EP1527900B1 - Thermosensitive recording material, its' use and its' method of preparation. - Google Patents

Thermosensitive recording material, its' use and its' method of preparation. Download PDF

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Publication number
EP1527900B1
EP1527900B1 EP04025536A EP04025536A EP1527900B1 EP 1527900 B1 EP1527900 B1 EP 1527900B1 EP 04025536 A EP04025536 A EP 04025536A EP 04025536 A EP04025536 A EP 04025536A EP 1527900 B1 EP1527900 B1 EP 1527900B1
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EP
European Patent Office
Prior art keywords
recording material
material according
recording
calcium carbonate
layer
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EP04025536A
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German (de)
French (fr)
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EP1527900A1 (en
Inventor
Wolfgang Dr. Wagner
Gerhard Dr. Stork
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Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
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Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
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Priority to PL04025536T priority Critical patent/PL1527900T3/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
    • 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
    • B41M5/30—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
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids

Definitions

  • the present invention relates to a recording material having a substrate and a heat-sensitive recording layer as the outer uppermost layer.
  • the heat-sensitive recording layer contains calcium carbonate and binder one or more dye precursors and a compound from the group of Np-toluenesulfonyl-N '- (3-ptoluenesulfonyloxy-phenyl) ureas, which as a developer under the influence of heat, a color-forming reaction with the or the dye precursor (s) is received.
  • the invention further relates to the use of the recording material according to the invention and to a process for its preparation.
  • EP 1 321 306 A2 proposes a very slit-resistant coating structure Adjustment of a specific wetting ability on the surface of the heat-sensitive recording material. This wettability is described by a surface tension with a minimum contact angle of 20 ° when using distilled water.
  • the known recording material preferably has a protective layer in view of the underlying object mandatory crosslinking and bonding agents in the near-surface layer on.
  • EP-A-1 208 994 discloses, for a heat-sensitive recording layer, the combination of developers of the named group with one or more pigments selected from the group consisting of aluminum hydroxide, amorphous silica, kaolin and talc.
  • the objectives of this document are the resistance to water, heat, light and plasticizer and a high recording sensitivity. According to the examples of this document, since the recording layer is covered with a protective layer which increases the manufacturing cost, the results obtained indicate that the resistance to environmental influences is not yet fully satisfactory.
  • the object of the present invention is to provide a heat-sensitive recording material which has a simple structure and can be produced at low production costs.
  • the new recording material should require no additional protective layer to cover the recording layer, but nevertheless have a high storage stability of both the recording material itself and the generated typeface and ensure good contrast between the typeface and unlabeled recording layer.
  • the labeled recording material should have good resistance to substances such as fatliquoring agents, waxes, (poly) glycols and polypropylene derivatives commonly used in leather used for making purses, wallets and slip-in cases for driver's licenses.
  • substances such as fatliquoring agents, waxes, (poly) glycols and polypropylene derivatives commonly used in leather used for making purses, wallets and slip-in cases for driver's licenses.
  • thermosensitive recording material which can be used to issue receipts such as parking tickets, receipts, guarantee documents and receipts at a cash register with a thermal printer installed therein.
  • the invention also seeks to provide a method which enables a simple and inexpensive production of the recording material according to the invention.
  • the good resistance for example, to the substances used in the production of leather, which, when storing, for example, wallet and wallet receipts, on the thermal-printed recording material, is explained by: that the anionic group in the developer molecule greatly influences the surface electrochemical character of the developer. This bonds the polar groups and reduces the polar component of the surface tension. The inventors recognized that this effect is more pronounced when there are increased amounts of calcium carbonate particles in the environment of the developer. The best results in relation to the task result when the ratio of calcium carbonate to binder in the recording layer also containing the developer and one or more dye precursors is in the range of 1.8: 1 to 3.3: 1 according to the invention.
  • a ratio of calcium carbonate to binder in a range of 2.2: 1 to 3.2: 1 has been found to be suitable.
  • the statements made here in the description as well as in the claims concerning the ratio of calcium carbonate to binder in each case refer to the "atro" weight, which means to absolutely dry parts by weight.
  • the calcium carbonate present in the recording layer is precipitated calcium carbonate.
  • the calcium carbonate has an average particle size of 0.20 ⁇ m ⁇ rounding convention, ie the range from 0.15 ⁇ m to 0.24 ⁇ m, and a specific surface area (BET) according to DIN 66132 of 10 m 2 / g ⁇ rounding convention, which has the range from 5 m 2 / g to 14 m 2 / g.
  • BET specific surface area
  • binders starch cellulose derivatives such as CMC and plastic dispersions based on acrylate, butadiene styrene, polyvinyl acetate alone or in admixture in the recording layer.
  • polyvinyl alcohol is suitable alone or in admixture with other binders.
  • it is partially or completely saponified polyvinyl alcohol, which is incorporated alone, in combination with other polyvinyl alcohols or in general with other binders in the heat-sensitive recording layer.
  • the recording layer can be present with a relatively low coating thickness, namely with a basis weight of 2.0 to 3.8 g / m 2 , in particular with a basis weight ⁇ 3.3 g / m 2 , wherein the statements made here in the description as well as in the claims relating to the surface masses of the recording layer in each case on the "atro" weight, which means to absolutely dry parts by weight, relate.
  • a relatively low coating thickness namely with a basis weight of 2.0 to 3.8 g / m 2 , in particular with a basis weight ⁇ 3.3 g / m 2
  • curtain coaters or leveling commissioned works of knife and roller doctor type are used.
  • a flat recording layer is effected which can not cause any interference with the passage of the thermal head during the thermal printing process.
  • the coating color used to form the thermosensitive recording layer is aqueous.
  • the subsequent drying of the coating color can be done by means of microwave irradiation.
  • heat is supplied, as is done by hot-air floatation dryer or contact dryer, such as drying cylinders.
  • contact dryer such as drying cylinders.
  • a combination of the listed dry processes is also conceivable.
  • an intermediate layer containing a binder and an oil-absorbing pigment is suitably disposed between the recording layer and the substrate of the recording material of the present invention.
  • an oil-absorbing pigment is suitably disposed.
  • the pigments of the intermediate layer in addition to the inorganic oil-absorbing pigments selected from the group comprising natural and calcined kaolin, silicon (di) oxide, bentonite, calcium carbonate and aluminum (di) oxide and, in particular, boehmite, organic hollow-wall pigments have proved to be preferred, the pigments can be used individually as well as in combination with each other.
  • such an intermediate layer can make a positive contribution to equalization of the substrate surface, whereby the amount of coating color necessarily to be applied for the heat-sensitive recording layer is further reduced to a preferred range of 1.0 to 3.0 g / m 2 .
  • the pigments of this intermediate layer can absorb the heat-liquefied wax components of the thermosensitive recording layer in the typeface formation, thus promoting a safe and rapid operation of the heat-induced recording.
  • the preferred intermediate layer also comprises at least one oil or wax-absorbing pigment.
  • the basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 10 g / m 2 (atro).
  • a paper web is particularly suitable, although the invention is not limited to paper as a substrate.
  • the paper web on the side opposite to the side with the recording layer may be provided with a preparation preferably based on starch, which is ideally applied in a range of 0.1 to 0.5 g / m 2 .
  • the recording material has, at least on its side provided with the recording layer, a Bekkglätte of 400 to 1000 sec.
  • the recording material preferably has a whiteness in a range of 90 to 98% as measured by ISO 2469 / ISO 2470, but D65 light is used at an observation angle of 8 °.
  • the recording material according to the invention is particularly suitable for issuing receipts, in particular for producing receipts and guarantee certificates on a cash register equipped with a thermal printer.
  • the simple structure of the recording material without protective layer and the consequently cost-effective manufacturability of considerable advantage is particularly suitable for issuing receipts, in particular for producing receipts and guarantee certificates on a cash register equipped with a thermal printer.
  • a suitable method for producing the recording material according to the invention in one of its possible embodiments initially comprises the provision of a substrate.
  • a paper web which has a surface-related mass in a range from 40 to 75 g / m 2 (atro) is particularly suitable for this purpose.
  • the components of the paper web are not restricted within the meaning of the invention, but on the one hand, in particular, a polyolefin-coated base paper or a base paper sized with an applied intermediate layer in a flattened design is recommended.
  • the base paper usually bleached and ground pulps in addition to the usual admixtures such as retention centers preferably resin glue in a range of 0.3 to 1.2 wt .-% (atro) and more preferably from 0.45 to 0.9 Wt .-% (atro), based on the solids weight of the base paper on.
  • the intermediate layer In addition to binders, there are primarily one or more inorganic oil absorption pigments and, optionally, organic voiding pigments which are then capable of reflecting heat from the thermal head for printing image formation in the recording layer, which has first penetrated the recording layer, back to the recording layer , Such ability of the cavity pigments in the intermediate layer contributes to better efficiency of the thermosensitive recording material.
  • the application of the intermediate layer is usually done with a leveling coating, as it represents, for example, a roller coater, a doctor blade or (roll) doctor blade.
  • the basis weight with which the recording layer is applied should preferably be in a range of 2.0 to 3.8 g / m 2 or less than or equal to 3.3 g / m 2 and most preferably in a range of 2, 0 to 3.3 g / m 2 (atro).
  • the recording layer is preferably applied with a curtain coater, a doctor blade or a rotary doctor applicator.
  • the subsequent drying is preferably done with a Heated hot air dryer in combination with drying cylinders, between which the formed recording material is performed meandering. Between heated air-suspended dryer and drying cylinders, the recording material can be moistened again on one or both sides. This moistening can be done with a steam box or by means of moistening cylinders or applicators.
  • both calender and calender each comprise a plurality of nips, in which the rollers for setting a suitable friction with each other and also with respect to the recording material carried through may have different speeds.
  • a substrate web is made of bleached and ground hardwood and softwood pulps with the addition of 0.6% by weight (atro) rosin size as engine sizing and other typical admixtures, based on the solids content (atro) of the substrate web, with a basis weight of (A) g / m 2 produced.
  • a calcined kaolin pigment, styrene-butadiene latex binder and starch co-binder is applied to the respective substrate webs of Examples 1 and 2 in addition to further auxiliary agents having a basis weight of 9 g / m 2 ;
  • the backing paper is provided with a starch preparation having a basis weight of 0.2 g / m 2 .
  • a heat-sensitive recording layer with a basis weight of (C) g / m 2 with the composition to be taken from Table 1 is applied by means of a coating device (B), all data being understood as parts by weight.
  • the paper web After drying the coating composition, the paper web is treated on a supercalender so that the heat-sensitive recording layer has a Bekkglätte of (D) sec.
  • the Bekkglätte is determined by the method specified in DIN 53107. For details of the measuring method, reference is made to DE 100 14 351 A1 .
  • a thermal print-out is made with a Atlantek 400 instrument from Atlantek (USA) and the print density is measured with the Gretag MacBeth TYPE D19C NB / U densitometer (Gretag MacBeth, 8105 Regensdorf, Switzerland). It was determined with a thermal head with 300 dpi at 11mJ / mm 2, a print density of (E).
  • the measurement of the surface tension was carried out with a device of the type DSA10 MK2 from KRÜSS GmbH (Hamburg). A polar fraction of the surface tension of (Y) in mN / m and a ratio of the disperse part to the polar part of the surface tension of (Z) were determined.
  • the heat-sensitive recording materials according to the invention produced in the context of Examples 1 to 3 have the required However, a simple structure, but nevertheless have a high storage stability of both the recording material itself and the generated typeface and ensure a good contrast between typeface and unlabeled recording layer. Furthermore, the recording materials according to the invention are characterized by good resistance to substances such as fatliquors, waxes, (poly) glycols and polypropylene derivatives, as are commonly used in leather for purses and wallets.

