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EP2174794B1 - Heat-sensitive recording material with printed recording layer - Google Patents

Heat-sensitive recording material with printed recording layer Download PDF

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Publication number
EP2174794B1
EP2174794B1 EP09164951A EP09164951A EP2174794B1 EP 2174794 B1 EP2174794 B1 EP 2174794B1 EP 09164951 A EP09164951 A EP 09164951A EP 09164951 A EP09164951 A EP 09164951A EP 2174794 B1 EP2174794 B1 EP 2174794B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
layer
recording material
printed
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.)
Active
Application number
EP09164951A
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German (de)
French (fr)
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EP2174794A1 (en
Inventor
Wolfgang Dr. 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 HiTec Paper Europe GmbH
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Mitsubishi HiTec Paper Europe GmbH
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Publication of EP2174794A1 publication Critical patent/EP2174794A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • 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

Definitions

  • the invention relates to a heat-sensitive recording material having a substrate which has on at least one side a pigmented intermediate layer covering the entire surface of the substrate and a heat-sensitive recording layer containing printed color formers and color acceptors.
  • the primer layers preferably used for this purpose which are applied underneath the heat-sensitive recording layer and are ideally used for heat reflection, were regrettably found to be too abrasive in the experimental work on which this invention is based, as being in direct contact with the print heads of Thermal printers are suspend.
  • the inventors recognized that the full-surface printing of the pigmented intermediate layer recognized as being necessary according to the invention with a heat-sensitive recording layer is too expensive and economically not sensible either.
  • the heat-sensitive recording material according to the invention comprises a substrate, a pigmented intermediate layer covering at least one side of the substrate over its entire area and at least one heat-sensitive recording layer containing printed color formers and color acceptors.
  • the invention is characterized in that the at least one printed heat-sensitive recording layer is applied in the form of geometric, patterned and / or alphanumeric figures, optional further recording layers in the form of geometric, patterned and / or alphanumeric figures are applied and not by the one or more recording layers covered areas of the pigmented intermediate layer are covered by a non-color-forming printing layer.
  • the thermal head initiating the color-forming reaction of the color formers with the color acceptors in the heat-sensitive recording layer causes the waxy constituents in the recording layer to melt.
  • an intermediate layer completely covering the substrate is positioned between the substrate and the recording layer, which preferably contains either exclusively organic hollow-body pigments as pigment or even more preferably a pigment mixture of inorganic and organic pigment.
  • the inorganic pigment of this intermediate layer causes absorption of the melt. It is particularly advantageous if the inorganic pigment 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, has.
  • the inorganic pigment may preferably be selected from the list comprising calcined kaolin, calcium carbonate, silica and kaolin which have been found to be particularly useful due to their high absorbency. Also mixtures of several different types of inorganic pigments are conceivable.
  • organic pigments most preferably organic hollow body pigments, in the intermediate layer
  • organic pigments are beneficial to a very special extent high heat reflectivity of the intermediate layer and the heat reflectivity, in a weak extent even with an intermediate layer exclusively with given inorganic pigments, can increase significantly.
  • the organic hollow body pigments disposed in an intermediate layer of a thermosensitive recording material have air inside thereof, 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.
  • the quantitative ratio between organic and inorganic pigment is a compromise between the effects caused by the two types of pigment, which is achieved particularly advantageously if the pigment mixture contains 15 to 50% by weight. % or better to 20 to 50 wt .-% of organic and 85 to 50 wt .-% or better to 80 to 50 wt .-% of inorganic Pigment exists. It is very particularly preferred if the pigment mixture consists of 25 to 40% by weight of organic and 75 to 60% by weight of inorganic pigment.
  • the organic hollow body pigments have a wall of thermoplastic resin which preferably comprises (meth) acrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene acrylate, polyacrylonitrile or polyacrylic acid ester.
  • thermoplastic resin which preferably comprises (meth) acrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene acrylate, polyacrylonitrile or polyacrylic acid ester.
  • Pigment mixtures of different organic pigments are conceivable.
  • a glass transition temperature greater than or equal to 100 ° C and preferably greater than or equal to 105 ° C was found to be advantageous because below these temperatures, an increased degree of yellowing was detected.
  • the particle size of the organic hollow body pigments in the intermediate layer is ideally in a range from 0.75 ⁇ m to less than 1.5 ⁇ m, very particularly preferably in a range from 0.9 ⁇ m to 1.2 ⁇ m. Particle sizes below 0.75 microns prohibit due to rheological processing difficulties. Particle sizes above 1.5 microns show too coarse-grained behavior and prevent a preferred leveling effect of the intermediate layer.
  • a particle size of less than 2 ⁇ m, determined as D 50 value is particularly recommended. Pigments which have a particle size distribution of from 34 to 40% by weight of less than 1 ⁇ m and from 57 to 63% by weight of less than 2 ⁇ m have proved to be advantageous.
  • the intermediate layer further comprises one or more binders selected from the group consisting of polyvinyl alcohol, styrene-butadiene latex, starch, carboxymethyl cellulose, cellulose derivatives, styrene-butadiene latex being particularly preferred.
  • the binder content in the intermediate layer preferably consists of 69 to 76 wt .-% of styrene-butadiene latex.
  • an intermediate layer positioned between the substrate and the heat-sensitive recording layer can positively contribute to the leveling of the substrate layer surface, thus reducing the amount of ink for the heat-sensitive recording layer.
  • To order the intermediate layer offer so far preferably equalizing commissioned works such as Roller blade and doctor or blade on. It is also possible to print on the interlayer, in which case the flexographic printing process is the most economical, gives the best results and is particularly preferred.
  • the formation of the intermediate layer with a basis weight in a range of 5 g / m 2 to 20 g / m 2 and more preferably between 7 g / m 2 and 10 g / m 2 .
  • 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 and diphenyl sulfone, 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 and methyl acrylate-butadiene copolymers 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 or calcium stearate; Waxes, for example paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides and castor wax.
  • Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 18% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred.
  • a binder-to-pigment ratio of between 2: 1 and 1: 1 and in particular between 1.8: 1 and 1.2: 1 is particularly preferred in the at least one printed heat-sensitive recording layer.
  • the at least one printed heat-sensitive recording layer all possible printing methods of the analog printing can be used.
  • analog printing all printing processes that work with printing plate or cylinder, including gravure, screen printing, offset printing and in a very particularly preferred embodiment flexographic belongs.
  • the printing inks for forming the at least one printed heat-sensitive recording layer should be UV-crosslinking.
  • the at least one heat-sensitive recording layer should preferably be printed directly onto the intermediate layer.
  • the other recording layers are also sensitive to heat.
  • they should preferably contain the sensitizers, binders, pigments, lubricants and release agents which are also preferred for the at least one heat-sensitive recording layer printed on.
  • the heat-sensitive further recording layers according to the preferred embodiment have as color formers at least one substance selected from the group of known from the prior art phthalide, xanthene, fluoran, triarylmethane, diphenylmethane, fluorene, oxazine, thiazine or Spiropyran compounds, with xanthene compounds are considered preferred.
  • Typical compounds of this type are, for example:
  • the further recording layers may also contain, for example, one or more of the following near infrared absorbing compounds:
  • Very particular preferred color formers for the further recording layers 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 further recording layers are preferably those which are color-forming under the influence of heat. Very particular preference is given to those embodiments in which the colors formed in the further recording layers are different from the color which arises in the at least one printed heat-sensitive recording layer under the action of heat.
  • the further recording layers comprise encapsulated color formers and / or color acceptors. These capsules, or so-called microcapsules, are designed so that they break under the influence of pressure or heat, thus releasing the encapsulated color formers and / or dye acceptors.
  • the further recording layers are formed as pressure-sensitive or else as heat-sensitive recording layers.
  • the regions of the pigmented intermediate layer which are not covered by the one or more recording layers are covered by a non-color-forming printing layer according to the invention. It is considered preferable if both all the recording layers and also the non-color-forming printing layer are formed by the same printing method, particularly preferably within the same pass through a single printing press. Gravure printing, offset printing or flexographic printing are considered to be the printing process offering a particular degree.
  • the non-color-forming printing layer is particularly preferably formed with the exact same, not necessary for the color formation, components in the same quantitative proportions to each other as the at least one printed heat-sensitive recording layer.
  • the non-color-forming printing layer comprises 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, which can be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as
  • polyvinyl alcohol alone and / or in combination with acrylate copolymers and / or in combination with methyl cellulose, are considered to be particularly preferred binders which together in a range of 12, based on the total weight (atro) of the non-color-forming printing layer to 25 wt .-% (atro), preferably in a range of 18 to 22 wt .-% (atro) are incorporated into the non-color-forming printing layer.
  • Further constituents of the non-color-forming printing layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 18% by weight, based on the total weight of the non-color-forming printing layer to be incorporated in the non-color-forming printing layer, is considered preferable.
  • pigments preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 18% by weight, based on the total weight of the non-color-forming printing layer to be incorporated in the non-color-forming printing layer, is considered preferable.
  • a binder-to-pigment ratio of between 2: 1 and 1: 1 and in particular between 1.8: 1 and 1.2: 1 is particularly preferred in the non-color-forming printing layer.
  • UV and electron radiation are particularly suitable for crosslinking the protective layer, with UV radiation being particularly preferred.
  • the protective layer contains photoinitiators in a range from 2 to 20% by weight and the weight% data for the one or more (meth) acrylates, photoinitiators and wax add up to 67.5 to 100% by weight. % of the protective layer.
  • Examples of the (meth) acrylates according to the proposed protective layer or composition for the protective layer are dipentaerythritol penta (meth) acrylate and can be found, for example, in the literature US 4,485,123 and EP 0 209 684 A1 ,
  • the amine-modified (meth) acrylate used is preferably amine-modified polyether acrylate.
  • photoinitiators it is possible to use those which initiate the curing or radical polymerization by using UV radiation and absorb, for example, in the wavelength range from 190 to 400 nm.
  • photoinitiators are, for example, chlorine-containing photoinitiators, aromatic ketones, hydroxyphenylphenones, phosphine oxides.
  • Preferred photoinitiators are benzophenone derivatives, phenyl ketones and phenol phosphenates.
  • waxes for example, polyethylene waxes, such as PTFE-modified polyethylene wax used.
  • the protective layer can be applied with only one application level, in which case a surface-related mass of the protective layer in a range from 0.5 to 4.5 g / m 2 is particularly suitable.
  • the basis weight of the entire protective layer is preferably in a range from 1.2 to 6 g / m 2 and more preferably between 1.5 and 4 g / m 2 .
  • paper As a substrate according to a first alternative form, paper, and more particularly a non-surface treated base paper, is preferred, without the invention being restricted to such a substrate.
  • a non-surface treated base paper is to be understood as meaning a base paper not treated in a size press or coater.
  • papers coated with polyolefin are equally possible as a substrate.
  • a film is preferred as the substrate, with very particular preference being given to those films selected from the list comprising polyethylene film, polypropylene film and, in particular, polyester film which offers itself to a particular extent for good processing advantages. If film is used as the substrate for the present invention, its previous corona treatment is necessary. In the context of this second alternative form, it is particularly preferred if the pigmented intermediate layer is printed on the substrate.

