EP2033800B1 - Heat-sensitive recording material - Google Patents

Heat-sensitive recording material Download PDF

Info

Publication number
EP2033800B1
EP2033800B1 EP07017264A EP07017264A EP2033800B1 EP 2033800 B1 EP2033800 B1 EP 2033800B1 EP 07017264 A EP07017264 A EP 07017264A EP 07017264 A EP07017264 A EP 07017264A EP 2033800 B1 EP2033800 B1 EP 2033800B1
Authority
EP
European Patent Office
Prior art keywords
methyl
heat
sensitive recording
anilinofluoran
recording layer
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
EP07017264A
Other languages
German (de)
French (fr)
Other versions
EP2033800A1 (en
Inventor
Gerhard Stork
Annette Schreiber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
Original Assignee
Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi HiTech Paper Flensburg GmbH, Stora Spezialpapiere GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Priority to EP07017264A priority Critical patent/EP2033800B1/en
Priority to AT07017264T priority patent/ATE458620T1/en
Priority to ES07017264T priority patent/ES2339166T3/en
Priority to DE502007002944T priority patent/DE502007002944D1/en
Priority to US12/231,653 priority patent/US8198212B2/en
Publication of EP2033800A1 publication Critical patent/EP2033800A1/en
Application granted granted Critical
Publication of EP2033800B1 publication Critical patent/EP2033800B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Definitions

  • the present invention relates to a thermosensitive recording material having a substrate, optionally a pigmented intermediate layer applied to the substrate, and a thermosensitive recording layer containing a color former and color acceptors.
  • the present invention also relates to the use of the thus proposed heat-sensitive recording material as a ticket or as a ticket.
  • Heat-sensitive recording materials of the type described above with, for example, a sheet of paper, a synthetic paper sheet or a plastic film as a substrate are known since the early years of chemically reactive recording materials and enjoy a constantly growing popularity, which is due, inter alia, that their use in particular as a ticket for the Ticket issuing is associated with great benefits. Because the color-forming components are stuck in the recording material itself in the heat-sensitive recording method, the toner and color-cartridge-free printers, which in their function no longer need to be controlled by anyone, can be set up in large numbers. Thus, this innovative technology has prevailed especially in public passenger transport, buses and trains as well as in air traffic, stadium and museum funds and parking ticket issuers.
  • thermoformed prints To increase the resistance of thermoformed prints to water, aqueous alcohol solutions and plasticizers suggests the DE10 2004 044 204A1 a heat-sensitive recording material, whose heat-sensitive recording layer has conventional dye precursors and the combination of a phenolic color developer and a urea-urethane-based color developer.
  • Urea urethane compounds as developers which can be used to increase the print density of thermoformed prints also in combination generally with Suffonylhamstoff are from the EP1 116 713A1 as well as from the DE 692 04 777T2 It is not known that these documents refer to the outstanding effect of N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea.
  • thermosensitive recording material containing at least the components of two color forming systems to form an irreversible printed image, one being a chelate-type system and the other being a conventional leuco-dye system.
  • a variety of sulfonylureas including N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea, called in one embodiment in combination with urea urethane compounds can be combined as a second developer.
  • a disadvantage of the recording materials according to the writings discussed above is in particular in the first case too low plasticizer resistance, associated with very low whiteness of the recording material, as well as the much too complex manufacturing processes that often preclude the use of the proposals in everyday life.
  • the present invention therefore has the object to provide a suitable in particular as a ticket and / or as a ticket heat-sensitive recording material available, which must be produced due to high sales volumes in a fiercely competitive market at low production costs and therefore has to dispose of a simple structure.
  • the new recording material should not require an additional protective layer for covering the heat-sensitive recording layer, because such a protective layer is too costly both in terms of the necessary raw materials as well as in terms of the necessary machinery and process energies.
  • the new recording material should have excellent resistance to ethanol solutions, water and plasticizers.
  • the new recording material requirements for good Bestkovbarkarkeit and Entwertraj are made, which is to be understood in the sense of this invention underlying task that stamped Entwerter Schweizer after about 10 seconds neither dry nor wet can be completely wiped away.
  • the present invention extends to the same extent to the use of such a heat-sensitive recording material described as a ticket or as a ticket.
  • thermo-print print For metrological recording of the print density, a black-and-white checkered thermo-print print is made with an Atlantek 400 from Viex (USA) using a thermal head with a resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 comes.
  • the print density even of the black-colored areas are measured with the densitometer Gretag MacBeth TYPE D19C NB / U (Gretag MacBeth, 8105 Regensdorf, Switzerland), where the dynamic printing densities are measured at three points for each measured value and the arithmetic mean is formed from the three individual values becomes.
  • each black / white checkered-designed Thermoprobeaustike with a device of the type Atlantek 400 made by Viex (USA) created using a thermal head with resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used.
  • the dynamic print density of the black-colored surfaces is first measured at a Thermoprobeaustik at three points with the densitometer Gretag MacBeth TYPE D19C NB / U (Fa Gretag MacBeth, 8105 Regensdorf, Switzerland). Subsequently, the respective treatment of the Thermoprobeausdrucks.
  • This treatment in the case of percent resistance to a 25% ethanol solution, provides immersion of the Thermoprobertextes in an ethanol bath (25 vol .-% solution, 23 ° C) over 20 minutes. The printout is then carefully blotted with blotting paper and allowed to rest for 24 hours at 23 ° and 50% humidity.
  • thermoprobe print In the case of percent resistance to water, the thermoprobe print is placed in a water bath (deionized water, 23 ° C) for 20 minutes. Dabing and resting is then carried out as in the ethanol treatment.
  • the determination of the dynamic print density at three points of the black-colored areas is carried out again with the Gretag MacBeth TYPE D19C NB / U densitometer.
  • the respective mean values of the measurements before / after the bath in the ethanol solution or in water are formed, and the average value after the bath as a percentage of the mean value before the bath.
  • TESA ® graphic film 57331 For each individual determination of the percentage resistance of a Thermoprobeaustikes against plasticizer, a 10 cm long piece of TESA ® graphic film 57331 is first glued to a prepared by means of equipment type Atlantek 400 from Viex (USA) Thermoprobeaustik. Subsequently, the dynamic print density of the black-colored areas is measured immediately at three points using the densitometer Gretag MacBeth TYPE D19C NB / U. The print will then rest for 24 hours at 23 ° and 50% humidity. After resting, the determination of the dynamic print density at three points of the black-colored areas is carried out again with the Gretag MacBeth TYPE D19C NB / U densitometer. The respective mean values of the measurements before / after resting are formed and the average value after resting can be left to rest before the mean value.
  • thermosensitive recording layer it is possible for the thermosensitive recording layer to comprise more than one color former, each selected from the color formers listed above in paragraph [0009].
  • the recording material according to the invention may, in addition to these substances specified as fabifiers, also contain one or more of the following compounds absorbing in the near infrared range:
  • the two dye acceptors of the formula (1) and the formula (2) can constitute up to 35% by weight, but preferably within the range of 25 to 30% by weight of the heat-sensitive recording layer.
  • the effect that the mixture of the two color acceptors brings about in their entirety is a combination resulting from the peculiarities of the two individual color acceptors: While N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy -phenyl) urea according to formula (1) has been recognized as a color acceptor after numerous individual and cross experiments, which is expected to high sensitivity of the heat-sensitive recording layer to energy exposure, urea-urethane compounds according to the formula (2) may be more such as color acceptors be described in which the induced by energy print image has a high stability against counterfeiting and environmental influences.
  • thermosensitive recording material which has a tendency of little background graying and has a heat-induced printed image resistant to environmental influences.
  • 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.
  • binders may 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.
  • polyvinyl alcohol in combination with acrylate copolymers are considered to be particularly preferred binders which are incorporated together in the heat-sensitive recording layer in a range of 12 to 21% by weight, based on the total weight of the recording layer.
  • the coating composition for forming the heat-sensitive recording layer may further contain lubricants and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as 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 20% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred.
  • the recording layer preferably has a whiteness in a range of 79 to 85% when using light with no UV content and a whiteness ranging from 87 to 93% when using UV light. Proportion measured in accordance with ISO 2469 / ISO 2470, but D65 light is used at a viewing angle of 8 °.
  • roller coater, knife coater, curtain coater or air brush are particularly suitable as coating apparatus for applying the heat-sensitive recording layer.
  • the coating composition used to form the recording layer is aqueous.
  • the subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.3 to 5.8 g / m 2 .
  • a pigmented intermediate layer is expediently arranged between the recording layer and the substrate of the heat-sensitive recording material according to the invention.
  • the intermediate layer is applied in a preferred embodiment with leveling coating devices, such as, for example, roller coater, doctor blade or doctor blade coaters, the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount necessarily applied to apply coating composition for the heat-sensitive recording layer.
  • leveling coating devices such as, for example, roller coater, doctor blade or doctor blade coaters
  • the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount necessarily applied to apply coating composition for the heat-sensitive recording layer.
  • For the basis weight of the intermediate layer a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
  • inorganic oil-absorbing pigments When inorganic oil-absorbing pigments are incorporated into the intermediate layer sandwiched between the recording layer and the substrate, these pigments can absorb the thermoset liquefied wax components of the thermosensitive recording layer in the typeface formation and thus promote still safer and faster operation of the thermally-induced recording, thus such an embodiment preferably applies.
  • the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, is having.
  • Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities.
  • the following inorganic pigments are also very well suited as constituents of the intermediate layer: silicon oxide, bentonite, calcium carbonate and aluminum oxide and, in particular, boehmite here. Also mixtures of several different types of inorganic pigments are conceivable.
  • the ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved when the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt .-% consists of inorganic pigment.
  • Pigment mixtures of different organic pigments are conceivable.
  • the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results.
  • a synthetic binder with the admixture of at least one natural polymer, more preferably starch, is a particularly suitable embodiment.
  • a non-surface treated base paper is to be understood as meaning a base paper which has not been treated in a size press or in a coating device.
  • a non-surface-treated, sized in the mass base paper with an inorganic pigment, in particular calcium carbonate is considered suitable in the mass.
  • films of, for example, polyolefin and polyolefin-coated papers as a substrate are possible to the same extent, without such an embodiment having an exclusive character.
  • a substrate is on a fourdrinier paper machine from bleached and ground hardwood and softwood pulps with the addition of 0.6 wt .-% (atro) resin size as engine sizing and other conventional admixtures, based on the total solids content (atro) of the pulp fed pulp, a backing paper having a basis weight of 53 g / m 2 made.
  • a calcined kaolin pigment, styrene-butadiene latex as a binder and, in addition to other aids, starch as cobinder-containing intermediate layer having a basis weight of 9 g / m 2 is applied using a doctor blade.
  • heat-sensitive recording layer which are not stated in percent and based on the total weight in% by weight (atro) include dispersants, defoamers, optical brighteners, thickeners, waxes and crosslinkers.
  • this ratio is 11: 1, which means that the very little amount of urea-urethane compound according to formula (2) relative to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl) Oxy-phenyl) urea according to formula (1) is used in the heat-sensitive recording layer.
  • this ratio is 1: 2, which means that a lot of urea-urethane compound of formula (2) in proportion to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea of the formula (1) is used in the heat-sensitive recording layer.
  • thermosensitive recording materials Upon completion of patterns of thermosensitive recording materials according to the two Comparative Examples 1 and 3 and Example 2 of the present invention, dynamic pressure densities and percent resistances to a 25% ethanol solution versus water and plasticizer are described in detail in the specification - created black and white checkered thermoprobaus réellee with a device of the type Atlantek 400 of the company Viex (USA), wherein a thermal head with resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 (dynamic printing densities) and 16 mJ / mm 2 (percent resistances) is used.