Abstract

In recording material with substrate (A) and heat-sensitive layer (B) containing dye precursor(s) (I), N-p-toluenesulfonyl-N'-(3-p-toluenesulfonyloxyphenyl)urea compound (II) as developer for (I) on heating, calcium carbonate (III) and binder (IV), the novel features are that (B) has polar component of surface tension of 5-9.5 mN/m by Owens-Wendt method and ratio of disperse:polar components of (3.5-7.0):1; (III):(IV) ratio is (1.8-3.3):1; and (III) is only pigment in (B). An independent claim is also included for production of this material.

Description

Die vorliegende Erfindung betrifft ein Aufzeichnungsmaterial mit einem Substrat und einer wärmeempfindlichen Aufzeichnungsschicht als nach außen abschließende obere Schicht. Dabei enthält die wärmeempfindliche Aufzeichnungsschicht neben Calciumcarbonat und Bindemittel einen oder mehrere Farbstoffvorläufer sowie eine Verbindung aus der Gruppe der N-p-toluenesulfonyl-N'-(3-ptoluenesulfonyloxy-phenyl)-Harnstoffe, die als Entwickler unter dem Einfluss von Wärme eine farbbildende Reaktion mit dem oder den Farbstoffvorläufer(n) eingeht.
Die Erfindung betrifft ferner die Verwendung des erfindungsgemäßen Aufzeichnungsmaterials und ein Verfahren zu seiner Herstellung.The present invention relates to a recording material having a substrate and a heat-sensitive recording layer as the outer uppermost layer. In this case, the heat-sensitive recording layer contains calcium carbonate and binder one or more dye precursors and a compound from the group of Np-toluenesulfonyl-N '- (3-ptoluenesulfonyloxy-phenyl) ureas, which as a developer under the influence of heat, a color-forming reaction with the or the dye precursor (s) is received.
The invention further relates to the use of the recording material according to the invention and to a process for its preparation.

Aus den die Herstellung der vorstehend genannten Entwickler betreffenden WO 00 / 35679 A1 und US 6,624,117 B1 ist auch ein Aufzeichnungsmaterial der eingangs beschriebenen Art bekannt. Ein Einsatzgebiet für das bekannte Aufzeichnungsmaterial ist aus der Schrift nicht ersichtlich. Es wird offenbart, dass die neben Calciumcarbonat weitere Pigmente aufweisende Aufzeichnungsschicht bevorzugt mit einer Schutzschicht abzudecken ist.From WO 00/35679 A1 and US Pat. No. 6,624,117 B1 relating to the preparation of the abovementioned developers, a recording material of the type described in the introduction is also known. A field of application for the known recording material is not apparent from the document. It is disclosed that the recording layer containing further pigments in addition to calcium carbonate is preferably to be covered with a protective layer.