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

Abstract

An imprinted heat-sensitive recording layer is applied in the form of geometric, pattern-like and/or alphanumeric figures. As an option, further recording layers are applied in the form of geometric, pattern-like and/or alphanumeric figures. Areas in a pigmented intermediate layer not covered by one or more recording layers are covered by a non-color-forming printed layer.

Description

Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial mit einem Substrat, das auf mindestens einer Seite eine das Substrat vollflächig abdeckende pigmentierte Zwischenschicht und eine aufgedruckte, Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht aufweist.The invention relates to a heat-sensitive recording material having a substrate which has on at least one side a pigmented intermediate layer covering the entire surface of the substrate and a heat-sensitive recording layer containing printed color formers and color acceptors.

Der dieser Schrift zugrunde liegende Wunsch nach drucktechnischer Aufbringung der wärmeempfindlichen Aufzeichnungsschicht liegt in der größeren Flexibilität des Druckprozesses gegenüber dem Streichprozess unter Verwendung der dort üblichen Streichmaschinen beispielsweise mit Streichmesser-, Rollstab- oder Farbvorhang-Auftragsaggregaten begründet. Durch diese größere Flexibilität kann in einem verstärkten Maße auf Kundenwünsche nach sehr individuellen Aufzeichnungsschichten eingegangen werden.The underlying requirement of this document for printing application of the heat-sensitive recording layer is due to the greater flexibility of the printing process compared to the coating process using the coating machines customary there, for example with doctor blade, roll bar or color curtain application units. Due to this greater flexibility, customer requirements for very individual recording layers can be addressed to a greater extent.

In diesem Sinne sind Gegenstand zahlreicher Vorschläge in der EP-A-0 623 909 Aufzeichnungsmaterialien, die in ihren Aufzeichnungsschichten durch Druck- oder Hitzeeinwirkung Schriftbilder in mehreren verschiedenen Farben entwickeln können. Die einzelnen Aufzeichnungsschichten der derart bekannten Aufzeichnungsmaterialien weisen zu diesem Zweck nebeneinander liegende, zueinander abgegrenzte Bereiche auf, die verschiedenartige zum Teil eingekapselte Farbstoffvorläufer und Entwickler aufweisen. Sowohl die jeweils eine Aufzeichnungsschicht ausmachenden Bereiche verschiedenartiger Farbstoffvorläufer und Entwickler wie auch eine optional vorgesehene, die Aufzeichnungsschicht abdeckende Schutzschicht werden mittels Drucktechnik aufgebracht. Somit zielt die Lehre dieser Schrift in eine Richtung, welche die Verwendung von Streichmaschinen zur Aufbringung von druck- oder wärmeempfindlichen Aufzeichnungsschichten zu überwinden sucht.In this sense, are the subject of numerous proposals in the EP-A-0 623 909 Recording materials that can develop typefaces in several different colors in their recording layers by pressure or heat. For this purpose, the individual recording layers of the recording materials known in this way have juxtaposed, mutually delimited areas which have various partially encapsulated dye precursors and developers. Both the areas of different dye precursors and developers constituting a recording layer and an optional protective layer covering the recording layer are applied by printing technique. Thus, the teaching of this document is directed in a direction which seeks to overcome the use of coating machines for applying pressure or heat sensitive recording layers.