Landscapes

  • 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

The thermosensitive recording material comprises a substrate, color former and two color acceptors containing heat sensitive recording layer. A pigmented intermediate layer is formed between the substrate and the heat sensitive recording layer. The color acceptors are N-(p-toluenesulfonyl)-N'-(3-p- toluenesulfonyl-oxy-phenyl)urea and a urea-urethane compound, where the wt.% proportion of the N-(p-toluenesulfonyl)-N'-(3-p- toluenesulfonyl-oxy-phenyl)urea and the urea-urethane compound is 10:1-1:1.

Description

Die vorliegende Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial mit einem Substrat, optional einer auf das Substrat aufgebrachten pigmentierten Zwischenschicht sowie einer Farbbildner und Farbakzeptoren enthaltenden wärmeempfindlichen Aufzeichnungsschicht. Die vorliegende Erfindung betrifft genauso die Verwendung des derart vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials als Ticket bzw. als Fahrschein.The present invention relates to a thermosensitive recording material having a substrate, optionally a pigmented intermediate layer applied to the substrate, and a thermosensitive recording layer containing a color former and color acceptors. The present invention also relates to the use of the thus proposed heat-sensitive recording material as a ticket or as a ticket.

Wärmeempfindliche Aufzeichnungsmaterialien der eingangs beschriebenen Art mit beispielsweise einem Papierbogen, einem Synthesepapierbogen oder einer Kunststofffolie als Substrat sind seit den frühen Jahren chemisch reagierender Aufzeichnungsmaterialien bekannt und erfreuen sich einer ständig wachsenden Beliebtheit, was unter anderem darauf zurückzuführen ist, dass ihre Verwendung insbesondere als Ticket für den Ticketausgebenden mit großen Vorteilen verbunden ist. Weil die farbbildenden Komponenten bei dem wärmeempfindlichen Aufzeichnungsverfahren in dem Aufzeichnungsmaterial selbst stecken, können die Toner- und Farbkartuschen-freien Drucker, die in ihrer Funktion von niemandem mehr kontrolliert werden brauchen, in großer Zahl aufgestellt werden. So hat sich diese innovative Technologie insbesondere im öffentlichen Personenverkehr, bei Bussen und Bahnen genauso wie im Flugverkehr, an Stadion- und Museumskassen sowie bei Parkausweisgebern durchgesetzt.Heat-sensitive recording materials of the type described above with, for example, a sheet of paper, a synthetic paper sheet or a plastic film as a substrate are known since the early years of chemically reactive recording materials and enjoy a constantly growing popularity, which is due, inter alia, that their use in particular as a ticket for the Ticket issuing is associated with great benefits. Because the color-forming components are stuck in the recording material itself in the heat-sensitive recording method, the toner and color-cartridge-free printers, which in their function no longer need to be controlled by anyone, can be set up in large numbers. Thus, this innovative technology has prevailed especially in public passenger transport, buses and trains as well as in air traffic, stadium and museum funds and parking ticket issuers.