Mit dem Ziel, ein hochsensitives wärmeempfindliches Aufzeichnungsmaterial zur Verfügung zu stellen, das über eine hervorragende Lagerungsstabilität und Beständigkeit gegenüber Chemikalien verfügen soll und mit dem ein dichtes Druckbild unter Minimierung einer Hintergrundvergrauung ermöglicht wird, schlägt die EP 1 321 306 A2 für eine sehr spaltfeste Beschichtungsstruktur die Einstellung eines bestimmten Benetzungsvermögens an der Oberfläche des wärmeempfindlichen Aufzeichnungsmaterials vor. Beschrieben wird dieses Benetzungsvermögen durch eine Oberflächenspannung mit einem Mindestkontaktwinkel von 20° bei Verwendung von destilliertem Wasser. Das bekannte Aufzeichnungsmaterial weist mit Blick auf die zugrunde liegende Aufgabe bevorzugt eine Schutzschicht sowie zwingend Vernetzungs- und verklebende Mittel in der oberflächennahen Schicht auf.With the aim of providing a highly sensitive thermosensitive recording material which is said to have excellent storage stability and resistance to chemicals and which enables a dense printed image while minimizing background graying, EP 1 321 306 A2 proposes a very slit-resistant coating structure Adjustment of a specific wetting ability on the surface of the heat-sensitive recording material. This wettability is described by a surface tension with a minimum contact angle of 20 ° when using distilled water. The known recording material preferably has a protective layer in view of the underlying object mandatory crosslinking and bonding agents in the near-surface layer on.

Die EP-A-1 208 994 offenbart für eine wärmeempfindliche Aufzeichnungsschicht die Kombination von Entwicklern der benannten Gruppe mit einem oder mehreren Pigmenten aus der Gruppe bestehend aus Aluminiumhydroxid, amorphem Siliziumdioxid, Kaolin und Talkum. Als Ziele dieser Schrift werden die Beständigkeit gegenüber Wasser, Hitze, Licht und Weichmacher sowie eine hohe Aufzeichnungsempfindlichkeit angegeben. Da gemäß den Beispielen dieser Schrift die Aufzeichnungsschicht mit einer die Herstellungskosten verteuernden Schutzschicht abgedeckt ist, lassen die erzielten Ergebnisse darauf schließen, dass die Beständigkeit gegenüber Umwelteinflüssen noch nicht voll befriedigend ist. EP-A-1 208 994 discloses, for a heat-sensitive recording layer, the combination of developers of the named group with one or more pigments selected from the group consisting of aluminum hydroxide, amorphous silica, kaolin and talc. The objectives of this document are the resistance to water, heat, light and plasticizer and a high recording sensitivity. According to the examples of this document, since the recording layer is covered with a protective layer which increases the manufacturing cost, the results obtained indicate that the resistance to environmental influences is not yet fully satisfactory.

Die vorliegende Erfindung hat die Aufgabe, ein wärmeempfindliches Aufzeichnungsmaterial zur Verfügung zu stellen, das über einen einfachen Aufbau verfügt und zu geringen Herstellungskosten herstellbar ist. Insbesondere soll das neue Aufzeichnungsmaterial keiner zusätzlichen Schutzschicht zur Abdeckung der Aufzeichnungsschicht bedürfen, aber gleichwohl eine hohe Lagerstabilität sowohl des Aufzeichnungsmaterials selbst als auch des erzeugten Schriftbildes aufweisen und einen guten Kontrast zwischen Schriftbild und unbeschrifteter Aufzeichnungsschicht gewährleisten.The object of the present invention is to provide a heat-sensitive recording material which has a simple structure and can be produced at low production costs. In particular, the new recording material should require no additional protective layer to cover the recording layer, but nevertheless have a high storage stability of both the recording material itself and the generated typeface and ensure good contrast between the typeface and unlabeled recording layer.

Des weiteren soll das beschriftete Aufzeichnungsmaterial über eine gute Beständigkeit gegenüber Substanzen wie Fettungsmitteln, Wachsen, (Poly-) Glykolen und Polypropylenabkömmlingen verfügen, die üblicherweise bei Leder eingesetzt werden, das zur Herstellung von Geldbörsen, Brieftaschen und Einstecketuis für Führerscheine verwendet wird. Durch die Analyse von Verbrauchern und deren Verhalten wurde zuvor erkannt, dass speziell ein Bedarf an möglichst kostengünstigen wärmeempfindlichen Aufzeichnungsmaterialien insbesondere mit den zuvor aufgeführten Beständigkeiten besteht, da Parktickets und Buchungsund/oder Kaufbelege oft wochenlang in den Geldbörsen bzw. Brieftaschen verweilen, bis sie später zum Nachweis getätigter Zahlungen vorgezeigt und noch über einen längeren Zeitraum archiviert werden. Dabei darf es auch nach längeren Aufbewahrungszeiten zu keinen nennenswerten Einschränkungen bei der Entzifferung ausgebildeter Thermodruckbilder kommen.Furthermore, the labeled recording material should have good resistance to substances such as fatliquoring agents, waxes, (poly) glycols and polypropylene derivatives commonly used in leather used for making purses, wallets and slip-in cases for driver's licenses. Through the analysis of consumers and their behavior was previously recognized that there is a particular need for low-cost heat-sensitive recording materials, especially with the resistances listed above, as parking tickets and Buchungsund / or vouchers often spend weeks in the purses or wallets, until later Proof of payments made and over be archived for a longer period of time. It may come even after prolonged storage times to no significant restrictions in the deciphering trained thermo prints.

Folgerichtig sieht die Erfindung ein weiteres Ziel in der Entwicklung eines wärmeempfindlichen Aufzeichnungsmaterials, das zur Ausstellung von Belegen wie Parktickets, Kassenbons, Garantiebelegen und Quittungen an einer Registrierkasse mit einem darin installierten Thermodrucker verwendet werden kann.Consequently, the invention provides a further object in the development of a thermosensitive recording material which can be used to issue receipts such as parking tickets, receipts, guarantee documents and receipts at a cash register with a thermal printer installed therein.

Schließlich will die Erfindung auch ein Verfahren zur Verfügung stellen, das eine einfache und kostengünstige Herstellung des erfindungsgemäßen Aufzeichnungsmaterials ermöglicht.Finally, the invention also seeks to provide a method which enables a simple and inexpensive production of the recording material according to the invention.

Zur Lösung der Aufgabe sieht die Erfindung ein Aufzeichnungsmaterial mit einem Substrat und einer wärmeempfindlichen Aufzeichnungsschicht als nach außen abschließende obere Schicht vor, wobei die Aufzeichnungsschicht

  • a) einen oder mehrere Farbstoffvorläufer,
  • b) als Entwickler eine Verbindung aus der Gruppe der N-p-toluenesulfonyl-N'-(3-p-toluenesulfonyloxyphenyl) Harnstoffe, der unter Einfluss von Wärme eine farbbildende Reaktion mit dem oder den Farbstoffvorläufer(n) eingeht,
  • c) Calciumcarbonat sowie
  • d) Bindemittel enthält
    und das Aufzeichnungsmaterial dadurch gekennzeichnet ist, dass
  • e) die Aufzeichnungsschicht einen polaren Teil der Oberflächenspannung von 5 bis 9,5 mN/m nach Owens-Wendt aufweist und das Verhältnis des dispersen Teils zum polaren Teil zwischen 3,5 :1 und 7,0 : 1 liegt,
  • f) das Verhältnis von Calciumcarbonat zu Bindemittel in der Aufzeichnungsschicht in einem Bereich von 1,8 : 1 bis 3,3 : 1 liegt und
  • g) Calciumcarbonat als einziges Pigment in der Aufzeichnungsschicht vorliegt.
In order to achieve the object, the invention provides a recording material having a substrate and a heat-sensitive recording layer as an outwardly-terminating upper layer, wherein the recording layer
  • a) one or more dye precursors,
  • b) as developer a compound from the group of Np-toluenesulfonyl-N '- (3-p-toluenesulfonyloxyphenyl) ureas, which undergoes a color-forming reaction with the dye or the precursor (s) under the influence of heat,
  • c) calcium carbonate as well
  • d) binder
    and the recording material is characterized in that
  • e) the recording layer has a polar part of the surface tension of 5 to 9.5 mN / m according to Owens-Wendt and the ratio of the disperse part to the polar part is between 3.5: 1 and 7.0: 1,
  • f) the ratio of calcium carbonate to binder in the recording layer is in a range of 1.8: 1 to 3.3: 1 and
  • g) calcium carbonate is the only pigment in the recording layer.

