorzugt eine Schutzschicht auf, auch um jeglichen Hinweis auf ein mögliches Authentifikationsmerkmal oder dessen Form zu verhindern.In particular, when the solution containing a member of the list comprising guanidine carbonate, lysine and arginine is stamped on the heat-sensitive recording layer, the proposed recording material preferably has a protective layer, including any indication of a possible authentication feature or its shape prevent.

Zur Ausbildung einer solchen Schutzschicht eignen sich beispielsweise Streichfarben, wie sie zum einen in der EP-B-0 909 242 und zum anderen in der EP-B-1 333 991 vorgeschlagen werden. In beiden Fällen verbindet die Schutzschicht hohe Umweltresistenz mit Entwertbarkeit sowie mit guter Bedruckbarkeit im Naßoffsetverfahren. Die genannten Schutzschichten sind beide relativ preisgünstig herzustellen und einlagig aufzutragen.To form such a protective layer, for example, coating colors, as they are used in the EP-B-0 909 242 and secondly in the EP-B-1 333 991 be proposed. In both cases, the protective layer combines high environmental resistance with recyclability and good printability in the wet offset process. The protective layers mentioned are both relatively cheap to produce and apply in one layer.

Als anorganische Pigmente sind für die Schutzschicht natürliches oder gefälltes Calciumcarbonat, Kaolin oder Titanoxid möglich Als Vernetzungsmittel für die Schutzschicht bieten sich insbesondere zyklischer Harnstoff, Methylolharnstoff, Polyamidepichlorhydrinharz, Amoniumzirkoniumkarbonat an.As inorganic pigments, natural or precipitated calcium carbonate, kaolin or titanium oxide are possible for the protective layer. Crosslinking agents for the protective layer are, in particular, cyclic urea, methylolurea, polyamide-epichlorohydrin resin, ammonium zirconium carbonate.

Es ist bevorzugt, die Schutzschicht mit einer flächenbezogenen Masse in einem Bereich von 1,5 bis 6 g/m2 und besonders zwischen 1,8 und 4 g/m2 aufzutragen, wobei sich insbesondere Walzenstreichwerke, Streichmesser- oder (Roll-) Rakelstreichwerke, aber auch Curtain Coater und Luftbürsten-Auftragswerke als Streichaggregate zur Aufbringung der Schutzschicht anbieten.It is preferred to apply the protective layer with a basis weight in a range of 1.5 to 6 g / m 2 and especially between 1.8 and 4 g / m 2 , in particular roller coater, doctor blade or (roll) doctor blade coater, but also curtain coater and air brush application unit offer as coating units for applying the protective layer.

In einem besonderen Maße gilt die drucktechnische Aufbringung einer Schutzschicht als bevorzugt. Verarbeitungstechnisch und hinsichtlich ihrer technologischen Eigenschaften besonders geeignet sind solche Schutzschichten, die mittels aktinischer Strahlung härtbar sind. Unter dem Begriff "aktinische Strahlung" sind UV- oder ionisierende Strahlungen, wie beispielsweise Elektronenstrahlen, zu verstehen.To a particular extent, the printing technology application of a protective layer is preferred. Processing technology and in terms of their technological properties are particularly suitable such protective layers which are curable by means of actinic radiation. The term "actinic radiation" UV or ionizing radiation, such as electron beams to understand.

Auch wenn nicht auf Papier als Substrat beschränkt, ist Papier und hier speziell ein nicht oberflächenbehandeltes Streichrohpapier bevorzugt in einem Bereich für die flächenbezogene Masse zwischen 45 und 130 g/m2 das Substrat, das sich am Markt auch mit Blick auf die gute Umweltverträglichkeit wegen der guten Recyclingfähigkeit durchgesetzt hat und das im Sinne der Erfindung bevorzugt ist. Unter einem nicht oberflächenbehandelten Streichrohpapier ist ein nicht in einer Leimpresse oder in einer Beschichtungsvorrichtung behandeltes Streichrohpapier zu verstehen. Im Sinne der vorliegenden Erfindung wird dabei insbesondere ein nicht oberflächenbehandeltes, in der Masse geleimtes Streichrohpapier mit einem anorganischem Pigment, insbesondere Kalziumkarbonat, in der Masse als geeignet angesehen. Für die Erfindung sind im gleichen Maße Folien beispielsweise aus Polyolefin und mit Polyolefin beschichtete Papiere als Substrat möglich, ohne dass eine solche Ausführung ausschließenden Charakter aufweist.Although not limited to paper as a substrate, paper and especially a non-surface treated base paper preferred in a range for the basis weight between 45 and 130 g / m 2, the substrate, which is also in the market with regard to the good environmental performance because of Good recycling ability has prevailed and is preferred for the purposes of the invention. A non-surface treated base paper is to be understood as meaning a base paper which has not been treated in a size press or in a coating device. For the purposes of the present invention, in particular a non-surface-treated, sized in the mass base paper with an inorganic pigment, in particular calcium carbonate, is considered suitable in the mass. For the invention, films of, for example, polyolefin and polyolefin-coated papers as a substrate are possible to the same extent, without such an embodiment having an exclusive character.