Mit dem Ziel, die wärmeempfindlichen Aufzeichnungsmaterialien insbesondere in ihrer Verwendung als Tickets hinsichtlich ihrer Resistenz gegenüber Umwelteinflüssen wie Wärme und Feuchtigkeit zu verbessern, flossen immer wieder Neuerungen in die zugrunde liegende Chemie und die Herstellungstechnik zur Erzeugung solcher Aufzeichnungsmaterialien ein.With the aim of improving the heat-sensitive recording materials, especially in their use as tickets, in terms of their resistance to environmental influences such as heat and moisture, innovations in the underlying chemistry and the production technique for producing such recording materials have always been incorporated.

Zur Steigerung der Beständigkeiten ausgebildeter Thermoausdrucke gegenüber Wasser, wässerigen Alkohollösungen und Weichmachern schlägt die DE10 2004 044 204A1 ein wärmeempfindliches Aufzeichnungsmaterial vor, dessen wärmeempfindliche Aufzeichnungsschicht übliche Farbstoffvorläufer sowie die Kombination eines phenolischen Farbentwicklers und eines Farbentwickler auf Hamstoff-Urethan-Basis aufweist.To increase the resistance of thermoformed prints to water, aqueous alcohol solutions and plasticizers suggests the DE10 2004 044 204A1 a heat-sensitive recording material, whose heat-sensitive recording layer has conventional dye precursors and the combination of a phenolic color developer and a urea-urethane-based color developer.

Hamstoff-Urethanverbindungen als Entwickler, die zur Steigerung der Druckdichte ausgebildeter Thermoausdrucke auch in Kombination allgemein mit Suffonylhamstoff verwendet werden können, sind aus der EP1 116 713A1 genauso wie aus der DE 692 04 777T2 bekannt, ohne dass diesen Schriften ein Hinweis auf die herausragende Wirkung des N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoffs zu entnehmen ist.Urea urethane compounds as developers which can be used to increase the print density of thermoformed prints also in combination generally with Suffonylhamstoff are from the EP1 116 713A1 as well as from the DE 692 04 777T2 It is not known that these documents refer to the outstanding effect of N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea.

Gegenstand der US2005/0148467 A1 ist ein wärmeempfindlichesAufzeichnungsmaterial, das zur Ausbildung eines irreversiblen Druckbildes mindestens die Komponenten zweier farbbildender Systeme enthält, wobei das eine System vom Chelat-Typ und das andere ein konventionelles Leuko-Farbstoff-System ist. Für einen ersten Entwickler werden eine Vielzahl von Sulfonylharnstoffen, unter anderem auch N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff, genannt, die in einer Ausführungsform in Kombination mit Harnstoff-Urethanverbindungen als zweiten Entwickler kombiniert werden können.Subject of the US2005 / 0148467 A1 is a thermosensitive recording material containing at least the components of two color forming systems to form an irreversible printed image, one being a chelate-type system and the other being a conventional leuco-dye system. For a first developer, a variety of sulfonylureas, including N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea, called in one embodiment in combination with urea urethane compounds can be combined as a second developer.

Nachteilig an den Aufzeichnungsmaterialien entsprechend den oben diskutierten Schriften ist insbesondere im ersten Fall eine zu geringe Weichmacherbeständigkeit, verbunden mit sehr geringer Weiße des Aufzeichnungsmaterials, sowie die viel zu aufwändigen Herstellungsprozesse, die den Gebrauch der Vorschläge im Alltag oft ausschließen.A disadvantage of the recording materials according to the writings discussed above is in particular in the first case too low plasticizer resistance, associated with very low whiteness of the recording material, as well as the much too complex manufacturing processes that often preclude the use of the proposals in everyday life.

Die vorliegende Erfindung hat deshalb die Aufgabe, ein insbesondere als Ticket und/oder als Fahrschein geeignetes wärmeempfindliches Aufzeichnungsmaterial zur Verfügung zu stellen, das aufgrund hoher Absatzmengen in einem heftig umkämpften Markt zu geringen Produktionskosten herstellbar sein muss und deshalb über einen einfachen Aufbau zu verfügen hat. Insbesondere soll das neue Aufzeichnungsmaterial keiner zusätzlichen Schutzschicht zur Abdeckung der wärmeempfindlichen Aufzeichnungsschicht bedürfen, weil eine solche Schutzschicht zu kostenintensiv sowohl hinsichtlich der dafür notwendigen Rohstoffe wie auch hinsichtlich der dafür notwendigen Maschinen und Prozessenergien ist. Gleichzeitig soll das neue Aufzeichnungsmaterial jedoch eine ausgezeichnete Beständigkeit gegenüber Ethanollösungen, Wasser und Weichmacher aufweisen. Auch werden an das neue Aufzeichnungsmaterial Anforderungen hinsichtlich einer guten Bestempelbarkarkeit und Entwertbarkeit gestellt, worunter im Sinne der dieser Erfindung zugrunde liegenden Aufgabe zu verstehen ist, dass aufgestempelte Entwerterzeichen nach ca. 10 Sekunden weder trocken noch genässt vollständig weggewischt werden können.The present invention therefore has the object to provide a suitable in particular as a ticket and / or as a ticket heat-sensitive recording material available, which must be produced due to high sales volumes in a fiercely competitive market at low production costs and therefore has to dispose of a simple structure. In particular, the new recording material should not require an additional protective layer for covering the heat-sensitive recording layer, because such a protective layer is too costly both in terms of the necessary raw materials as well as in terms of the necessary machinery and process energies. At the same time, however, the new recording material should have excellent resistance to ethanol solutions, water and plasticizers. Also, the new recording material requirements for good Bestempelbarkarkeit and Entwertbarkeit are made, which is to be understood in the sense of this invention underlying task that stamped Entwerterzeichen after about 10 seconds neither dry nor wet can be completely wiped away.

Die vorgegebene Aufgabe wird gelöst mit einem wärmeempfindlichen Aufzeichnungsmaterial, umfassend ein Substrat und eine Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht, wobei

  • ■ die Farbbildner ausgesucht sind aus der Liste, umfassend: 3-diethylamino-6 methyl-7-Anilinofluoran, 3-dibutylamin-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,
  • ■ die wärmeempfindliche Aufzeichnungsschicht zwei Farbakzeptoren aufweist, das sind: N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß der folgenden Formel (1):
    Figure imgb0001
     sowie eine Harnstoff-Urethan-Verbindung gemäß der folgenden Formel (2):
    Figure imgb0002
  • ■ wobei das auf Gew.-% in der warmeempfindlichen Aufzeichnungsschicht bezogene Verhältnis der beiden Farbakzeptoren N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1) zu der Harnstoff-Urethan-Verbindung gemäß Formel (2) in einem Bereich von 10 1 bis 1 : 1 liegt.
The object is achieved with a heat-sensitive recording material comprising a substrate and a thermosensitive recording layer containing color formers and color acceptors, wherein
  • ■ the color formers are selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamine-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 heat-sensitive recording layer has two color acceptors which are: N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea according to the following formula (1):
    Figure imgb0001
     and a urea-urethane compound according to the following formula (2):
    Figure imgb0002
  • Wherein the ratio of the two dye acceptors based on wt.% In the heat-sensitive recording layer N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1) to the urea Urethane compound according to formula (2) in a range of 10 1 to 1: 1.