Auch ist generell die Bedruckung und Kaschierung flexibler Materialien mit strahlenhärtbaren Druckfarben aus der DE-A-199 12 054 bekannt. Diese eher dem entfernteren Stand der Technik zuzurechnende Schrift zielt auf die Herstellung von Verbundstoffen und vermag insofern dem Fachmann auf dem Gebiet der wärmeempfindlichen Aufzeichnungsmaterialien sicherlich keine Hinweise zur Entwicklung wärmeempfindlicher Aufzeichnungsmaterialien mit aufgedruckter wärmeempfindlicher Aufzeichnungsschicht zu geben.Also, in general, the printing and lamination of flexible materials with radiation-curable inks from the DE-A-199 12 054 known. This document, which is more in the background of the prior art, aims at the production of composites and, to that extent, certainly does not give the skilled person in the field of heat-sensitive recording materials any indication of the development of heat-sensitive materials To give recording materials with printed heat-sensitive recording layer.

Die derart bekannten Verfahren zur Herstellung wärmeempfindlicher Aufzeichnungsmaterialien mit aufgedruckter Aufzeichnungsschicht konnten - genauso wenig wie die entsprechenden Aufzeichnungsmaterialien selbst - innerhalb der Massenproduktion überzeugen. Insbesondere stellten sich keineswegs die gleichsam erhofften monetären Einsparungen ein. Den Erfindern lag das Problem zugrunde, ein wirtschaftlich interessantes wärmeempfindliches Aufzeichnungsmaterial mit aufgedruckter Aufzeichnungsschicht zu entwickeln, das über ein überzeugendes thermisches Ansprechverhalten gegenüber Wärme verfügt und somit auch mit großer Druckgeschwindigkeit im Thermodrucker verarbeitet werden kann.The thus-known methods for producing heat-sensitive recording materials with a printed recording layer could - just as the corresponding recording materials themselves - convince within the mass production. In particular, the monetary savings that were hoped for did not materialize. The inventors had the problem to develop an economically interesting heat-sensitive recording material with printed recording layer, which has a convincing thermal response to heat and thus can be processed at high printing speed in the thermal printer.

Die aus diesem Grund bevorzugt eingesetzten Grundierschichten, die unterhalb der wärmeempfindlichen Aufzeichnungsschicht ausgebracht und im Idealfall Hohlkörperpigmente zur Wärmereflexion aufweisend eingesetzt werden, erwiesen sich im Rahmen der dieser Erfindung zugrunde liegenden Versuchsarbeiten bedauerlicherweise als viel zu abrasiv, als dass sie dem direkten Kontakt mit den Druckköpfen von Thermodruckern auszusetzen sind. Hingegen erkannten die Erfinder, dass die vollflächige Bedruckung der als erfindungsgemäß notwendig erkannten pigmentierten Zwischenschicht mit einer wärmeempfindlichen Aufzeichnungsschicht zu teuer und wirtschaftlich auch nicht sinnvoll ist.The primer layers preferably used for this purpose, which are applied underneath the heat-sensitive recording layer and are ideally used for heat reflection, were regrettably found to be too abrasive in the experimental work on which this invention is based, as being in direct contact with the print heads of Thermal printers are suspend. On the other hand, the inventors recognized that the full-surface printing of the pigmented intermediate layer recognized as being necessary according to the invention with a heat-sensitive recording layer is too expensive and economically not sensible either.

Das hier vorgeschlagene Aufzeichnungsmaterial vermag die gestellten Aufgaben eines wirtschaftlich interessanten wärmeempfindlichen Aufzeichnungsmaterials mit hohem thermischen Ansprechverhalten und Druckkopf-geschmeidigem Druckverhalten nachhaltig zu lösen. Dabei weist das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial ein Substrat, eine mindestens eine Seite des Substrats vollflächig abdeckende pigmentierte Zwischenschicht und mindestens eine aufgedruckte, Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht auf. Gekennzeichnet wird die Erfindung dadurch, dass die mindestens eine aufgedruckte wärmeempfindliche Aufzeichnungsschicht in Form geometrischer, musterartiger und/oder alphanumerischer Figuren aufgebracht ist, optional weitere Aufzeichnungsschichten in Form geometrischer, musterartiger und/oder alphanumerischer Figuren aufgebracht sind und die nicht durch die eine oder mehrere Aufzeichnungsschichten bedeckten Bereiche der pigmentierten Zwischenschicht durch eine nicht-farbbildende Druckschicht abgedeckt sind.The recording material proposed here can sustainably solve the objects of an economically interesting thermosensitive recording material having high thermal response and printhead-smooth printing performance. In this case, the heat-sensitive recording material according to the invention comprises a substrate, a pigmented intermediate layer covering at least one side of the substrate over its entire area and at least one heat-sensitive recording layer containing printed color formers and color acceptors. The invention is characterized in that the at least one printed heat-sensitive recording layer is applied in the form of geometric, patterned and / or alphanumeric figures, optional further recording layers in the form of geometric, patterned and / or alphanumeric figures are applied and not by the one or more recording layers covered areas of the pigmented intermediate layer are covered by a non-color-forming printing layer.

Der in der wärmeempfindlichen Aufzeichnungsschicht die farbbildende Reaktion der Farbbildner mit den Farbakzeptoren auslösende Thermokopf bewirkt ein Schmelzen der wachsartigen Bestandteile in der Aufzeichnungsschicht. Zur Vermeidung eines Anhaftens dieser wachsartigen Bestandteile als Schmelze am Thermokopf ist zwischen dem Substrat und der Aufzeichnungsschicht eine das Substrat vollständig abdeckende Zwischenschicht positioniert, die bevorzugt als Pigment entweder ausschließlich organische Hohlkörperpigmente oder noch weiter bevorzugt eine Pigmentmischung aus anorganischem und organischem Pigment enthält.The thermal head initiating the color-forming reaction of the color formers with the color acceptors in the heat-sensitive recording layer causes the waxy constituents in the recording layer to melt. To avoid adhesion of these waxy constituents as a melt to the thermal head, an intermediate layer completely covering the substrate is positioned between the substrate and the recording layer, which preferably contains either exclusively organic hollow-body pigments as pigment or even more preferably a pigment mixture of inorganic and organic pigment.

Das anorganische Pigment dieser Zwischenschicht bewirkt eine Absorption der Schmelze. Es ist dabei besonders vorteilhaft, wenn das anorganische Pigment 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, aufweist. Das anorganische Pigment kann bevorzugt ausgesucht sein aus der Liste, umfassend Calcinierter Kaolin, Calciumcarbonat, Siliziumdioxid und Kaolin, die sich aufgrund ihrer großen Absorptionsvermögen besonders bewährt haben. Auch Mischungen aus mehreren verschiedenartigen anorganischen Pigmenten sind vorstellbar.The inorganic pigment of this intermediate layer causes absorption of the melt. It is particularly advantageous if the inorganic pigment 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, has. The inorganic pigment may preferably be selected from the list comprising calcined kaolin, calcium carbonate, silica and kaolin which have been found to be particularly useful due to their high absorbency. Also mixtures of several different types of inorganic pigments are conceivable.