Die in der Beschreibung und in den Ansprüchen gemachten Angaben zur flächenbezogenen Masse, zu Gew.-% (Gewichts-%) beziehen sich jeweils auf das "atro"-Gewicht, d.h. absolut trockene Gewichtsteile.The basis weight,% by weight (% by weight) given in the specification and in the claims refer to the "atro" weight, respectively. absolutely dry parts by weight.

Die Erfindung soll anhand des folgenden Beispiels weiter verdeutlicht werden:The invention will be further clarified by the following example :

Als Substrat wird auf einer Langsieb-Papiermaschine aus gebleichten und gemahlenen Laub- und Nadelholzzellstoffen unter Zugabe von, bezogen auf den Gesamtfeststoffgehalt (atro) der der Papiermaschine zugeführten Pulpe, 0,6 Gew.-% (atro) Harzleim als Masseleimung sowie weiterer üblicher Beischlagstoffe ein Trägerpapier mit einer flächenbezogenen Masse von 53 g/m2 hergestellt. Frontseitig wird eine kalziniertes Kaolin als Pigment, Styrol-Butadien-Latex als Bindemittel und neben weiteren Hilfsmitteln Stärke als Cobinder aufweisende Zwischenschicht mit einer flächenbezogenen Masse von 9 g/m2 unter Nutzung eines Streichmessers aufgebracht.The substrate used on a fourdrinier paper machine made of bleached and ground hardwood and softwood pulps with the addition of, based on the total solids content (atro) of the pulp fed to the paper machine, 0.6 wt .-% (atro) Harzleim as engine sizing and other conventional admixtures a backing paper having a basis weight of 53 g / m 2 made. On the front side, a calcined kaolin pigment, styrene-butadiene latex as a binder and, in addition to other aids, starch as cobinder-containing intermediate layer having a basis weight of 9 g / m 2 is applied using a doctor blade.

Auf diese pigmentierte Zwischenschicht wird mittels Rollrakel-Streicheinrichtung eine wärmeempfindliche Aufzeichnungsschicht mit einer flächenbezogenen Masse von 5,4 g/m2 aufgetragen. Die dazu verwendete wässerige Streichmasse enthält die folgenden Komponenten nach der in Tabelle 1 wiedergegebenen Rezeptur: Tabelle 1: Angaben in Gew.-% (atro), bezogen auf das Gesamtgewicht der wärmeempfindlichen Aufzeichnungsschicht Farbbildner 3-dibutylamino-6-methyl-7-Anilinofluoran (ODB-2) 9 Farbakzeptor N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxyphenyl)-harnstoff gemäß Formel (2), das ist Pergafast® 201 (CIBA) 22 Sensibilisator Benzylnaphthylether (BNE) 22 Bindemittel Polyvinylalkohol (PVA) 7 Cobinder Acrylat-Copolymere 12 Methylcellulose 2 Pigment Kalziumkarbonat 16 90 Onto this pigmented intermediate layer, a heat-sensitive recording layer having a basis weight of 5.4 g / m 2 is applied by means of a roller doctor coater. The aqueous coating used for this purpose contains the following components according to the formulation shown in Table 1: <u> Table 1: </ u> Data in wt .-% (atro), based on the total weight of the heat-sensitive recording layer color formers 3-dibutylamino-6-methyl-7-anilinofluoran (ODB-2) 9 color acceptor N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxyphenyl) -urea according to formula (2), which is Pergafast ® 201 (CIBA) 22 sensitizer Benzylnaphthyl ether (BNE) 22 binder Polyvinyl alcohol (PVA) 7 co-binder Acrylate copolymers 12 methylcellulose 2 pigment calcium carbonate 16 90

Weitere nicht prozentual und bezogen auf das Gesamtgewicht in Gew.-% (atro) angegebene Bestandteile der wärmeempfindlichen Aufzeichnungsschicht sind unter anderem Dispergiermittel, Entschäumer, optische Aufheller, Verdicker, Wachse und Vernetzer.Other components of the heat-sensitive recording layer which are not stated in percent and based on the total weight in% by weight (atro) include dispersants, defoamers, optical brighteners, thickeners, waxes and crosslinkers.