Die vorliegende Erfindung erstreckt sich im gleichen Maße auf die Verwendung eines derart beschriebenen wärmeempfindlichen Aufzeichnungsmaterials als Ticket bzw. als Fahrschein.The present invention extends to the same extent to the use of such a heat-sensitive recording material described as a ticket or as a ticket.

Das wärmeempfindliche Aufzeichnungsmaterial it vorliegender Erfindung weist zur Kennzeichnung seiner Empfindlichkeit gegenüber zugeführter Thermoenergie durch einen Thermodruckkopf eine Druckdichte auf, die - ausgeführt mit einem Thermodruckkopf bei einer Auflösung von 300 dpi und einer Energie pro Flächeneinheit von 9 mJ/mm2 - bevorzugt in einem Bereich von 0,87 bis 1,07 ODU (= Optical Density Units, gemäß DIN 16536-1, Ausgabe Mai 1997) und ganz besonders bevorzugt in einem Bereich von 0,91 bis 1,03 ODU liegt.The thermosensitive recording material of the present invention has a print density for indicating its sensitivity to applied thermal energy by a thermal printhead, which is carried out with a thermal printhead at a resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 , preferably within a range of 0.87 to 1.07 ODU (= Optical Density Units, according to DIN 16536-1, May 1997 edition) and most preferably in a range from 0.91 to 1.03 ODU.

Zur messtechnischen Erfassung der Druckdichte wird ein schwarz/weiß kariert-gestalteter Thermoprobeausdruck mit einem Gerät der Type Atlantek 400 der Firma Printrex (USA) erstellt, wobei ein Thermokopf mit Auflösung von 300 dpi und einer Energie pro Flächeneinheit von 9 mJ/mm2 zum Einsatz kommt. Die Druckdichte selbst der schwarz gefärbten Flächen werden mit dem Densitometer Gretag MacBeth TYPE D19C NB/U gemessen (Fa Gretag MacBeth, 8105 Regensdorf, Schweiz), wobei für jeden Messwert die dynamischen Druckdichten an drei Stellen gemessen und aus den drei Einzelwerten das arithmetische Mittel gebildet wird.For metrological recording of the print density, a black-and-white checkered thermo-print print is made with an Atlantek 400 from Printrex (USA) using a thermal head with a resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 comes. The print density even of the black-colored areas are measured with the densitometer Gretag MacBeth TYPE D19C NB / U (Gretag MacBeth, 8105 Regensdorf, Switzerland), where the dynamic printing densities are measured at three points for each measured value and the arithmetic mean is formed from the three individual values becomes.

Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial weist bevorzugte Werte für die prozentuale Beständigkeit eines Thermoprobeausdruckes auf

  • in einem Bereich von 91,5% bis 96,5% und bevorzugt in einem Bereich von 92,5% bis 95,5% gegenüber einer 25%-tigen Ethanollösung,
  • in einem Bereich von 95,5% bis 99,5% und bevorzugt in einem Bereich von 96,5% bis 99,0% gegenüber Wasser,
  • in einem Beeich von 90,5% bis 95,5% und bevorzugt in einem Beeich von 91,5% bis 94,5% gegenüber Weichmacher (TESA®-Grafik-Film 57331).
The heat-sensitive recording material according to the invention has preferred values for the percentage resistance of a Thermoprobeausdruckes
  • in a range of 91.5% to 96.5% and preferably in a range of 92.5% to 95.5% over a 25% ethanol solution,
  • in a range from 95.5% to 99.5% and preferably in a range from 96.5% to 99.0% over water,
  • in a Beeich of 90.5% to 95.5% and preferably in a Beeich of 91.5% to 94.5% compared to plasticizer (TESA ® graphic film 57331).

Auch für die messtechnischen Erfassung der prozentualen Beständigkeit eines Thermoprobeausdruckes werden jeweils schwarz/weiß kariert-gestaltete Thermoprobeausdrucke mit einem Gerät der Type Atlantek 400 der Firma Printrex (USA) erstellt, wobei ein Thermokopf mit Auflösung von 300 dpi und einer Energie pro Flächeneinheit von 16 mJ/mm2 zum Einsatz kommt. Für jede Einzelbestimmung der prozentualen Beständigkeit eines Thermoprobeausdruckes gegenüber Ethanol oder Wasser wird zunächst bei einem Thermoprobeausdruck an drei Stellen die dynamischen Druckdichte der schwarz gefärbten Flächen mit dem Densitometer Gretag MacBeth TYPE D19C NB/U gemessen (Fa Gretag MacBeth, 8105 Regensdorf, Schweiz). Anschließend erfolgt die jeweilige Behandlung des Thermoprobeausdrucks.For the metrological recording of the percentage resistance of a Thermoprobeausdruckes each black / white checkered-designed Thermoprobeausdrucke with a device of the type Atlantek 400 made by Printrex (USA) created using a thermal head with resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used. For each individual determination of the percentage resistance of a Thermoprobeausdruckes against ethanol or water, the dynamic print density of the black-colored surfaces is first measured at a Thermoprobeausdruck at three points with the densitometer Gretag MacBeth TYPE D19C NB / U (Fa Gretag MacBeth, 8105 Regensdorf, Switzerland). Subsequently, the respective treatment of the Thermoprobeausdrucks.

Diese Behandlung sieht im Falle der prozentualen Beständigkeit gegenüber einer 25%-tigen Ethanollösung das Eintauchen des Thermoprobeausdruckes in ein Ethanolbad (25 Vol.-% Lösung, 23° C) über 20 Minuten vor. Der Ausdruck wird anschließend mit Löschpapier vorsichtig abgetupft und dann über 24 Stunden bei 23° und 50% Luftfeuchte ruhen lassen.This treatment, in the case of percent resistance to a 25% ethanol solution, provides immersion of the Thermoprobertextes in an ethanol bath (25 vol .-% solution, 23 ° C) over 20 minutes. The printout is then carefully blotted with blotting paper and allowed to rest for 24 hours at 23 ° and 50% humidity.

Im Falle der prozentualen Beständigkeit gegenüber Wasser wird der Thermoprobeausdruck über 20 Minuten in ein Wasserbad (entionisiertes Wasser, 23° C) gelegt. Abtupfen und ruhen lassen erfolgt anschließend wie bei der Ethanolbehandlung.In the case of percent resistance to water, the thermoprobe print is placed in a water bath (deionized water, 23 ° C) for 20 minutes. Dabing and resting is then carried out as in the ethanol treatment.