Die gute Beständigkeit beispielsweise gegenüber den Substanzen, die bei der Herstellung von Leder verwendet werden und die bei der Aufbewahrung von zum Beispiel Quittungen in Geldbörsen und Brieftaschen auf das mit einem durch Thermodruck beschriftete Aufzeichnungsmaterial einwirken, erklärt sich dadurch, dass durch die anionische Gruppe im Entwicklermolekül der elektrochemische Oberflächencharakter des Entwicklers stark beeinflusst wird. Hierdurch werden die polaren Gruppen abgebunden und der polare Anteil der Oberflächenspannung reduziert. Die Erfinder erkannten, dass sich dieser Effekt verstärkt zeigt, wenn in der Umgebung des Entwicklers Calciumcarbonat-Partikel im erhöhten Umfang vorliegen. Die in Bezug auf die Aufgabe besten Ergebnisse ergeben sich, wenn das Verhältnis von Calciumcarbonat zu Bindemittel in der auch den Entwickler und den einen oder mehrere Farbstoffvorläufer enthaltenden Aufzeichnungsschicht in dem erfindungsgemäßen Bereich von 1,8 : 1 bis 3,3 : 1 liegt.The good resistance, for example, to the substances used in the production of leather, which, when storing, for example, wallet and wallet receipts, on the thermal-printed recording material, is explained by: that the anionic group in the developer molecule greatly influences the surface electrochemical character of the developer. This bonds the polar groups and reduces the polar component of the surface tension. The inventors recognized that this effect is more pronounced when there are increased amounts of calcium carbonate particles in the environment of the developer. The best results in relation to the task result when the ratio of calcium carbonate to binder in the recording layer also containing the developer and one or more dye precursors is in the range of 1.8: 1 to 3.3: 1 according to the invention.

Insbesondere hat sich ein Verhältnis von Calciumcarbonat zu Bindemittel in einem Bereich von 2,2 : 1 bis 3,2 : 1 als geeignet erwiesen. Dabei beziehen sich die hier in der Beschreibung wie auch in den Ansprüchen gemachten Angaben zum Verhältnis von Calciumcarbonat zu Bindemittel jeweils auf das "atro"-Gewicht, das bedeutet auf absolut trockene Gewichtsteile.In particular, a ratio of calcium carbonate to binder in a range of 2.2: 1 to 3.2: 1 has been found to be suitable. In this case, the statements made here in the description as well as in the claims concerning the ratio of calcium carbonate to binder in each case refer to the "atro" weight, which means to absolutely dry parts by weight.

Gemäß einer bevorzugten Ausführungsform handelt es sich bei dem in der Aufzeichnungsschicht vorliegenden Calciumcarbonat um gefälltes Calciumcarbonat.According to a preferred embodiment, the calcium carbonate present in the recording layer is precipitated calcium carbonate.

In den dieser Schrift vorausgegangenen zahlreichen Versuchsreihen zeigte es sich als vorteilhaft und wird in Folge dessen besonders bevorzugt, wenn das Calciumcarbonat eine durchschnittliche Teilchengröße von 0,20 µm ± Rundungskonvention, d. i. der Bereich von 0,15 µm bis 0,24 µm, und eine spezifische Oberfläche (BET) nach DIN 66132 von 10 m2/g ± Rundungskonvention, d. i. der Bereich von 5 m2/g bis 14 m2/g, aufweist.In the numerous series of experiments preceding this document, it has proved to be advantageous and is consequently particularly preferred when the calcium carbonate has an average particle size of 0.20 μm ± rounding convention, ie the range from 0.15 μm to 0.24 μm, and a specific surface area (BET) according to DIN 66132 of 10 m 2 / g ± rounding convention, which has the range from 5 m 2 / g to 14 m 2 / g.

Gemäß der vorliegenden Erfindung können als Bindemittel Stärke, Zellulosederivate wie CMC und Kunststoffdispersionen auf Basis von Acrylat, Butadienstyrol, Polyvinylacetat allein oder in Abmischung in der Aufzeichnungsschicht eingesetzt werden. Insbesondere ist jedoch Polyvinylalkohol allein oder in Abmischung mit anderen Bindemitteln geeignet. In einer ganz besonders bevorzugten Ausführungsvariante handelt es sich um teilweise oder vollständig verseiften Polyvinylalkohol, der alleine, in Kombination mit anderen Polyvinylalkoholen oder allgemein mit anderen Bindemitteln in der wärmeempfindlichen Aufzeichnungsschicht eingebunden ist.According to the present invention can be used as binders starch, cellulose derivatives such as CMC and plastic dispersions based on acrylate, butadiene styrene, polyvinyl acetate alone or in admixture in the recording layer. In particular, however, polyvinyl alcohol is suitable alone or in admixture with other binders. In a most preferred embodiment, it is partially or completely saponified polyvinyl alcohol, which is incorporated alone, in combination with other polyvinyl alcohols or in general with other binders in the heat-sensitive recording layer.

Als besonders vorteilhaft hat sich überdies erwiesen, dass die Aufzeichnungsschicht mit einer relativ geringen Auftragsstärke vorliegen kann, nämlich mit einer flächenbezogenen Masse von 2,0 bis 3,8 g/m2, insbesondere mit einer flächenbezogenen Masse ≤ 3,3 g/m2, wobei sich die hier in der Beschreibung wie auch in den Ansprüchen gemachten Angaben zu den flächenbezogenen Massen der Aufzeichnungsschicht jeweils auf das "atro"-Gewicht, das bedeutet auf absolut trockene Gewichtsteile, beziehen. Zum Auftrag werden bevorzugt Vorhangbeschichter oder egalisierende Auftragswerke vom Messer- und Rollrakeltyp verwendet. So wird eine ebene Aufzeichnungsschicht bewirkt, die zu keinerlei Störungen beim Passieren des Thermokopfes während des Thermodruckprozesses führen kann. Entsprechend einer bevorzugten Ausführungsform ist die zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht genutzte Streichfarbe wässerig. Die anschließende Trocknung der Streichfarbe kann mittels Mikrowellenbestrahlung geschehen. Üblicherweise und bewährt ist ein Verfahren, bei dem Wärme zugeführt wird, wie es durch Heißluft-Schwebetrockner oder auch Kontakttrockner, wie beispielsweise Trockenzylinder, geschieht. Auch denkbar ist eine Kombination aus den aufgeführten Trockenverfahren.Moreover, it has proved to be particularly advantageous that the recording layer can be present with a relatively low coating thickness, namely with a basis weight of 2.0 to 3.8 g / m 2 , in particular with a basis weight ≤ 3.3 g / m 2 , wherein the statements made here in the description as well as in the claims relating to the surface masses of the recording layer in each case on the "atro" weight, which means to absolutely dry parts by weight, relate. To order preferably curtain coaters or leveling commissioned works of knife and roller doctor type are used. Thus, a flat recording layer is effected which can not cause any interference with the passage of the thermal head during the thermal printing process. According to a preferred embodiment, the coating color used to form the thermosensitive recording layer is aqueous. The subsequent drying of the coating color can be done by means of microwave irradiation. Usually and proven is a method in which heat is supplied, as is done by hot-air floatation dryer or contact dryer, such as drying cylinders. Also conceivable is a combination of the listed dry processes.