Die Einbindung von organischen Pigmenten, ganz besonders bevorzugt organischen Hohlkörperpigmenten, in die Zwischenschicht wird damit begründet, dass solche organischen Pigmente in einem ganz besonderen Maße einem hohen Wärmereflexionsvermögen der Zwischenschicht zuträglich sind und das Wärmereflexionsvermögen, das in einem schwachen Maße auch bei einer Zwischenschicht ausschließlich mit anorganischen Pigmenten gegeben ist, signifikant steigern können. Die in einer Zwischenschicht eines wärmeempfindlichen Aufzeichnungsmaterials angeordneten organischen 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.The inclusion of organic pigments, most preferably organic hollow body pigments, in the intermediate layer is justified by the fact that such organic pigments are beneficial to a very special extent high heat reflectivity of the intermediate layer and the heat reflectivity, in a weak extent even with an intermediate layer exclusively with given inorganic pigments, can increase significantly. The organic hollow body pigments disposed in an intermediate layer of a thermosensitive recording material have air inside thereof, 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.

Wird als Pigment in der Zwischenschicht eine Pigmentmischung aus anorganischen Pigmenten und organischen Hohlkörperpigmenten gewählt, ist das Mengenverhältnis zwischen organischem und anorganischem Pigment ein Kompromiss der von den beiden Pigmentarten bewirkten Effekte, der besonders vorteilhaft gelöst wird, wenn die Pigmentmischung zu 15 bis 50 Gew.-% bzw. besser zu 20 bis 50 Gew.-% aus organischem und zu 85 bis 50 Gew.-% bzw. besser zu 80 bis 50 Gew.-% aus anorganischem Pigment besteht. Ganz besonders bevorzugt ist es, wenn die Pigmentmischung zu 25 bis 40 Gew.-% aus organischem und zu 75 bis 60 Gew.-% aus anorganischem Pigment besteht.If a pigment mixture of inorganic pigments and organic hollow-body pigments is selected as the pigment in the intermediate layer, the quantitative ratio between organic and inorganic pigment is a compromise between the effects caused by the two types of pigment, which is achieved particularly advantageously if the pigment mixture contains 15 to 50% by weight. % or better to 20 to 50 wt .-% of organic and 85 to 50 wt .-% or better to 80 to 50 wt .-% of inorganic Pigment exists. It is very particularly preferred if the pigment mixture consists of 25 to 40% by weight of organic and 75 to 60% by weight of inorganic pigment.

Die organischen Hohlkörperpigmente weisen eine Wandung aus thermoplastischem Harz auf, der bevorzugt (Meth)Acrylnitril-Copolymer, Polyvinylchlorid, Polyvinylidenchlorid, Polystyrol, Styrolacrylat, Polyacrylnitril oder Polyacrylsäureester umfasst. Pigmentmischungen aus unterschiedlichen organischen Pigmenten sind vorstellbar. Eine Glasübergangstemperatur größer oder gleich 100°C und bevorzugt größer oder gleich 105°C wurde als vorteilhaft erkannt, weil unterhalb dieser Temperaturen ein erhöhter Vergilbungsgrad festgestellt wurde.The organic hollow body pigments have a wall of thermoplastic resin which preferably comprises (meth) acrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene acrylate, polyacrylonitrile or polyacrylic acid ester. Pigment mixtures of different organic pigments are conceivable. A glass transition temperature greater than or equal to 100 ° C and preferably greater than or equal to 105 ° C was found to be advantageous because below these temperatures, an increased degree of yellowing was detected.

Die Teilchengröße der organischen Hohlkörperpigmente in der Zwischenschicht liegt idealerweise in einem Bereich von 0,75 µm bis kleiner 1,5 µm, ganz besonders bevorzugt in einem Bereich von 0,9 µm bis 1,2 µm, liegt. Teilchengrößen unterhalb von 0,75 µm verbieten sich auf Grund rheologischer Verarbeitungsschwierigkeiten. Teilchengrößen oberhalb von 1,5 µm zeigen ein zu grobkörniges Verhalten und verhindern eine bevorzugte egalisierende Wirkung der Zwischenschicht. Für die anorganischen Pigmente empfiehlt sich besonders eine Teilchengröße von kleiner 2 µm, bestimmt als D50-Wert. Als vorteilhaft haben sich Pigmente erwiesen, bei denen eine Teilchengrößenverteilung von 34 bis 40 Gew.-% kleiner 1 µm und 57 bis 63 Gew.-% kleiner 2 µm vorliegt. Eine weitere geeignete Teilchengrößenverteilung ergibt sich, wenn 88 Gew.-% kleiner 1 µm sind. In Versuchen zeigte es sich als vorteilhaft, wenn das Verhältnis der Teilchengröße des organischen Pigments zur Teilchengröße des anorganischen Pigments in einem Bereich von 1 : 0,38 bis 1 : 1,5 liegt.The particle size of the organic hollow body pigments in the intermediate layer is ideally in a range from 0.75 μm to less than 1.5 μm, very particularly preferably in a range from 0.9 μm to 1.2 μm. Particle sizes below 0.75 microns prohibit due to rheological processing difficulties. Particle sizes above 1.5 microns show too coarse-grained behavior and prevent a preferred leveling effect of the intermediate layer. For the inorganic pigments, a particle size of less than 2 μm, determined as D 50 value, is particularly recommended. Pigments which have a particle size distribution of from 34 to 40% by weight of less than 1 μm and from 57 to 63% by weight of less than 2 μm have proved to be advantageous. Another suitable particle size distribution results when 88 wt .-% are less than 1 micron. In experiments, it has proved to be advantageous if the ratio of the particle size of the organic pigment to the particle size of the inorganic pigment is in a range from 1: 0.38 to 1: 1.5.

Die Zwischenschicht umfasst ferner ein oder mehrere Bindemittel ausgewählt aus der Gruppe umfassend Polyvinylalkohol, Styrol-Butadien-Latex, Stärke, CarboxyMethyl-Cellulose, Cellulosederivate, wobei besonders Styrol-Butadien-Latex bevorzugt ist. Bei Bindemittelmischungen besteht der Bindemittelanteil in der Zwischenschicht bevorzugt zu 69 bis 76 Gew.-% aus Styrol-Butadien-Latex.The intermediate layer further comprises one or more binders selected from the group consisting of polyvinyl alcohol, styrene-butadiene latex, starch, carboxymethyl cellulose, cellulose derivatives, styrene-butadiene latex being particularly preferred. For binder mixtures, the binder content in the intermediate layer preferably consists of 69 to 76 wt .-% of styrene-butadiene latex.