Nach dem Ruhen lassen erfolgt erneut die Bestimmung der dynamischen Druckdichte an drei Stellen der schwarz gefärbten Flächen mit dem Densitometer Gretag MacBeth TYPE D19C NB/U. Die jeweiligen Mittelwerte der Messungen vor/nach dem Bad in der Ethanollösung bzw. in Wasser werden gebildet und der Mittelwert nach dem Bad prozentual bezogen auf den Mittelwert vor dem Bad.After resting, the determination of the dynamic print density at three points of the black-colored areas is carried out again with the Gretag MacBeth TYPE D19C NB / U densitometer. The respective mean values of the measurements before / after the bath in the ethanol solution or in water are formed, and the average value after the bath as a percentage of the mean value before the bath.

Für jede Einzelbestimmung der prozentualen Beständigkeit eines Thermoprobeausdruckes gegenüber Weichmacher wird zunächst auf einen mittels Gerät der Type Atlantek 400 der Firma Printrex (USA) erstellten Thermoprobeausdruck ein ca. 10 cm langes Stück TESA®-Grafik-Film 57331 aufgeklebt. Anschließend wird unverzüglich an drei Stellen die dynamischen Druckdichte der schwarz gefärbten Flächen mit dem Densitometer Gretag MacBeth TYPE D19C NB/U gemessen. Der Ausdruck wird dann über 24 Stunden bei 23° und 50% Luftfeuchte ruhen lassen. Nach dem Ruhen lassen erfolgt erneut die Bestimmung der dynamischen Druckdichte an drei Stellen der schwarz gefärbten Flächen mit dem Densitometer Gretag MacBeth TYPE D19C NB/U. Die jeweiligen Mittelwerte der Messungen vor/nach dem ruhen lassen werden gebildet und der Mittelwert nach dem ruhen lassen bezogen auf den Mittelwert vor dem ruhen lassen.For each individual determination of the percentage resistance of a Thermoprobeausdruckes against plasticizer, a 10 cm long piece of TESA ® graphic film 57331 is first glued to a prepared by means of equipment type Atlantek 400 from Printrex (USA) Thermoprobeausdruck. Subsequently, the dynamic print density of the black-colored areas is measured immediately at three points using the densitometer Gretag MacBeth TYPE D19C NB / U. The print will then rest for 24 hours at 23 ° and 50% humidity. After resting, the determination of the dynamic print density at three points of the black-colored areas is carried out again with the Gretag MacBeth TYPE D19C NB / U densitometer. The respective mean values of the measurements before / after resting are formed and the average value after resting can be left to rest before the mean value.

In einer bevorzugten Ausführungsform ist es möglich, dass die wärmeempfindliche Aufzeichnungsschicht mehr als einen Farbbildner aufweist, jeweils ausgesucht aus den oben in Absatz [0009] aufgelisteten Farbbildnern. Das erfindungsgemäße Aufzeichnungsmaterial kann jedoch neben diesen als Fabbildner angegebenen Substanzen weiterhin auch eine oder mehrere der folgenden, im nahen Infrarot-Bereich absorbierenden Verbindungen enthalten:In a preferred embodiment, it is possible for the thermosensitive recording layer to comprise more than one color former, each selected from the color formers listed above in paragraph [0009]. However, the recording material according to the invention may, in addition to these substances specified as fabifiers, also contain one or more of the following compounds absorbing in the near infrared range:

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

In zahlreichen Versuchsreihen, die der vorliegenden Schrift zugrunde liegen, zeigte sich, dass das auf Gew.-% in der wärmeempfindlichen Aufzeichnungsschicht bezogene Verhältnis der beiden Farbakzeptoren N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-hamstoff gemäß Formel (1) zu der Harnstoff-Urethan-Verbindung gemäß Formel (2) zur Erzielung bester Ergebnisse idealerweise in einem ganz besonders bevorzugten Bereich von 5 : 1 bis 2,5 : 1 liegt. Zur Erzielung gewünschter Weißegrade der wärmeempfindlichen Aufzeichnungsschicht ist es notwendig, die Harnstoff-Urethan-Verbindungen gemäß Formel (2) vor ihrer Vermischung mit dem anderen Farbakzeptor und/oder mit anderen Komponenten der wärmeempfindlichen Aufzeichnungsschicht auf 60° C zu erwärmen und diese Wärmebehandlung 24 Stunden ununterbrochen fortzusetzen.Numerous experimental series on which the present specification is based showed that the ratio of the two dye acceptors, based on wt.% In the heat-sensitive recording layer, of N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy) phenyl) -urea according to formula (1) to the urea-urethane compound according to formula (2) for best results ideally in a most preferred range of 5: 1 to 2.5: 1. In order to obtain desired whiteness of the heat-sensitive recording layer, it is necessary to heat the urea-urethane compounds of the formula (2) to 60 ° C before blending with the other color acceptor and / or other components of the heat-sensitive recording layer, and to conduct this heat treatment continuously for 24 hours continue.

Bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, können die beiden Farbakzeptoren der Formel (1) und der Formel (2) bis zu 35 Gew.-%, bevorzugt jedoch einen Anteil in einem Bereich von 25 bis 30 Gew.-% der wärmeempfindlichen Aufzeichnungsschicht ausmachen, Der Effekt, den die Mischung aus den beiden Farbakzeptoren in ihrer Gesamtheit bewirkt, ist eine Kombination, die sich aus den Eigenheiten der beiden einzelnen Farbakzeptoren ergibt: Während N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1) als ein Farbakzeptor nach zahlreichen Einzel- und Kreuzversuchen erkannt wurde, der eine hohe Empfindlichkeit der wärmeempfindlichen Aufzeichnungsschicht auf Energieeinwirkung erwarten lässt, können Harnstoff-Urethan-Verbindungen gemäß der Formel (2) eher als solche Farbakzeptoren beschrieben werden, bei denen das durch Energieeinwirkung induzierte Druckbild eine hohe Stabilität gegenüber Fälschungsversuchen und Umwelteinflüssen aufweist. Werden beide Farbakzeptoren in einem Mischungsverhältnis in der Aufzeichnungsschicht eingesetzt, wie es von den Erfindern erkannt wurde, ist das Ergebnis ein schnell ansprechendes wärmeempfindliches Aufzeichnungsmaterial, das zu wenig Hintergrundvergrauung neigt und ein gegenüber Umwelteinflüssen stabiles Wärme induziertes Druckbild aufweist.Based on the total weight of the recording layer, the two dye acceptors of the formula (1) and the formula (2) can constitute up to 35% by weight, but preferably within the range of 25 to 30% by weight of the heat-sensitive recording layer. The effect that the mixture of the two color acceptors brings about in their entirety is a combination resulting from the peculiarities of the two individual color acceptors: While N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy -phenyl) urea according to formula (1) has been recognized as a color acceptor after numerous individual and cross experiments, which is expected to high sensitivity of the heat-sensitive recording layer to energy exposure, urea-urethane compounds according to the formula (2) may be more such as color acceptors be described in which the induced by energy print image has a high stability against counterfeiting and environmental influences. When both color acceptors are used in a compounding ratio in the recording layer as recognized by the present inventors, the result is a fast-response thermosensitive recording material which has a tendency of little background graying and has a heat-induced printed image resistant to environmental influences.