Ohne auf die im Folgenden genannten Farbstoffvorläufer beschränkt zu sein, haben sich die folgenden Komponenten in einem besonderen Maße bewährt und gelten aus diesem Grund als besonders bevorzugt:

  • 3-N-propyl-N-methylamino-6-methyl-7-anilinofluoran
  • 6'-(dibutylamino)-3'-methyl-2'-(phenylamino)-spiro[isobenzofuran-1 (3H),9'-[9H]xanthen]-3-one sowie
  • 3,3-Bis-(p-dimethyl-aminophenyl)-6-dimethylaminophthalid
sowie weitere Fluoranverbindungen, wie
  • 3-(Ethylisoamylamino)-6-methyl-7-anilinofluoran.
Without being limited to the dye precursors mentioned below, the following components have proven to be particularly effective and are therefore considered to be particularly preferred:
  • 3-N-propyl-N-methylamino-6-methyl-7-anilinofluoran
  • 6 '- (dibutylamino) -3'-methyl-2' - (phenylamino) -spiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one and also
  • 3,3-bis (p-dimethyl-aminophenyl) -6-dimethylaminophthalide
as well as other fluoran compounds, such as
  • 3- (Ethylisoamylamino) -6-methyl-7-anilinofluoran.

Zwischen der Aufzeichnungsschicht und dem Substrat des erfindungsgemäßen Aufzeichnungsmaterials ist zweckmäßigerweise eine Bindemittel und ölabsorbierendes Pigment enthaltende Zwischenschicht angeordnet. Als Pigmente der Zwischenschicht haben sich neben den anorganischen ölabsorbierenden Pigmenten bevorzugt ausgewählt aus der Gruppe, umfassend natürliches wie kalziniertes Kaolin, Silizium(di)oxid, Bentonit, Calciumcarbonat sowie Aluminium(di)oxid und hier besonders Böhmit auch organische Hohlraumpigmente bewährt, wobei die Pigmente einzeln wie auch in Kombination untereinander eingesetzt werden können. Eine solche Zwischenschicht kann einerseits einen positiven Beitrag zur Egalisierung der Substratoberfläche leisten, womit sich die Menge an notwendigerweise aufzubringender Streichfarbe für die wärmeempfindliche Aufzeichnungsschicht noch weiter reduziert auf einen bevorzugten Bereich von 1,0 bis 3,0 g/m2. Aus diesem Grund bieten sich zum Auftrag der Zwischenschicht egalisierende Streichwerke an, wie beispielsweise Walzenstreichwerke, Streichmesser- oder (Roll-) Rakelstreichwerke. Andererseits können die Pigmente dieser Zwischenschicht die durch Hitzeeinwirkung verflüssigten Wachsbestandteile der wärmeempfindlichen Aufzeichnungsschicht bei der Schriftbildausbildung aufnehmen und begünstigen so eine sichere und schnelle Funktionsweise der wärmeinduzierten Aufzeichnung. Aus diesem Grund umfasst die bevorzugt vorgesehene Zwischenschicht auch mindestens ein öl- bzw. wachsabsorbierendes Pigment. Die flächenbezogene Masse der pigmentierten Zwischenschicht liegt bevorzugt zwischen 5 und 20 g/m2 und noch besser zwischen 7 und 10 g/m2 (atro).Between the recording layer and the substrate of the recording material of the present invention, an intermediate layer containing a binder and an oil-absorbing pigment is suitably disposed. As pigments of the intermediate layer, in addition to the inorganic oil-absorbing pigments selected from the group comprising natural and calcined kaolin, silicon (di) oxide, bentonite, calcium carbonate and aluminum (di) oxide and, in particular, boehmite, organic hollow-wall pigments have proved to be preferred, the pigments can be used individually as well as in combination with each other. On the one hand, such an intermediate layer can make a positive contribution to equalization of the substrate surface, whereby the amount of coating color necessarily to be applied for the heat-sensitive recording layer is further reduced to a preferred range of 1.0 to 3.0 g / m 2 . For this reason, offer to coat the intermediate layer leveling strokes, such as Walzenstreichwerke, doctor blade or (roll) doctor blade coating. On the other hand, the pigments of this intermediate layer can absorb the heat-liquefied wax components of the thermosensitive recording layer in the typeface formation, thus promoting a safe and rapid operation of the heat-induced recording. For this reason, the preferred intermediate layer also comprises at least one oil or wax-absorbing pigment. The basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 10 g / m 2 (atro).

Als Substrat zur Herstellung des erfindungsgemäßen Aufzeichnungsmaterials ist insbesondere eine Papierbahn geeignet, auch wenn die Erfindung nicht auf Papier als Substrat beschränkt ist. Dabei kann die Papierbahn auf der Seite, die der Seite mit der Aufzeichnungsschicht gegenüberliegt, mit einer Präparation bevorzugt auf Stärkebasis versehen sein, die idealerweise in einem Bereich von 0,1 bis 0,5 g/m2 aufgetragen ist.As a substrate for producing the recording material of the present invention, a paper web is particularly suitable, although the invention is not limited to paper as a substrate. In this case, the paper web on the side opposite to the side with the recording layer may be provided with a preparation preferably based on starch, which is ideally applied in a range of 0.1 to 0.5 g / m 2 .

In geeigneter Weise weist das Aufzeichnungsmaterial zumindest auf seiner mit der Aufzeichnungsschicht versehenen Seite eine Bekkglätte von 400 bis 1000 sec auf.Suitably, the recording material has, at least on its side provided with the recording layer, a Bekkglätte of 400 to 1000 sec.

Es ist weiterhin bevorzugt, dass das Aufzeichnungsmaterial unmittelbar nach einer mit einer Energie von 10 bis 11,5 mJ/mm2 durchgeführten Bedruckung bei 300 dpi Auflösung eine Bilddichte von 1,20 bis 1,35 ODU (= Optical Density Units) aufweist.It is furthermore preferred for the recording material to have an image density of 1.20 to 1.35 ODU (= Optical Density Units) immediately after printing at 300 dpi resolution with an energy of 10 to 11.5 mJ / mm 2 .

Zur Gewährleistung eines guten Kontrasts zwischen Schriftbild und unbeschrifteter Aufzeichnungsschicht weist das Aufzeichnungsmaterial bevorzugt eine Weiße in einem Bereich von 90 bis 98 %, gemessen nach ISO 2469 / ISO 2470, auf, wobei jedoch D65-Licht verwendet wird bei einem Betrachtungswinkel von 8°.To ensure good contrast between the typeface and unlabelled recording layer, the recording material preferably has a whiteness in a range of 90 to 98% as measured by ISO 2469 / ISO 2470, but D65 light is used at an observation angle of 8 °.