Nach Trocknung der wärmeempfindlichen Aufzeichnungsschicht und Glättung des Aufzeichnungsmaterials, wobei hier ein Wert von 150 Bekk Sek gemessen wird, erfolgt unter Zuhilfenahme eines Stempels die Aufbringung einer wässerigen Lösung auf die wärmeempfindliche Aufzeichnungsschicht, wobei für die Lösung die folgenden Komponenten nach der in Tabelle 2 wiedergegebenen Rezeptur eingesetzt werden: Tabelle 2: Angaben in Gew.% (atro), bezogen auf das Gesamtgewicht der wässerigen Argininlösung Feststoffpartikel Arginin gemäß Formel (1) 4 Netzmittel Olfin 0,5 Bindemittel Polyvinylalkohol 1 After drying the thermosensitive recording layer and smoothing the recording material, here a value of 150 Bekk sec is measured, carried out with the aid of a stamp, the application of an aqueous solution to the heat-sensitive recording layer, wherein for the solution, the following components according to the reproduced in Table 2 recipe be used: <u> Table 2: </ u> Data in% by weight (atro), based on the total weight of the aqueous arginine solution Solid particles Arginine according to formula (1) 4 wetting agent Olfin 0.5 binder polyvinyl alcohol 1

Bezogen auf 100 Teile der fertig gestellten Argininlösung werden schließlich noch 7 Teile Ethanol zugegeben.Finally, 7 parts of ethanol are added based on 100 parts of the finished arginine solution.

Zur Kenntlichmachung des derart ausgebildeten Authentifikationsmerkmals wird das wärmeempfindliche Aufzeichnungsmaterial für 2 min in einen Trockenschrank bei 120 °C Hitze gelegt. Die Hitze bewirkt eine Schwärzung der wärmeempfindlichen Aufzeichnungsschicht in Folge der farbbildenden Reaktion von Farbbildner und Farbakzeptor, wobei diese Schwärzung jedoch scharfkantig an den Stellen nicht erfolgt, wo zuvor die wässerige Argininlösung aufgebracht worden war.To identify the thus formed authentication feature, the heat-sensitive recording material is placed for 2 min in a drying oven at 120 ° C heat. The heat causes blackening of the heat-sensitive recording layer as a result of the color-forming reaction of color former and color acceptor, but this blackening does not occur in sharp-edged places where the aqueous arginine solution had previously been applied.

Der Versuch zeigt sehr anschaulich, dass es mit der vorgeschlagenen Erfindung überzeugend gelungen ist, für ein Aufzeichnungsmaterial ein Authentifikationsmerkmal zur Verfügung zu stellen, das nicht unmittelbar, sondern nur ab einem gewünschten Zeitpunkt, in dem die Echtheit des das Merkmal tragenden Aufzeichnungsmaterials nachgewiesen werden soll, sichtbar gemacht werden kann. Dieser Zeitpunkt ist im beschriebenen Fall die Ausbildung der wärmeinduzierten Schwärzung der Aufzeichnungsschicht, die selbstverständlich nicht nur flächendeckend, sondern genauso auch unter Zuhilfenahme eines Thermodruckers gemäß eines Druckbildes erfolgen kann. Genauso ist es möglich, im Rahmen eines Schnelltests eine Lösemitteltinktur auf die Aufzeichnungsschicht mit der zusätzlichen Schicht als Authentifikationsmerkmal aufzubringen, beispielsweise mit einem entsprechend präparierten Filzstiftes. In diesem Fall würde das Lösemittel eine Schwärzung der Aufzeichnungsschicht bewirken, wobei diese Schwärzung jedoch scharfkantig an den Stellen nicht erfolgt, wo zuvor die wässerige Argininlösung aufgebracht worden war.The experiment very clearly shows that the proposed invention has convincingly succeeded in providing an authentication feature for a recording material which is not directly but only from a desired point in time at which the authenticity of the recording material carrying the feature is to be demonstrated. can be made visible. This time is in the case described, the formation of heat-induced blackening of the recording layer, which of course not only nationwide, but also with the aid of a thermal printer according to a printed image can be done. It is equally possible to apply a solvent tincture to the recording layer with the additional layer as an authentication feature in the context of a rapid test, for example with a correspondingly prepared felt-tip pen. In this case, the solvent would cause blackening of the recording layer, but this blackening does not occur in sharp-edged places where the aqueous arginine solution had previously been applied.