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, wobei die Bindemittel 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 in Verbindung mit Acrylat-Copolymere als besonders bevorzugte Bindemittel, die zusammen, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in einem Bereich von 12 bis 21 Gew.-% 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 binders may 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, polyvinyl alcohol in combination with acrylate copolymers are considered to be particularly preferred binders which are incorporated together in the heat-sensitive recording layer in a range of 12 to 21% by weight, based on the total weight of the recording layer.

Zur Vermeidung des Klebens an einem Thermokopf und zur Vermeidung einer übermäßigen Abnutzung des Thermokopfes kann die Beschichtungsmasse zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht weiterhin Gleit- und Trennmittel enthalten wie Metallsalze höherer Fettsäuren, zum Beispiel Zinkstearat, Kalziumstearat sowie Wachse, wie 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 20 Gew.-%, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in die Aufzeichnungsschicht eingebunden sein soll, als bevorzugt gilt.In order to prevent sticking to a thermal head and to prevent excessive wear of the thermal head, the coating composition for forming the heat-sensitive recording layer may further contain lubricants and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as 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 20% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred.

Zur Gewährleistung eines guten Kontrasts zwischen Schriftbild und unbeschrifteter Aufzeichnungsschicht weist die Aufzeichnungsschicht bevorzugt eine Weiße in einem Bereich von 79 bis 85 % bei Verwendung von Licht ohne UV-Anteil und eine Weiße in einem Bereich von 87 bis 93 % bei Verwendung von Licht mit UV-Anteil, gemessen nach ISO 2469 / ISO 2470, auf, wobei jedoch D65-Licht verwendet wird bei einem Betrachtungswinkel von 8°.To ensure a good contrast between the typeface and the unlabelled recording layer, the recording layer preferably has a whiteness in a range of 79 to 85% when using light with no UV content and a whiteness ranging from 87 to 93% when using UV light. Proportion measured in accordance with ISO 2469 / ISO 2470, but D65 light is used at a viewing angle of 8 °.

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

Zwischen der Aufzeichnungsschicht und dem Substrat des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials ist zweckmäßigerweise eine pigmentierte Zwischenschicht angeordnet. Ist die Zwischenschicht in einer bevorzugten Ausführungsform mit egalisierenden Beschichtungsvorrichtungen aufgetragen, wie sie beispielsweise Walzenstreichwerke, Streichmesser- oder (Roll-) Rakelstreichwerke darstellen, kann die Zwischenschicht ferner einen positiven Beitrag zur Egalisierung der Substratoberfläche leisten, womit sich die Menge an notwendigerweise aufzubringender Beschichtungsmasse für die wärmeempfindliche Aufzeichnungsschicht reduziert. Für die flächenbezogene Masse der Zwischenschicht hat sich ein bevorzugter Bereich zwischen 5 und 20 g/m2 und noch besser zwischen 7 und 12 g/m2 bewährt.Between the recording layer and the substrate of the heat-sensitive recording material according to the invention, a pigmented intermediate layer is expediently arranged. If the intermediate layer is applied in a preferred embodiment with leveling coating devices, such as, for example, roller coater, doctor blade or doctor blade coaters, the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount necessarily applied to apply coating composition for the heat-sensitive recording layer. For the basis weight of the intermediate layer, a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.

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

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

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

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

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

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

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

Die Erfindung soll anhand des folgenden Beispiels 2 und der beiden Vergleichsbeispiele 1 und 3 weiter verdeutlicht werden:The invention will be further illustrated by the following example 2 and the two comparative examples 1 and 3:

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

Auf diese pigmentierte Zwischenschicht wird mittels Rollrakel-Streicheinrichtung jeweils eine von drei verschiedenen wärmeempfindlichen Aufzeichnungsschichten mit einer jeweiligen flächenbezogenen Masse von 5,4 g/m2 aufgetragen. Die dazu verwendeten wässerigen Streichmassen enthalten die folgenden Komponenten nach den in Tabelle 1 wiedergegebenen Rezepturen:

  • Farbbildner (Fb): 3-dibutylamino-6-methyl-7-Anilinofluoran,
  • Farbakzeptor (Fa) 1: N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1),
  • Farbakzeptor (Fa) 2: Harnstoff-Urethan-Verbindung gemäß Formel (2),
  • Sensibilisator (Sb): Benzyl-naphthylether,
  • Bindemittel (Bm): Polyvinylalkohol,
  • Cobinder (Cb): Acrylat-Copolymere,
  • Pigment (Pm): Kalziumkarbonat
Tabelle 1: Angaben in Gew.-% (atro), bezogen auf das Gesamtgewicht der wärmeempfindlichen Aufzeichnungsschicht Vergleichsbeispiel 1 Erfindungsgemäßes Beispiel 2 Vergleichsbeispiel 3 Fb (ODB-2) 9 9 9 Fa 1 (Pergafast® 201, Bezug: CIBA) 25,7 22,4 9,3 Fa 2 (UU, Bezug: Asahi) 2,3 5,6 18,7 Sb (BNE) 20 20 20 Bm (PVA) 7 7 7 Cb 6 6 6 Pm (Kalziumkarbonat) 15 15 15 In each case one of three different heat-sensitive recording layers with a respective basis weight of 5.4 g / m 2 is applied to this pigmented intermediate layer by means of a roller doctor coater. The aqueous coating compositions used for this purpose contain the following components according to the formulations reproduced in Table 1:
  • Color former (Fb): 3-dibutylamino-6-methyl-7-anilinofluoran,
  • Color acceptor (Fa) 1: N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1),
  • Color acceptor (Fa) 2: urea-urethane compound according to formula (2),
  • Sensitizer (Sb): benzyl naphthyl ether,
  • Binder (Bm): polyvinyl alcohol,
  • Cobinder (Cb): acrylate copolymers,
  • Pigment (Pm): calcium carbonate
<u> Table 1: </ u> Data in wt .-% (atro), based on the total weight of the heat-sensitive recording layer Comparative Example 1 Inventive Example 2 Comparative Example 3 Fb (ODB-2) 9 9 9 Fa 1 (Pergafast ® 201, reference: CIBA) 25.7 22.4 9.3 Fa 2 (UU, cover: Asahi) 2.3 5.6 18.7 Sb (GNI) 20 20 20 Bm (PVA) 7 7 7 cb 6 6 6 Pm (calcium carbonate) 15 15 15

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

Bei dem erfindungsgemäßen Beispiel 2 liegt das auf die Gew.-% (atro) bezogene Verhältnis Farbakzeptor (Fa) 1 = N-(p-toluensulphonyl)-N'-3-(p-toluen-sulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1) : Farbakzeptor (Fa) 2 = Harnstoff-Urethan-Verbindung gemäß Formel (2) innerhalb der wärmeempfindlichen Aufzeichnungsschicht bei 4 : 1 und somit inmitten des hier besonders bevorzugten Bereichs. Bei dem Vergleichsbeispiel 1 liegt dieses Verhältnis bei 11 : 1, was bedeutet, das sehr wenig an Harnstoff-Urethan-Verbindung gemäß Formel (2) im Verhältnis zu N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1) in der wärmeempfindlichen Aufzeichnungsschicht eingesetzt wird. Bei dem Vergleichsbeispiel 3 liegt dieses Verhältnis bei 1 : 2, was bedeutet, das sehr viel an Harnstoff-Urethan-Verbindung gemäß Formel (2) im Verhältnis zu N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1) in der wärmeempfindlichen Aufzeichnungsschicht eingesetzt wird.In Example 2 according to the invention, the ratio (% by weight) of the color acceptor (Fa) 1 = N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1): color acceptor (Fa) 2 = urea-urethane compound according to formula (2) within the heat-sensitive recording layer at 4: 1 and thus within the range particularly preferred herein. In Comparative Example 1, this ratio is 11: 1, which means that the very little amount of urea-urethane compound according to formula (2) relative to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl) Oxy-phenyl) urea according to formula (1) is used in the heat-sensitive recording layer. In Comparative Example 3, this ratio is 1: 2, which means that a lot of urea-urethane compound of formula (2) in proportion to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea of the formula (1) is used in the heat-sensitive recording layer.