Eine Verwendung des erfindungsgemäßen Aufzeichnungsmaterials ist in vielen Bereichen möglich. Infolge der überraschend hohen Alterungsbeständigkeit des erzeugten Schriftbildes als auch des Aufzeichnungsmaterials bzw. seiner Aufzeichnungsschicht ist das Aufzeichnungsmaterial nach der vorliegenden Erfindung jedoch ganz besonders zur Ausstellung von Belegen insbesondere zur Erstellung von Quittungen und Garantiescheinen an einer mit einem Thermodrucker ausgerüsteten Registrierkasse geeignet. Hierbei ist der einfache Aufbau des Aufzeichnungsmaterials ohne Schutzschicht und die infolgedessen kostengünstige Herstellbarkeit von erheblichem Vorteil.A use of the recording material according to the invention is possible in many areas. However, due to the surprisingly high resistance to aging of the generated typeface as well as the recording material or its recording layer, the recording material according to the present invention is particularly suitable for issuing receipts, in particular for producing receipts and guarantee certificates on a cash register equipped with a thermal printer. Here, the simple structure of the recording material without protective layer and the consequently cost-effective manufacturability of considerable advantage.

Ein geeignetes Verfahren zur Herstellung des erfindungsgemäßen Aufzeichnungsmaterials in einer seiner möglichen Ausführungsformen umfasst zunächst die Bereitstellung eines Substrates. Hierzu bietet sich insbesondere eine Papierbahn an, die eine flächenbezogene Masse bevorzugt in einem Bereich von 40 bis 75 g/m2 (atro) aufweist. Die Komponenten der Papierbahn sind im Sinne der Erfindung nicht eingeschränkt, jedoch bietet sich besonders zum einen ein Polyolefin beschichtetes Rohpapier oder ein in der Masse geleimtes Rohpapier mit aufgetragener Zwischenschicht in eingeebneter Ausführung an. In diesem Fall weist das Rohpapier gewöhnlich aus gebleichten und gemahlenen Zellstoffen neben den üblichen Beischlagstoffen wie z.B. Retentionsmitten bevorzugt Harzleim in einem Bereich von 0,3 bis 1,2 Gew.-% (atro) und noch besser von 0,45 bis 0,9 Gew.-% (atro), bezogen auf das Feststoffgewicht des Rohpapiers, auf. Die Zwischenschicht weist neben Bindemitteln in erster Linie ein oder mehrere anorganische Pigmente zur Ölabsorption und gegebenenfalls auch organische Hohlraumpigmente auf, die dann geeignet sind, vom Thermokopf zur Druckbildausbildung in der Aufzeichnungsschicht stammende Hitze, die zunächst durch die Aufzeichnungsschicht hindurch gedrungen ist, auf die Aufzeichnungsschicht zurück zu reflektieren. Eine solche Fähigkeit der Hohlraumpigmente in der Zwischenschicht trägt zu einer besseren Effektivität des wärmeempfindlichen Aufzeichnungsmaterials bei. Bei vorgesehener Zwischenschicht geschieht die Auftragung der Zwischenschicht in der Regel mit einem egalisierenden Streichwerk, wie es z.B. ein Walzenstreichwerk, ein Streichmesser- oder (Roll) Rakelstreichwerk darstellt.A suitable method for producing the recording material according to the invention in one of its possible embodiments initially comprises the provision of a substrate. In particular, a paper web which has a surface-related mass in a range from 40 to 75 g / m 2 (atro) is particularly suitable for this purpose. The components of the paper web are not restricted within the meaning of the invention, but on the one hand, in particular, a polyolefin-coated base paper or a base paper sized with an applied intermediate layer in a flattened design is recommended. In this case, the base paper usually bleached and ground pulps in addition to the usual admixtures such as retention centers preferably resin glue in a range of 0.3 to 1.2 wt .-% (atro) and more preferably from 0.45 to 0.9 Wt .-% (atro), based on the solids weight of the base paper on. The intermediate layer In addition to binders, there are primarily one or more inorganic oil absorption pigments and, optionally, organic voiding pigments which are then capable of reflecting heat from the thermal head for printing image formation in the recording layer, which has first penetrated the recording layer, back to the recording layer , Such ability of the cavity pigments in the intermediate layer contributes to better efficiency of the thermosensitive recording material. When provided intermediate layer, the application of the intermediate layer is usually done with a leveling coating, as it represents, for example, a roller coater, a doctor blade or (roll) doctor blade.

Das vorgeschlagene Verfahren zur Herstellung des wärmeempfindlichen Aufzeichnungsmaterials entsprechend der vorliegenden Erfindung umfasst dann das flächige Auftragen einer bevorzugt wässerigen Beschichtungsmasse für die wärmeempfindliche Aufzeichnungsschicht mit

  • einem oder mehreren Farbstoffvorläufer(n),
  • einer Verbindung aus der Gruppe der N-p-toluenesulfonyl-N'-(3-ptoluenesulfonyloxyphenyl) Harnstoffe als Entwickler, der unter Einfluss von Wärme eine farbbildende Reaktion mit dem oder den Farbstoffvorläufer(n) eingeht,
  • Calciumcarbonat, insbesondere gefälltes Calciumcarbonat, als einziges Pigment,
  • Bindemittel, wobei hier insbesondere teilweise oder vollständig verseifter Polyvinylalkohol bevorzugt ist,
wobei das Verhältnis von Calciumcarbonat zu Bindemittel in der Aufzeichnungsschicht in einem Bereich von 1,8 : 1 bis 3,3 : 1 liegt (atro).The proposed method for producing the thermosensitive recording material according to the present invention then comprises coating a preferred aqueous coating composition for the thermosensitive recording layer with
  • one or more dye precursors,
  • a compound of the group of Np-toluenesulfonyl-N '- (3-p-toluenesulfonyloxyphenyl) ureas as a developer which undergoes a color-forming reaction with the dye precursor (s) under the influence of heat,
  • Calcium carbonate, in particular precipitated calcium carbonate, as sole pigment,
  • Binder, in which case in particular partially or completely saponified polyvinyl alcohol is preferred,
wherein the ratio of calcium carbonate to binder in the recording layer is in a range of 1.8: 1 to 3.3: 1 (atro).

Die flächenbezogene Masse, mit der die Aufzeichnungsschicht aufgetragen wird, soll dabei bevorzugt in einem Bereich von 2,0 bis 3,8 g/m2 bzw. kleiner gleich 3,3 g/m2 und ganz besonders bevorzugt in einem Bereich von 2,0 bis 3,3 g/m2 (atro) liegen. Die Aufzeichnungsschicht wird dabei bevorzugt mit einem Vorhangbeschichter, einem Streichmesser- oder einem Rollrakel-Auftragswerk aufgetragen. Die sich anschließende Trocknung geschieht bevorzugt mit einem Heizluft-Schwebetrockner in Kombination mit Trockenzylindern, zwischen denen das ausgebildete Aufzeichnungsmaterial mäanderförmig durchgeführt wird. Zwischen Heizluft-Schwebetrockner und Trockenzylindern kann das Aufzeichnungsmaterial nochmals ein- oder beidseitig befeuchtet werden. Diese Befeuchtung kann mit einem Dampfblaskasten oder mittels Befeuchtungszylindern bzw. - auftragswerken geschehen. Vor der endgültigen Aufrollung des wärmeempfindlichen Aufzeichnungsmaterials wird dieses bevorzugt zunächst einer Glättwerkbehandlung und zusätzlich einer Kalanderbehandlung unterzogen. Während das Aufzeichnungsmaterial bei der Glättwerkbehandlung durch die Spalten (Nips) von jeweils zwei, gegebenenfalls unterschiedlich beschichteten, Stahlwalzen durchgeführt wird, sieht die Kalanderbehandlung eine Durchführung des Aufzeichnungsmaterials durch die Spalten (Nips) von jeweils einer papierbeschichten Walze und einer Stahlwalze vor. Dabei umfassen sowohl Glättwerk wie auch Kalander jeweils mehrere Nips, bei denen die Walzen zur Einstellung einer geeigneten Friktion untereinander und auch in Bezug auf das durchgeführte Aufzeichnungsmaterial unterschiedliche Geschwindigkeiten aufweisen können.The basis weight with which the recording layer is applied should preferably be in a range of 2.0 to 3.8 g / m 2 or less than or equal to 3.3 g / m 2 and most preferably in a range of 2, 0 to 3.3 g / m 2 (atro). The recording layer is preferably applied with a curtain coater, a doctor blade or a rotary doctor applicator. The subsequent drying is preferably done with a Heated hot air dryer in combination with drying cylinders, between which the formed recording material is performed meandering. Between heated air-suspended dryer and drying cylinders, the recording material can be moistened again on one or both sides. This moistening can be done with a steam box or by means of moistening cylinders or applicators. Before the final reeling of the heat-sensitive recording material, this is preferably first subjected to a calendering treatment and additionally to a calendering treatment. While the recording material in the calender processing by the nips (columns) of two, optionally differently coated steel rollers is performed, the calender treatment provides a passage of the recording material through the nips of each of a paper-coated roller and a steel roller. In this case, both calender and calender each comprise a plurality of nips, in which the rollers for setting a suitable friction with each other and also with respect to the recording material carried through may have different speeds.