Ergänzend sei angemerkt, dass eine zwischen Substrat und wärmeempfindlicher Aufzeichnungsschicht positionierte Zwischenschicht einen positiven Beitrag zur Egalisierung der Substratschichtoberfläche leisten kann, womit sich die Menge an Druckfarbe für die wärmeempfindliche Aufzeichnungsschicht reduziert. Zum Auftrag der Zwischenschicht bieten sich insofern bevorzugt egalisierende Auftragswerke wie beispielsweise Rollrakel und Streichmesser bzw. -klinge an. Es ist auch möglich, die Zwischenschicht aufzudrucken, wobei hier das Flexodruckverfahren am wirtschaftlichsten ist, die besten Ergebnisse lieferte und des halb besonders bevorzugt ist.In addition, it should be noted that an intermediate layer positioned between the substrate and the heat-sensitive recording layer can positively contribute to the leveling of the substrate layer surface, thus reducing the amount of ink for the heat-sensitive recording layer. To order the intermediate layer offer so far preferably equalizing commissioned works such as Roller blade and doctor or blade on. It is also possible to print on the interlayer, in which case the flexographic printing process is the most economical, gives the best results and is particularly preferred.

Besonders vorteilhaft wirkt sich die Ausbildung der Zwischenschicht mit einer flächenbezogenen Masse in einem Bereich von 5 g/m2 bis 20 g/m2 und noch besser zwischen 7 g/m2 und 10 g/m2 aus.Particularly advantageous is the formation of the intermediate layer with a basis weight in a range of 5 g / m 2 to 20 g / m 2 and more preferably between 7 g / m 2 and 10 g / m 2 .

Die mindestens eine aufgedruckte wärmeempfindliche Aufzeichnungsschicht kann grundsätzlich alle bekannten Farbbildner sowie dazu im einzelnen passende Farbakzeptoren, insbesondere organische Farbakzeptoren beinhalten. Besonders bevorzugt sind als Farbbildner

  • 6'-(dipentylamino)-3'-methyl-2'-(phenylamino)-spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one sowie
  • Spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one-6'-(diethylamino)-3'-methyl-2'-(3-tolylamino)
und solche, ausgewählt aus der Gruppe der Fluoranverbindungen, wie insbesondere
  • 3-(Ethylisoamylamino)-6-methyl-7-anilinofluoran und
  • 3-Dibutylamino-6-methyl-7-anilinofluoran,
und dazu im einzelnen passende organische Farbakzeptoren, ausgewählt aus der Gruppe, umfassend
  • 2,2 bis (4-hydroxyphenyl)-propan,
  • 4-[(4-(1-methylethoxy)phenyl)sulfonyl]phenol,
  • 4,4'-dihydroxy-diphenylsulfon,
  • N-(p-toluensulphonyl)-N'-(3-p-toluensulphonyl-oxy-phenyl)-harnstoff,
  • 2,4'-dihydroxy-diphenylsulfon,
  • N-(2-hydroxyphenyl)-2-[(4-hydroxyphenyl)thio]acetamid,
freilich ohne auf die genannten Farbakzeptoren beschränkt zu sein. Für die Farbbildner empfiehlt sich eine mittlere Teilchengröße in einem Bereich von größer 0,3 µm bis maximal 1 µm, insbesondere von 0,45 µm bis 0,9 µm. Die Grenzen werden nach oben durch eine zu geringe Empfindlichkeit und nach unten durch eine sonst zu starke Neigung des wärmeempfindlichen Aufzeichnungsmaterials zur Vergrauung vorgegeben.The at least one printed heat-sensitive recording layer may in principle include all known color formers as well as in particular suitable color acceptors, in particular organic color acceptors. Particularly preferred are color formers
  • 6 '- (dipentylamino) -3'-methyl-2' - (phenylamino) -spiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one and
  • Spiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one 6' - (diethylamino) -3'-methyl-2 '- (3-tolylamino)
and those selected from the group of fluoran compounds, in particular
  • 3- (ethylisoamylamino) -6-methyl-7-anilinofluoran and
  • 3-dibutylamino-6-methyl-7-anilinofluoran,
and in particular, suitable organic color acceptors selected from the group comprising
  • 2,2 bis (4-hydroxyphenyl) -propane,
  • 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol,
  • 4,4'-dihydroxy-diphenylsulfone,
  • N- (p-toluensulphonyl) -N '- (3-p-toluensulphonyl-oxy-phenyl) -urea,
  • 2,4'-dihydroxy-diphenyl sulfone,
  • N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] acetamide,
Of course, without being limited to the color acceptors mentioned. For the color formers, an average particle size in a range from greater than 0.3 μm to a maximum of 1 μm, in particular from 0.45 μm to 0.9 μm, is recommended. The limits are given upwards by a too low sensitivity and down by an otherwise too strong inclination of the heat-sensitive recording material for graying.

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 und Diphenylsulfon, 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 and diphenyl sulfone, 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, die allein oder in Kombination untereinander eingesetzt werden können; auch wasserunlösliche Latexbinder wie Styrol-Butadiene-Copolymere, Acrylnitril-Butadien-Copolymere und Methyl-Acrylat-Butadien-Copolymere 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 which can be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers 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 oder Kalziumstearat; Wachse, zum Beispiel Paraffin, oxidiertes Paraffin, Polyethylen, Polyethylenoxid, Stearamide und Kastorwachs. 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. Im Sinne der vorliegenden Erfindung gilt in der mindestens einen aufgedruckten wärmeempfindlichen Aufzeichnungsschicht ein Bindemittel-Pigment-Verhältnis zwischen 2 : 1 und 1 : 1 und insbesondere zwischen 1,8 : 1 und 1,2 : 1 als besonders bevorzugt.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 or calcium stearate; Waxes, for example paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides and castor wax. Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 18% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred. For the purposes of the present invention, a binder-to-pigment ratio of between 2: 1 and 1: 1 and in particular between 1.8: 1 and 1.2: 1 is particularly preferred in the at least one printed heat-sensitive recording layer.

Zur Ausbildung der mindestens einen aufgedruckten wärmeempfindlichen Aufzeichnungsschicht können alle möglichen Druckverfahren des Analogdrucks benutzt werden. Dabei werden als Analogdruck im Sinne dieser Erfindung alle Druckverfahren bezeichnet, die mit Druckplatte bzw. -zylinder arbeiten, wozu Tiefdruck, Siebdruck, Offsetdruck und in einer ganz besonders bevorzugten Ausführung Flexodruck gehört. Aus Gründen großer Praktikabilität sollen die Druckfarben zur Ausbildung der mindestens einen aufgedruckten wärmeempfindlichen Aufzeichnungsschicht UV-vernetzend sein. Im Sinne der vorliegenden Erfindung soll die mindestens eine wärmeempfindliche Aufzeichnungsschicht bevorzugt direkt auf die Zwischenschicht aufgedruckt sein. Alternativ vorstellbar ist es aber auch, zwischen der mindestens einen wärmeempfindlichen Aufzeichnungsschicht und der Zwischenschicht eine Membranschicht, beispielsweise zur Haftungsverbesserung, auszubilden.To form the at least one printed heat-sensitive recording layer, all possible printing methods of the analog printing can be used. Here are referred to as analog printing in the context of this invention, all printing processes that work with printing plate or cylinder, including gravure, screen printing, offset printing and in a very particularly preferred embodiment flexographic belongs. For reasons of great practicability, the printing inks for forming the at least one printed heat-sensitive recording layer should be UV-crosslinking. For the purposes of the present invention, the at least one heat-sensitive recording layer should preferably be printed directly onto the intermediate layer. Alternatively, it is also conceivable to form a membrane layer between the at least one heat-sensitive recording layer and the intermediate layer, for example to improve the adhesion.