Nach Fertigstellung von Mustern wärmeempfindlicher Aufzeichnungsmaterialien gemäß der zwei Vergleichsbeispiele 1 und 3 und des erfindungsgemäßen Beispiels 2 werden zur Bestimmung der dynamischen Druckdichten und der prozentualen Beständigkeiten gegenüber einer 25%-tigen Ethanollösung, gegenüber Wasser und gegenüber Weichmacher - wie weiter oben in der Beschreibung ausführlich beschrieben - schwarz/Weiß kariert-gestaltete Thermoprobeausdrucke mit einem Gerät der Type Atlantek 400 der Firma Printrex (USA) erstellt, wobei ein Thermokopf mit Auflösung von 300 dpi und einer Energie pro Flächeneinheit von 9 mJ/mm2 (dynamische Druckdichten) bzw. von 16 mJ/mm2 (prozentuale Beständigkeiten) zum Einsatz kommt. Die jeweilige Druckdichte selbst der schwarz gefärbten Flächen werden mit dem Densitometer Gretag MacBeth TYPE D19C NB/U (Fa Gretag MacBeth, 8105 Regensdorf, Schweiz) gemessen. Es ergeben sich die folgenden Messwerte It. Tabelle 2. Tabelle 2: Vergleichsbeispiel 1 Erfindungsgemäßes Beispiel 2 Vergleichsbeispiel 3 dynamische Druckdichte [ODU] 1,09 0,97 0,80 prozentuale Beständigkeit gegenüber einer 25%-tigen Ethanollösung [%] 89 94 95 prozentuale Beständigkeit gegenüber Wasser [%] 97 98 99 prozentuale Beständigkeit gegenüber Weichmacher [%] 76 93 95 Weiße* [%] 81,7 81,1 81,3 * gemessen nach ISO 2469 / ISO 2470 unter Verwendung von D65-Licht ohne UV-Anteil bei einem Betrachtungswinkel von 8° Upon completion of patterns of thermosensitive recording materials according to the two Comparative Examples 1 and 3 and Example 2 of the present invention, dynamic pressure densities and percent resistances to a 25% ethanol solution versus water and plasticizer are described in detail in the specification - created black and white checkered thermoprobausdrucke with a device of the type Atlantek 400 of the company Printrex (USA), wherein a thermal head with resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 (dynamic printing densities) and 16 mJ / mm 2 (percent resistances) is used. The respective print density even of the black colored areas are measured with the Gretag MacBeth TYPE D19C NB / U densitometer (Gretag MacBeth, 8105 Regensdorf, Switzerland). This results in the following measured values It. Table 2. <u> Table 2: </ u> Comparative Example 1 Inventive Example 2 Comparative Example 3 dynamic printing density [ODU] 1.09 0.97 0.80 Percent resistance to a 25% ethanol solution [%] 89 94 95 Percent resistance to water [%] 97 98 99 percent plasticizer resistance [%] 76 93 95 White * [%] 81.7 81.1 81.3 * measured according to ISO 2469 / ISO 2470 using D65 light without UV content at a viewing angle of 8 °

In aufwendigen Marktanalysen zeigt sich, dass wärmeempfindliche Aufzeichnungsmaterialien gemäß Vergleichsbeispiel 1 als zu wenig lagerbeständig innerhalb von Einsteckhüllen mit Weichmachern, aber auch als zu wenig beständig gegenüber Ethanol angesehen werden, während die dynamische Druckdichte als hervorragend angesehen wird. Auf der anderen Seite wird die dynamische Druckdichte von wärmeempfindlichen Aufzeichnungsmaterialien gemäß Vergleichsbeispiel 3 als eindeutig zu gering charakterisiert. Einzig wärmeempfindliche Aufzeichnungsmaterialien gemäß des erfindungsgemäßen Beispiels 2 überzeugen hinsichtlich Empfindlichkeit und Beständigkeit gegenüber Umwelteinflüssen. Auch wird eine ausreichend große Bestempelbarkeit und Entwertbarkeit festgestellt.Extensive market analyzes show that heat-sensitive recording materials according to Comparative Example 1 are regarded as having insufficient storage stability within plastic-coated envelopes, but also being insufficiently resistant to ethanol, while the dynamic printing density is considered excellent. On the other hand, the dynamic printing density of heat-sensitive recording materials according to Comparative Example 3 is characterized as clearly too low. Only heat-sensitive recording materials according to Example 2 of the invention are convincing in terms of sensitivity and resistance to environmental influences. Also, a sufficiently large stampability and Desertability is found.

Das obige erfindungsgemäße Beispiel sowie die beiden Vergleichsbeispiele belegen, dass erfindungsgemäße wärmeempfindliche Aufteichnungsmaterialien die an sie gestellten Anforderungen überzeugend erfüllen können.The above example according to the invention as well as the two comparative examples show that heat-sensitive Aufteichnungsmaterialien invention can meet the demands placed on them convincing.

Claims (7)