Die Bestimmung der Oberflächenspannung nach Owens Wendt erfolgt wie in Journal of Applied Polymer Science, Vol. 13, 1969, Seiten 1741-1747: Estimation of the Surface Free Energy of Polymers; D.K. Owens, R.C. Wendt angegeben.The determination of the surface tension according to Owens Wendt is carried out as described in Journal of Applied Polymer Science, Vol. 13, 1969, pages 1741-1747: Estimation of the Surface Free Energy of Polymers; D. K. Owens, R.C. Wendt stated.

Die nachfolgenden Beispiele 1 bis 3 dienen der Erläuterung der Erfindung:The following examples 1 to 3 serve to illustrate the invention:

Herstellung einer Substrat-Bahn:Production of a substrate web:

Eine Substratbahn wird aus gebleichten und gemahlenen Laub- und Nadelholzzellstoffen unter Zugabe von 0,6 Gew.-% (atro) Harzleim als Masseleimung sowie weiterer üblicher Beischlagstoffe, bezogen auf den Feststoffgehalt (atro) der Substratbahn, mit einer flächenbezogenen Masse von (A) g/m2 hergestellt. Frontseitig wird auf die jeweiligen Substratbahnen der Beispiele 1 und 2 eine kalziniertes Kaolin als Pigment, Styrol-Butadien-Latex als Bindemittel und Stärke als Cobinder neben weiteren Hilfsmitteln aufweisende Zwischenschicht mit einer flächenbezogenen Masse von 9 g/m2 aufgebracht; rückseitig wird das Trägerpapier mit einer Stärkepräparation mit einer flächenbezogenen Masse von 0,2 g/m2 versehen.A substrate web is made of bleached and ground hardwood and softwood pulps with the addition of 0.6% by weight (atro) rosin size as engine sizing and other typical admixtures, based on the solids content (atro) of the substrate web, with a basis weight of (A) g / m 2 produced. On the front side, a calcined kaolin pigment, styrene-butadiene latex binder and starch co-binder is applied to the respective substrate webs of Examples 1 and 2 in addition to further auxiliary agents having a basis weight of 9 g / m 2 ; At the back, the backing paper is provided with a starch preparation having a basis weight of 0.2 g / m 2 .

Herstellung und Auftrag der Aufzeichnungsschicht:Production and application of the recording layer:

Auf die Zwischenschicht wird mittels einer Beschichtungsvorrichtung (B) eine wärmeempfindliche Aufzeichnungsschicht mit einer flächenbezogenen Masse von (C) g/m2 mit der Tabelle 1 zu entnehmenden Zusammensetzung aufgetragen, wobei alle Angaben als atro- Gewichtsteile, zu verstehen sind.On the intermediate layer, a heat-sensitive recording layer with a basis weight of (C) g / m 2 with the composition to be taken from Table 1 is applied by means of a coating device (B), all data being understood as parts by weight.

Nach Trocknung der Beschichtungsmasse wird die Papierbahn auf einem Superkalander behandelt, so dass die wärmeempfindliche Aufzeichnungsschicht eine Bekkglätte von (D) sec aufweist. Die Bekkglätte wird nach dem in der DIN 53107 angegebenen Verfahren bestimmt. Zu den Einzelheiten des Messverfahrens wird auf die DE 100 14 351 A1 verwiesen.After drying the coating composition, the paper web is treated on a supercalender so that the heat-sensitive recording layer has a Bekkglätte of (D) sec. The Bekkglätte is determined by the method specified in DIN 53107. For details of the measuring method, reference is made to DE 100 14 351 A1 .

Zur Erklärung der Zusammensetzungen der Beschichtungsmassen für die Aufzeichnungsschicht, deren Auftragsgewicht, zu den eingesetzten Beschichtungsvorrichtungen und zu den erzielten Prüfdaten wird auf die Tabellen 1 und 2 bzw. deren Anhang verwiesen. Tabelle 1 Polyvinylalkohol * 11,5 Entwickler** 20,0 Farbstoffvorläufer*** (X) 8,7 Sensibilisator (BNE)**** ™ 20,0 Pigment***** 25,0 Optischer Aufheller 0,5 Anhang zu Tabelle 1
*Mowiol 15-99™ ; Verseifungsgrad 99%
**N-p-toluenesulfonyl-N'-(3-p-toluenesulfonyloxyphenyl) Harnstoff (C21 H20O6N2S2)
*** siehe Tabelle 2
****Benzylnaphthylether
*****gefälltes Calciumcarbonat, Teilchengröße D50-Wert 0,2 µm Tabelle 2. Beispiele 1- 3: Beispiel 1 2 3 Einheit A 41 43 45 g/m2 B Vorhangbeschichter Rollrakel Rollrakel C 2,5 2,8 3,0 g/m2 D 900 620 650 sec E 1,34 1,31 1,28 ODU X ODB2TM: 8,7 ODB2 TM: 8,7 ODB2 TM: 7,8 & 0,9 S205™ Gew.- Teile Y 6,3 8,3 7,9 mN/m Z 5,65 : 1 4,14 : 1 4,25 : 1 For an explanation of the compositions of the coating compositions for the recording layer, their application weight, the coating apparatuses used and the test data obtained, reference is made to Tables 1 and 2 and their appendices, respectively. <u> Table 1 </ u> Polyvinyl alcohol * 11.5 Developer** 20.0 Dye precursor *** (X) 8.7 Sensitizer (BNE) **** ™ 20.0 Pigment***** 25.0 Optical brightener 0.5 Annex to Table 1
* Mowiol 15-99 ™; Degree of saponification 99%
** Np-Toluenesulfonyl-N '- (3-p-toluenesulfonyloxyphenyl) urea (C 21 H 20 O 6 N 2 S 2 )
*** see Table 2
**** benzyl naphthyl
***** precipitated calcium carbonate, particle size D 50 value 0.2 microns Examples 1-3: example 1 2 3 unit A 41 43 45 g / m 2 B curtain roll doctor roll doctor C 2.5 2.8 3.0 g / m 2 D 900 620 650 sec e 1.34 1.31 1.28 OH YOU X ODB2 ™ : 8.7 ODB2 ™ : 8.7 ODB2 ™ : 7.8 & 0.9 S205 ™ Parts by weight Y 6.3 8.3 7.9 mN / m Z 5.65: 1 4,14: 1 4,25: 1

Es wird ein Thermoprobeausdruck mit einem Gerät der Type Atlantek 400 der Fa. Atlantek (USA) durchgeführt und die Druckdichte mit dem Densitometer Gretag MacBeth TYPE D19C NB/U gemessen (Fa Gretag MacBeth, 8105 Regensdorf, Schweiz).
Dabei wurde mit einem Thermokopf mit 300 dpi bei 11mJ/mm2 eine Druckdichte von (E) ermittelt.A thermal print-out is made with a Atlantek 400 instrument from Atlantek (USA) and the print density is measured with the Gretag MacBeth TYPE D19C NB / U densitometer (Gretag MacBeth, 8105 Regensdorf, Switzerland).
It was determined with a thermal head with 300 dpi at 11mJ / mm 2, a print density of (E).