Erfindungsgemäß wird die mindestens eine aufgedruckte wärmeempfindliche Aufzeichnungsschicht in Form geometrischer, musterartiger und/oder alphanumerischer Figuren aufgebracht. Das soll bedeuten, das die mindestens eine aufgedruckte wärmeempfindliche Aufzeichnungsschicht in Form

  • von Rechtecken entsprechend zuvor entworfener Formulare,
  • von Barcode-Darstellungen und
  • von Buchstaben beispielsweise zur Darstellung einer Verwendung und/oder als Authentifikationsnachweis
ausgebracht sein kann, ohne auf die genannten Formen beschränkt zu sein.According to the invention, the at least one printed heat-sensitive recording layer is applied in the form of geometric, pattern-like and / or alphanumeric figures. This should mean that the at least one printed heat-sensitive recording layer in the form
  • rectangles according to previously designed forms,
  • of barcode representations and
  • of letters, for example, for representing a use and / or as proof of authentication
can be applied without being restricted to the forms mentioned above.

Optional weist das erfindungsgemäße Aufzeichnungsmaterial weitere Aufzeichnungsschichten in Form geometrischer, musterartiger und/oder alphanumerischer Figuren auf, wobei auch diese weiteren Aufzeichnungsschichten in Form

  • von Rechtecken entsprechend zuvor entworfener Formulare,
  • von Barcode-Darstellungen und
  • von Buchstaben beispielsweise zur Darstellung einer Verwendung und/oder als Authentifikationsnachweis
ausgebracht sein können.Optionally, the recording material according to the invention has further recording layers in the form of geometric, pattern-like and / or alphanumeric figures, whereby these further recording layers also have a shape
  • rectangles according to previously designed forms,
  • of barcode representations and
  • of letters, for example, for representing a use and / or as proof of authentication
can be applied.

In einer ganz besonders bevorzugten Ausführungsform sind auch die weiteren Aufzeichnungsschichten wärmeempfindlich. In diesem Fall sollen sie bevorzugt die Sensibilisatoren, Bindemittel, Pigmente, Gleit- und Trennmittel enthalten, die auch für die mindestens eine aufgedruckte wärmeempfindliche Aufzeichnungsschicht bevorzugt sind.In a very particularly preferred embodiment, the other recording layers are also sensitive to heat. In this case, they should preferably contain the sensitizers, binders, pigments, lubricants and release agents which are also preferred for the at least one heat-sensitive recording layer printed on.

Die laut bevorzugter Ausführungsform wärmeempfindlichen weiteren Aufzeichnungsschichten weisen als Farbbildner mindestens eine Substanz auf, 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 further recording layers according to the preferred embodiment have as color formers at least one substance selected from the group of known from the prior art phthalide, xanthene, fluoran, triarylmethane, diphenylmethane, fluorene, oxazine, thiazine or Spiropyran compounds, with 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-Diethyl-amino-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-anilinofluoran, 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-anilinofluoran, 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-Dimethylamino-phenyl-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-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylamino-phenyl-3 (1-methylpyrrol-2-yl) 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-dichloro-spirodinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)spiropyran, 3-propyl-spiro-benzopyran, etc.3-methylspiro-dinaphthopyran, 3-ethylspiro-dinaphthopyran, 3,3-dichloro-spirodinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho (3-methoxy-benzo) spiropyran, 3-propyl-spiro-benzopyran, etc ,

Weiterhin können die weiteren Aufzeichnungsschichten beispielsweise auch eine oder mehrere der folgenden, im nahen Infrarot-Bereich absorbierenden Verbindungen enthalten:Furthermore, the further recording layers may 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-(di-ethylamino)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-dimethylaminophenyl)-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 (di-ethylamino) 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-dimethylaminophenyl) -2- (4-methoxyphenyl) -ethenyl] -4,5,6,7-tetrachlorophthalide, etc.

Als ganz besonders bevorzugte Farbbildner für die weiteren Aufzeichnungsschichten 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 for the further recording layers 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.

Es bleibt also festzuhalten, dass die weiteren Aufzeichnungsschichten bevorzugt solche sind, die unter der Einwirkung von Hitze farbbildend sind. Ganz besonders bevorzugt sind dabei solche Ausführungsformen, bei denen die in den weiteren Aufzeichnungsschichten ausgebildeten Farben unterschiedlich sind zu der Farbe, die in der mindestens einen aufgedruckten wärmeempfindlichen Aufzeichnungsschicht unter der Einwirkung von Hitze entsteht.It is therefore to be noted that the further recording layers are preferably those which are color-forming under the influence of heat. Very particular preference is given to those embodiments in which the colors formed in the further recording layers are different from the color which arises in the at least one printed heat-sensitive recording layer under the action of heat.

In einer weiteren und genauso bevorzugten Ausführungsform im Sinne der vorliegenden Erfindung weisen die weiteren Aufzeichnungsschichten eingekapselte Farbbildner und/oder Farbakzeptoren auf. Diese Kapseln, bzw. so genannte Mikrokapseln, sind so gestaltet, dass sie unter dem Einfluss von Druck oder von Wärme aufbrechen und so die eingekapselten Farbbildner und/oder Farbakzeptoren freigeben. Insofern sind die weiteren Aufzeichnungsschichten als druckempfindliche oder auch als wärmeempfindliche Aufzeichnungsschichten ausgebildet.In a further and equally preferred embodiment according to the present invention, the further recording layers comprise encapsulated color formers and / or color acceptors. These capsules, or so-called microcapsules, are designed so that they break under the influence of pressure or heat, thus releasing the encapsulated color formers and / or dye acceptors. In this respect, the further recording layers are formed as pressure-sensitive or else as heat-sensitive recording layers.

Die nicht durch die eine oder mehrere Aufzeichnungsschichten bedeckten Bereiche der pigmentierten Zwischenschicht sind erfindungsgemäß durch eine nicht-farbbildende Druckschicht abgedeckt. Dabei gilt es als bevorzugt, wenn sowohl alle Aufzeichnungsschichten wie auch die nicht farbbildende Druckschicht durch das gleiche Druckverfahren, besonders bevorzugt innerhalb des gleichen Durchlaufs durch eine einzige Druckmaschine ausgebildet werden. Dabei gelten Tiefdruck, Offsetdruck oder Flexodruck als die sich in einem besonderen Maße anbietenden Druckverfahren.The regions of the pigmented intermediate layer which are not covered by the one or more recording layers are covered by a non-color-forming printing layer according to the invention. It is considered preferable if both all the recording layers and also the non-color-forming printing layer are formed by the same printing method, particularly preferably within the same pass through a single printing press. Gravure printing, offset printing or flexographic printing are considered to be the printing process offering a particular degree.