  1. Heat-sensitive recording material having a substrate and also having a heat-sensitive recording layer comprising colour formers and colour acceptors,
    characterised in that
    ■ the colour formers are selected from the list consisting of: 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 heat-sensitive recording layer comprises two colour acceptors, which are: N-(p-toluenesulphonyl)-N'-3-(p-toluenesulphonyl-oxy-phenyl)-urea in accordance with the following formula (1):
    Figure imgb0007
     and also a urea-urethane compound in accordance with the following formula (2):
    Figure imgb0008
    ■ the ratio of the two colour acceptors N-(p-toluenesulphonyl)-N'-3-(p-toluenesulphonyl-oxy-phenyl)-urea according to formula (1) to the urea-urethane compound according to formula (2), based on % by weight in the heat-sensitive recording layer, is in a range of from 10 : 1 to 1 : 1.
  2. Heat-sensitive recording material according to patent claim 1, characterised in that the dynamic printing density of a thermal test print carried out using a thermal printing head at a resolution of 300 dpi and an energy per unit area of 9 mJ/mm2 is in a range of from 0.91 to 1.03 ODU.
  3. Heat-sensitive recording material according to either one of patent claims 1 and 2, characterised in that the percentage stability of a thermal test print carried out using a thermal printing head at a resolution of 300 dpi is
    - with respect to 25 % ethanol solution in a range of from 91.5 % to 96.5 %,
    - with respect to water in a range of from 95.5 % to 99.5 %,
    - with respect to plasticiser (TESA® Grafik film 57331) in a range of from 90.5 % to 95.5 %.
  4. Heat-sensitive recording material according to any one of patent claims 1 to 3, characterised in that the recording layer has a whiteness in a range of from 79 to 85 % using light without a UV component, measured in accordance with ISO 2469/ISO 2470 using D65 light at a viewing angle of 8°.
  5. Heat-sensitive recording material according to patent claim 4, characterised in that the recording layer has a whiteness in a range of from 87 to 93 % using light with a UV component, measured in accordance with ISO 2469/ISO 2470 using D65 light at a viewing angle of 8°.
  6. Heat-sensitive recording material according to any one of patent claims 1 to 5, characterised in that a pigmented intermediate layer is provided between the substrate and the heat-sensitive recording layer.
  7. Use of a heat-sensitive recording material having a substrate and also having a heat-sensitive recording layer comprising colour formers and colour acceptors as a ticket or a travel pass, wherein
    ■ the colour formers are selected from the list consisting of: 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 heat-sensitive recording layer comprises two colour acceptors, which are: N-(p-toluenesulphonyl)-N'-3-(p-toluenesulphonyl-oxy-phenyl)-urea in accordance with the following formula (1):
    Figure imgb0009
     and also a urea-urethane compound in accordance with the following formula (2):
    Figure imgb0010
    ■ the ratio of the two colour acceptors N-(p-toluenesulphonyl)-N'-3-(p-toluenesulphonyl-oxy-phenyl)-urea according to formula (1) to the urea-urethane compound according to formula (2), based on % by weight in the heat-sensitive recording layer, is in a range of from 10 : 1 to 1 : 1.
EP07017264A 2007-09-04 2007-09-04 Heat-sensitive recording material Active EP2033800B1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP07017264A EP2033800B1 (en) 2007-09-04 2007-09-04 Heat-sensitive recording material
AT07017264T ATE458620T1 (en) 2007-09-04 2007-09-04 HEAT SENSITIVE RECORDING MATERIAL
ES07017264T ES2339166T3 (en) 2007-09-04 2007-09-04 HEAT SENSITIVE RECORDING MATERIAL.
DE502007002944T DE502007002944D1 (en) 2007-09-04 2007-09-04 Heat-sensitive recording material
US12/231,653 US8198212B2 (en) 2007-09-04 2008-09-04 Heat-sensitive recording material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07017264A EP2033800B1 (en) 2007-09-04 2007-09-04 Heat-sensitive recording material

Publications (2)

Publication Number Publication Date
EP2033800A1 EP2033800A1 (en) 2009-03-11
EP2033800B1 true EP2033800B1 (en) 2010-02-24

Family

ID=38917830

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07017264A Active EP2033800B1 (en) 2007-09-04 2007-09-04 Heat-sensitive recording material

Country Status (5)

Country Link
US (1) US8198212B2 (en)
EP (1) EP2033800B1 (en)
AT (1) ATE458620T1 (en)
DE (1) DE502007002944D1 (en)
ES (1) ES2339166T3 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101101135B1 (en) * 2008-10-01 2012-01-05 삼성엘이디 주식회사 Light Emitting Diode Package Using Liquid Crystal Polymer

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5246906A (en) * 1991-08-02 1993-09-21 Oji Paper Co., Ltd. Thermosensitive recording material
CN1243728C (en) * 1998-09-04 2006-03-01 旭化成株式会社 Novel color-developing compound and recording material
EP1243437B1 (en) 2001-03-23 2004-11-17 Ricoh Company, Ltd. Leuco dye dispersion liquid and thermosensitive recording material using the same
FI110677B (en) * 2001-10-12 2003-03-14 Jujo Thermal Oy Heat-sensitive recording material for use in, e.g. stickers, has coating layer comprising chelate-type color forming system and leuco dye with urea-based developer
DE102004004204A1 (en) 2004-01-27 2005-08-11 Mitsubishi Hitec Paper Bielefeld Gmbh Heat-sensitive recording material for fax machines and thermal printers, has recording layer with sensitiser, pigment, binder, color formers and a color developer comprising Bisphenol A and a urea-urethane compound

Also Published As

Publication number Publication date
US20090088321A1 (en) 2009-04-02
US8198212B2 (en) 2012-06-12
EP2033800A1 (en) 2009-03-11
ES2339166T3 (en) 2010-05-17
ATE458620T1 (en) 2010-03-15
DE502007002944D1 (en) 2010-04-08

Similar Documents

Publication Publication Date Title
EP2033799B1 (en) Heat-sensitive recording material
DE60218221T2 (en) HEAT-SENSITIVE RECORDING MATERIAL
EP3305538A1 (en) Heat sensitive recording material
WO2011067004A1 (en) Heat-sensitive recording material with barrier coating
EP2279877B1 (en) Heat sensitive recording material
DE60216456T2 (en) HEAT-SENSITIVE RECORDING MATERIAL
DE60222210T2 (en) Heat-sensitive recording material
EP2033801B1 (en) Heat sensitive recording material
DE60315695T2 (en) HEAT-SENSITIVE RECORDING MEDIUM
DE102004004204A1 (en) Heat-sensitive recording material for fax machines and thermal printers, has recording layer with sensitiser, pigment, binder, color formers and a color developer comprising Bisphenol A and a urea-urethane compound
EP2033800B1 (en) Heat-sensitive recording material
EP2112000B1 (en) Heat sensitive recording material
EP2329955B1 (en) Heat-sensitive recording material with authenticity characteristic
DE102006050420B3 (en) Heat-sensitive recording material, useful for printing tickets, has recording layer containing fluoran derivative color former and sulfonyl-urea and diphenyl sulfone derivative dye acceptors
EP2765007B1 (en) Heat-sensitive recording material
DE202020005616U1 (en) A thermosensitive recording material comprising phenol-free organic color developers
EP2505374B1 (en) Heat-sensitive recording material, method for its manufacture and application
EP1925459B1 (en) Method of producing a heat-sensitive recording material with authentification feature
DE60123722T2 (en) Heat-sensitive recording material
DE102016219569A1 (en) Heat-sensitive recording material
EP2414173B1 (en) Heat-sensitive recording material
DE60103480T2 (en) Heat-sensitive recording material
EP2480415B1 (en) Heat-sensitive recording material with reverse face coating
DE10392446T5 (en) Thermal recording material for offset printing
DE102016219567A1 (en) Heat-sensitive recording material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

17P Request for examination filed

Effective date: 20090911

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502007002944

Country of ref document: DE

Date of ref document: 20100408

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2339166

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20100224

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20100224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100624

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100524

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

26N No opposition filed

Effective date: 20101125

BERE Be: lapsed

Owner name: MITSUBISHI HITEC PAPER FLENSBURG G.M.B.H.

Effective date: 20100930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100825

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100224

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 458620

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120904

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502007002944

Country of ref document: DE

Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH, DE

Free format text: FORMER OWNER: MITSUBISHI HITEC PAPER FLENSBURG GMBH, 24941 FLENSBURG, DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH

Effective date: 20181108

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20181105 AND 20181107

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230920

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230922

Year of fee payment: 17

Ref country code: DE

Payment date: 20230928

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20231002

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230927

Year of fee payment: 17