Die Messung der Oberflächenspannung erfolgte mit einem Gerät des Typs DSA10 MK2 der Firma KRÜSS GmbH (Hamburg).
Es wurde ein polarer Anteil der Oberflächenspannung von (Y) in mN/m sowie ein Verhältnis des dispersen Teils zum polaren Teil der Oberflächenspannung von (Z) ermittelt.The measurement of the surface tension was carried out with a device of the type DSA10 MK2 from KRÜSS GmbH (Hamburg).
A polar fraction of the surface tension of (Y) in mN / m and a ratio of the disperse part to the polar part of the surface tension of (Z) were determined.

Die im Rahmen der Beispiele 1 bis 3 hergestellten, erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterialien verfügen über den geforderten einfachen Aufbau, weisen jedoch gleichwohl eine hohe Lagerstabilität sowohl des Aufzeichnungsmaterials selbst als auch des erzeugten Schriftbildes auf und gewährleisten einen guten Kontrast zwischen Schriftbild und unbeschrifteter Aufzeichnungsschicht. Ferner überzeugen die erfindungsgemäßen Aufzeichnungsmaterialien durch gute Beständigkeit gegenüber Substanzen wie Fettungsmitteln, Wachsen, (Poly-) Glykolen und Polypropylenabkömmlingen, wie sie üblicherweise bei Leder für Geldbörsen und Brieftaschen eingesetzt werden.The heat-sensitive recording materials according to the invention produced in the context of Examples 1 to 3 have the required However, a simple structure, but nevertheless have a high storage stability of both the recording material itself and the generated typeface and ensure a good contrast between typeface and unlabeled recording layer. Furthermore, the recording materials according to the invention are characterized by good resistance to substances such as fatliquors, waxes, (poly) glycols and polypropylene derivatives, as are commonly used in leather for purses and wallets.

Claims (12)

  1. Recording material having a substrate and having, as an upper layer which is the final layer towards the outside, a heat-sensitive recording layer comprising
    a) one or more dye precursors,
    b) as developer, a compound from the group of the N-p-toluenesulphonyl-N'-(3-p-toluenesulphonyloxyphenyl) ureas, which under the influence of heat enters into a colour-forming reaction with the dye precursor(s),
    c) calcium carbonate,
    d) binder,
    characterised in that
    e) the recording layer has a polar portion of surface tension of from 5 to 9.5 mN/m in accordance with Owens-Wendt and the ratio of the disperse portion to the polar portion is between 3.5 : 1 and 7.0 : 1,
    f) the ratio of calcium carbonate : binder in the recording layer is in a range from 1.8 : 1 to 3.3 : 1 and
    g) calcium carbonate is present as sole pigment in the recording layer.
  2. Recording material according to claim 1, characterised in that the calcium carbonate is precipitated calcium carbonate.
  3. Recording material according to one of claims 1 to 2, characterised in that the binder is, or comprises, polyvinyl alcohol.
  4. Recording material according to one of claims 1 to 3, characterised in that the calcium carbonate has an average particle size of 0.20 µm and a specific surface area (BET) according to DIN 66132 of 10 m2/g.
  5. Recording material according to one of claims 1 to 4, characterised in that the recording layer is applied with a weight per unit area of from 2.0 to 3.8 g/m2.
  6. Recording material according to one of claims 1 to 5, characterised in that the recording layer is applied with a weight per unit area of ≤ 3.3 g/m2.
  7. Recording material according to one of claims 1 to 6, characterised in that between the recording layer and the substrate there is arranged an intermediate layer comprising binder and oil-absorbing pigment.
  8. Recording material according to one of claims 1 to 7, characterised in that at least that side of the recording material which is provided with the recording layer has a Bekk smoothness of from 400 to 1000 sec.
  9. Recording material according to one of claims 1 to 8, characterised in that the recording material, immediately after printing performed with an energy of from 10 to 11.5 mJ/mm2 at a resolution of 300 dpi, has an image density of from 1.20 to 1.35 ODU.
  10. Recording material according to one of claims 1 to 9, characterised in that the recording material has a whiteness in a range of from 90 to 98 % according to ISO 2469 / ISO 2470.
  11. Use of the recording material according to one of claims 1 to 10 in issuing receipts at a cash register provided with a thermal printer.
  12. Method of producing a heat-sensitive recording material according to one of claims 1 to 10, comprising the following method steps:
    • planar application of an aqueous coating mass comprising the components mentioned in claims 1 to 4, to a substrate, especially a web of paper, with a weight per unit area as mentioned in claims 5 and 6,
    • levelling and drying of the applied coating mass,
    characterised in that
    • the recording material is smoothed at least on the side on which the coating mass has been applied.
EP04025536A 2003-10-28 2004-10-27 Thermosensitive recording material, its' use and its' method of preparation. Active EP1527900B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04025536T PL1527900T3 (en) 2003-10-28 2004-10-27 Thermosensitive recording material, its' use and its' method of preparation.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10350406 2003-10-28
DE10350406 2003-10-28

Publications (2)

Publication Number Publication Date
EP1527900A1 EP1527900A1 (en) 2005-05-04
EP1527900B1 true EP1527900B1 (en) 2006-10-18

Family

ID=34399583

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04025536A Active EP1527900B1 (en) 2003-10-28 2004-10-27 Thermosensitive recording material, its' use and its' method of preparation.

Country Status (5)

Country Link
EP (1) EP1527900B1 (en)
AT (1) ATE342808T1 (en)
DE (1) DE502004001785D1 (en)
ES (1) ES2273142T3 (en)
PL (1) PL1527900T3 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9827569D0 (en) 1998-12-16 1999-02-10 Ciba Geigy Ag Heat sensitive recording material
DE10014351A1 (en) 2000-03-24 2001-09-27 Mitsubishi Hitec Paper Flensbu Recording paper with different printable front and back coats, useful e.g. for producing ticket with preprint on back, has specified Cobb value and Bekk smoothness on back
EP1208994B2 (en) 2000-11-24 2011-05-25 Oji Paper Co., Ltd. Heat-sensitive recording material
JP2003182235A (en) 2001-12-20 2003-07-03 Fuji Photo Film Co Ltd Thermal recording material

Also Published As

Publication number Publication date
ATE342808T1 (en) 2006-11-15
EP1527900A1 (en) 2005-05-04
DE502004001785D1 (en) 2006-11-30
PL1527900T3 (en) 2007-02-28
ES2273142T3 (en) 2007-05-01

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