Die nicht-farbbildende Druckschicht wird besonders bevorzugt mit den exakt gleichen, nicht für die Farbbildung notwendigen, Komponenten in den jeweils gleichen Mengenverhältnissen zueinander ausgebildet wie die mindestens eine aufgedruckte wärmeempfindliche Aufzeichnungsschicht. In diesem Sinne weist die nicht-farbbildende Druckschicht 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 auf, die allein oder in Kombination untereinander eingesetzt werden können; auch wasserunlösliche Latexbinder wie Styrol-Butadiene-Copolymere, Acrylnitril-Butadien-Copolymere und Methyl-Acrylat-Butadien-Copolymere bieten sich als Bindemittel zur Einbindung in die nicht-farbbildende Druckschicht 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 nicht-farbbildende Druckschicht, in einem Bereich von 12 bis 25 Gew.-% (atro), bevorzugt in einem Bereich von 18 bis 22 Gew.-% (atro) in die nicht-farbbildende Druckschicht eingebunden sind.The non-color-forming printing layer is particularly preferably formed with the exact same, not necessary for the color formation, components in the same quantitative proportions to each other as the at least one printed heat-sensitive recording layer. In this sense, the non-color-forming printing layer comprises 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, which can be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the non-color-forming printing layer. For the purposes of the present invention, polyvinyl alcohol, alone and / or in combination with acrylate copolymers and / or in combination with methyl cellulose, are considered to be particularly preferred binders which together in a range of 12, based on the total weight (atro) of the non-color-forming printing layer to 25 wt .-% (atro), preferably in a range of 18 to 22 wt .-% (atro) are incorporated into the non-color-forming printing layer.

Weitere Bestandteile der nicht-farbbildenden Druckschicht 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 nicht-farbbildenden Druckschicht, in die nicht-farbbildende Druckschicht eingebunden sein soll, als bevorzugt gilt. Im Sinne der vorliegenden Erfindung gilt in der nicht-farbbildende Druckschicht ein Bindemittel-Pigment-Verhältnis zwischen 2 : 1 und 1 : 1 und insbesondere zwischen 1,8 : 1 und 1,2 : 1 als besonders bevorzugt.Further constituents of the non-color-forming printing layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 18% by weight, based on the total weight of the non-color-forming printing layer to be incorporated in the non-color-forming printing layer, is considered preferable. For the purposes of the present invention, a binder-to-pigment ratio of between 2: 1 and 1: 1 and in particular between 1.8: 1 and 1.2: 1 is particularly preferred in the non-color-forming printing layer.

Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial kann eine die mindestens eine aufgedruckte wärmeempfindliche Aufzeichnungsschicht, die optionalen weitere Aufzeichnungsschichten sowie die nicht-farbbildende Druckschicht gemeinsam überdeckende Schutzschicht aufweisen. Eine solche Schutzschicht ist in diesem Fall bevorzugt aus einer nicht wässerigen Phase aufgedruckt und bevorzugt unter Einfluss von energiereicher Strahlung vernetzbar. Dabei enthält die Schutzschicht ganz besonders bevorzugt

  • ■ zu 65 bis 95 Gew.-% ein oder mehrere (Meth)acrylate, ausgewählt aus der Gruppe umfassend Polyether(meth)acrylat, Epoxy(meth)acrylat sowie Urethan(meth)acrylat,
  • ■ zu 0 bis 20 Gew.-% Photoinitiatoren und
  • ■ zu 0,5 bis 20 Gew.-% Wachs,
wobei mindestens ein (Meth)acrylat der genannten Gruppe ein aminmodifiziertes (Meth)acrylat ist und wobei sich die Gew.-%-Angaben zu 65,5 bis 100 Gew.-% der Schutzschicht addieren,The heat-sensitive recording material of the present invention may have a protective layer co-covering the at least one printed heat-sensitive recording layer, the optional further recording layers and the non-color-forming printing layer. Such a protective layer is preferably printed in this case from a non-aqueous phase and preferably crosslinkable under the influence of high-energy radiation. The protective layer very particularly preferably contains
  • At 65% to 95% by weight of one or more (meth) acrylates selected from the group comprising polyether (meth) acrylate, epoxy (meth) acrylate and urethane (meth) acrylate,
  • ■ to 0 to 20 wt .-% of photoinitiators and
  • ■ from 0.5 to 20% by weight of wax,
wherein at least one (meth) acrylate of said group is an amine-modified (meth) acrylate, and wherein the wt .-% information adds to 65.5 to 100 wt .-% of the protective layer,

Zur Vernetzung der Schutzschicht bieten sich insbesondere UV- und Elektronenstrahlung an, wobei UV-Strahlung besonders bevorzugt ist. In diesem Fall enthält die Schutzschicht Photoinitiatoren in einem Bereich von 2 bis 20 Gew.-% und die Gew.-%-Angaben für die ein oder mehrere (Meth)acrylate, Photoinitiatoren und Wachs addieren sich zu 67,5 bis 100 Gew.-% der Schutzschicht.UV and electron radiation are particularly suitable for crosslinking the protective layer, with UV radiation being particularly preferred. In this case, the protective layer contains photoinitiators in a range from 2 to 20% by weight and the weight% data for the one or more (meth) acrylates, photoinitiators and wax add up to 67.5 to 100% by weight. % of the protective layer.

Beispiele für die (Meth)acrylate gemäß der vorgeschlagenen Schutzschicht bzw. Zusammensetzung für die Schutzschicht sind Dipentaerythritolpenta(meth)acrylat und finden sich beispielsweise in den Literaturstellen US 4,485,123 und EP 0 209 684 A1 . Als aminmodifiziertes (Meth)acrylat wird bevorzugt aminmodifiziertes Polyether-acrylat eingesetzt.Examples of the (meth) acrylates according to the proposed protective layer or composition for the protective layer are dipentaerythritol penta (meth) acrylate and can be found, for example, in the literature US 4,485,123 and EP 0 209 684 A1 , The amine-modified (meth) acrylate used is preferably amine-modified polyether acrylate.

Als Photoinitiatoren können solche eingesetzt werden, welche die Härtung bzw. radikalische Polymerisation unter Anwendung von UV-Strahlung initiieren und beispielsweise im Wellenbereich von 190 bis 400 nm absorbieren. Derartige Photoinitiatoren sind beispielsweise chlorhaltige Photoinitiatoren, aromatische Ketone, Hydro-Xyalkylphenone, Phosphinoxide. Bevorzugte Photoinitiatoren sind Benzophenonderivate, Phenylketone und Phenyolphosphenate.As photoinitiators, it is possible to use those which initiate the curing or radical polymerization by using UV radiation and absorb, for example, in the wavelength range from 190 to 400 nm. Such photoinitiators are, for example, chlorine-containing photoinitiators, aromatic ketones, hydroxyphenylphenones, phosphine oxides. Preferred photoinitiators are benzophenone derivatives, phenyl ketones and phenol phosphenates.

Als Wachse sind bspw. Polyethylenwachse, wie beispielsweise PTFEmodifiziertes Polyethylenwachs verwendbar.As waxes, for example, polyethylene waxes, such as PTFE-modified polyethylene wax used.