Claims (9)

  1. Process for the production of a heat-sensitive recording material having an authentication feature, comprising a substrate and a heat-sensitive recording layer containing colour formers and colour acceptors, characterised in that a solution containing a member of the list comprising:
    - guanidine carbonate,
    - lysine and
    - arginine
    is applied on or underneath the heat-sensitive recording layer containing colour formers and colour acceptors and is then dried.
  2. Process for the production of a heat-sensitive recording material according to patent claim 1, characterised in that the solution is applied in the form of a pattern.
  3. Process for the production of a heat-sensitive recording material according to either one of patent claims 1 and 2, characterised in that the solution is applied to the recording layer by stamping.
  4. Process for the production of a heat-sensitive recording material according to either one of patent claims 1 and 2, characterised in that the solution is applied to the recording layer by printing.
  5. Heat-sensitive recording material having an authentication feature, comprising a substrate and a heat-sensitive recording layer containing colour formers and colour acceptors, characterised in that a solution containing a member of the list comprising:
    - guanidine carbonate,
    - lysine and
    - arginine has been applied on or underneath the heat-sensitive recording layer containing colour formers and colour acceptors and has been produced by a process in accordance with one of patent claims 1 to 4.
  6. Heat-sensitive recording material according to patent claim 5, characterised in that the recording material has a protective layer covering the recording layer having the applied solution.
  7. Heat-sensitive recording material according to either one of patent claims 5 and 6, characterised in that the heat-sensitive recording layer has a colour former selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-(N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isoamyl)amino-6-methyl-7-anilinofluoran, 3-(N-methyl-N-cyclohexyl)amino-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-anilinofluoran and 3-(N-ethyl-N-tetrahydrofuryl)-amino-6-methyl-7-anilinofluoran.
  8. Heat-sensitive recording material according to any one of patent claims 5 to 7, characterised in that the heat-sensitive recording layer has as colour acceptor N-(p-toluenesulphonyl)-N'-3-(p-toluenesulphonyloxyphenyl)-urea in accordance with formula (2),
    Figure imgb0004
  9. Heat-sensitive recording material according to any one of patent claims 5 to 8, characterised in that a pigmented intermediate layer is arranged between the substrate and the heat-sensitive recording layer.
EP07121262.5A 2006-11-24 2007-11-22 Method of producing a heat-sensitive recording material with authentification feature Not-in-force EP1925459B1 (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN111655501A (en) * 2018-01-31 2020-09-11 三菱高新技术纸业欧洲有限公司 Thermosensitive recording material

Citations (1)

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EP1032498B1 (en) * 1998-09-19 2002-07-24 Mitsubishi Hitec Paper Flensburg GmbH Heat-sensitive recording materials and method for authenticity checking

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US3916068A (en) 1972-11-08 1975-10-28 Mitsubishi Paper Mills Ltd Heat sensitive recording material containing decolorizing agent
DE4304413A1 (en) 1993-02-13 1994-08-18 Kanzan Spezialpapiere Gmbh Web-like carrier material for a thermosensitive recording layer
JP3025660B2 (en) 1996-08-12 2000-03-27 内外カーボンインキ株式会社 Multicolor thermal recording material
EP0844097B1 (en) 1996-11-21 2001-07-18 Ncr International Inc. Thermal paper with security features and security ink therefor
DE19713590C1 (en) 1997-04-02 1998-10-29 Stora Publication Paper Ag Heat-sensitive recording sheet
DE19911484B4 (en) * 1998-03-16 2008-04-03 Ricoh Co., Ltd. Material for indicating the history of the temperature, method for producing the same and method using the same
DE19842867C2 (en) * 1998-09-19 2000-08-03 Mitsubishi Hitec Paper Flensbu Heat-sensitive recording material and a method for checking authenticity
US6326332B1 (en) * 1999-03-31 2001-12-04 Kabushiki Kaisha Toshiba Decolorable material and method for decoloring the same
DE10051294C1 (en) 2000-10-16 2002-04-18 Mitsubishi Hitec Paper Flensbu Thermographic material useful for ticket, especially lottery ticket, has protective coating of water-insoluble, self-crosslinking acrylic polymer and crosslinker pigmented (mainly) with highly purified, alkali-treated bentonite

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EP1032498B1 (en) * 1998-09-19 2002-07-24 Mitsubishi Hitec Paper Flensburg GmbH Heat-sensitive recording materials and method for authenticity checking

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111655501A (en) * 2018-01-31 2020-09-11 三菱高新技术纸业欧洲有限公司 Thermosensitive recording material

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DE102006056003B4 (en) 2008-08-14
DE102006056003A1 (en) 2008-05-29
EP1925459A2 (en) 2008-05-28

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