Die Schutzschicht kann mit nur einer Auftragsebene aufgetragen sein, wobei dann eine flächenbezogenen Masse der Schutzschicht in einem Bereich von 0,5 bis 4,5 g/m2 besonders geeignet ist. Bei auch möglichen zwei oder mehr Auftragsebenen liegt die flächenbezogene Masse der gesamten Schutzschicht bevorzugt in einem Bereich von 1,2 bis 6 g/m2 und besonders bevorzugt zwischen 1,5 und 4 g/m2.The protective layer can be applied with only one application level, in which case a surface-related mass of the protective layer in a range from 0.5 to 4.5 g / m 2 is particularly suitable. With possible two or more application levels, the basis weight of the entire protective layer is preferably in a range from 1.2 to 6 g / m 2 and more preferably between 1.5 and 4 g / m 2 .

Als Substrat wird gemäß einer ersten Alternativform Papier und ganz besonders ein nicht oberflächenbehandeltes Streichrohpapier bevorzugt, ohne dass die Erfindung auf ein solches Substrat beschränkt ist. Unter einem nicht oberflächenbehandelten Streichrohpapier ist ein nicht in einer Leimpresse oder Streichvorrichtung behandeltes Streichrohpapier zu verstehen. Im Rahmen dieser ersten Alternativform gilt es als besonders bevorzugt, wenn die pigmentierte Zwischenschicht auf das Substrat unter Verwendung eines Streichaggregats, wie die zuvor bereits offenbarten Rollrakel und Streichmesser bzw. -klinge, aufgebracht ist.As a substrate according to a first alternative form, paper, and more particularly a non-surface treated base paper, is preferred, without the invention being restricted to such a substrate. A non-surface treated base paper is to be understood as meaning a base paper not treated in a size press or coater. In the context of this first alternative form, it is particularly preferred if the pigmented intermediate layer is applied to the substrate using a coating unit, such as the previously disclosed roller blade and doctor or blade, is applied.

Für die Erfindung sind im gleichen Maße auch mit Polyolefin beschichtete Papiere als Substrat möglich.For the invention, papers coated with polyolefin are equally possible as a substrate.

Gemäß einer zweiten Alternativform wird als Substrat eine Folie bevorzugt, wobei ganz besonders bevorzugt solche Folien sind, ausgesucht aus der Liste, umfassend Polyethylenfolie, Polypropylenfolie und insbesondere Polyesterfolie, die sich in einem besonderen Maße wegen guter Verarbeitungsvorteile anbietet. Sofern Folie als Substrat für die vorliegende Erfindung zum Einsatz kommt, ist deren vorherige Corronabehandlung notwendig. Im Rahmen dieser zweiten Alternativform gilt es als besonders bevorzugt, wenn die pigmentierte Zwischenschicht auf das Substrat aufgedruckt ist.According to a second alternative form, a film is preferred as the substrate, with very particular preference being given to those films selected from the list comprising polyethylene film, polypropylene film and, in particular, polyester film which offers itself to a particular extent for good processing advantages. If film is used as the substrate for the present invention, its previous corona treatment is necessary. In the context of this second alternative form, it is particularly preferred if the pigmented intermediate layer is printed on the substrate.

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.

Claims (10)

  1. Heat-sensitive recording material having
    □ a substrate,
    □ an intermediate layer covering over the entire area of at least one side of the substrate,
    □ at least one printed-on, heat-sensitive recording layer comprising colour formers and colour acceptors,
    the at least one printed-on, heat-sensitive recording layer having been applied in the form of geometric, pattern-like and/or alphanumeric elements,
    characterised in that
    ■ optionally further recording layers have been applied in the form of geometric, pattern-like and/or alphanumeric elements,
    ■ the intermediate layer is pigmented,
    ■ those areas of the pigmented intermediate layer which are not covered by the one or more recording layers have been covered over by a non-colour-forming print layer.
  2. Heat-sensitive recording material according to patent claim 1, characterised in that the intermediate layer comprises a pigment mixture of inorganic and organic pigment.
  3. Heat-sensitive recording material according to one of patent claims 1 or 2, characterised in that the at least one printed-on recording layer has a colour former selected from the list comprising 6'-(dipentylamino)-3'-methyl-2'-(phenylamino)-spiro[isobenzofuran-1 (3H),9'-[9H]xanthen]-3-one, spiro[isobenzofuran-1 (3H),9'-[9H]xanthen]-3-one-6'-(diethylamino)-3'-methyl-2'-(3-tolylamino), 3-(ethylisoamylamino)-6-methyl-7-anilinofluoran and 3-dibutylamino-6-methyl-7-anilinofluoran.
  4. Heat-sensitive recording material according to one of patent claims 1 to 3, characterised in that the at least one printed-on recording layer has a colour acceptor selected from the list comprising 2,2-bis(4-hydroxyphenyl)propane, 4-[(4-(1-methylethoxy)phenyl)sulfonyl]phenol, 4,4'-dihydroxydiphenyl sulfone, N-(p-toluenesulfonyl)-N'-(3-p-toluenesulfonyl-oxy-phenyl)urea, 2,4'-dihydroxydiphenyl sulfone, N-(2-hydroxyphenyl)-2-[(4-hydroxyphenyl)thio]acetamide.
  5. Heat-sensitive recording material according to one of patent claims 1 to 4, characterised in that the further recording layers are heat-sensitive.
  6. Heat-sensitive recording material according to patent claim 5, characterised in that the colours formed in the further recording layers under the action of heat are different to the colour produced in the at least one printed-on, heat-sensitive recording layer under the action of heat.
  7. Heat-sensitive recording material according to one of patent claims 1 to 4, characterised in that the further recording layers are pressure-sensitive.
  8. Heat-sensitive recording material according to one of patent claims 1 to 7, characterised in that the substrate is a non-surface-treated coating base paper.
  9. Heat-sensitive recording material according to one of patent claims 1 to 7, characterised in that the substrate is a polyester film.
  10. Heat-sensitive recording material according to one of patent claims 1 to 9, characterised in that the recording material furthermore has a protective layer jointly covering over
    - the at least one printed-on, heat-sensitive recording layer,
    - the optional further recording layers, and also
    - the non-colour-forming print layer.
EP09164951A 2008-10-13 2009-07-08 Heat-sensitive recording material with printed recording layer Active EP2174794B1 (en)

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US4485123A (en) 1982-02-12 1984-11-27 Union Carbide Corporation Process for producing textured coatings
DE3526016A1 (en) 1985-07-20 1987-01-22 Huels Chemische Werke Ag STORAGE-STABLE, RADIATION-HARDENABLE, NCO-FREE, AQUEOUS EMULSIONS
US5984363A (en) 1993-05-03 1999-11-16 The Standard Register Company Business record having a thermally imagable surface
DE19912054A1 (en) 1999-03-18 2000-09-21 Inst Oberflaechenmodifizierung Printing and laminating of flexible materials is carried out in a continuous process, by using ink and adhesives that can be hardened by UV radiation
US6881915B2 (en) * 2001-01-31 2005-04-19 Spectra Systems Corporation Contrast enhancing marking system for application of unobtrusive identification and other markings

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