EP1333991B1 - Heat-sensitive recording sheet and use of the same - Google Patents

Heat-sensitive recording sheet and use of the same Download PDF

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Publication number
EP1333991B1
EP1333991B1 EP01983538A EP01983538A EP1333991B1 EP 1333991 B1 EP1333991 B1 EP 1333991B1 EP 01983538 A EP01983538 A EP 01983538A EP 01983538 A EP01983538 A EP 01983538A EP 1333991 B1 EP1333991 B1 EP 1333991B1
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EP
European Patent Office
Prior art keywords
recording sheet
sheet according
protective layer
range
heat
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.)
Expired - Lifetime
Application number
EP01983538A
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German (de)
French (fr)
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EP1333991A1 (en
Inventor
Jutta Berndt
Matthias Marx
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi HiTech Paper Flensburg GmbH
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Mitsubishi HiTech Paper Flensburg GmbH
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Publication of EP1333991A1 publication Critical patent/EP1333991A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds

Definitions

  • the invention relates to a heat-sensitive recording sheet with a Substrate, a heat-sensitive recording layer containing color formers and color acceptors and a protective layer formed on the recording layer, which as a binder is a water-insoluble, self-crosslinking acrylic polymer, a crosslinking agent and contains as a pigment an alkaline bentonite, as well as its Use as a ticket.
  • a binder is a water-insoluble, self-crosslinking acrylic polymer, a crosslinking agent and contains as a pigment an alkaline bentonite, as well as its Use as a ticket.
  • a heat recording sheet of the type mentioned is known from WO 97-18091 A 1 and also from WO 98-43824 A 1 .
  • the protective layer of the known heat recording sheet contains not only water-insoluble but also water-soluble binder.
  • a pigment content of 12 to 20% by weight is to be provided, which can consist predominantly of alkaline digested bentonite
  • the pigment content of the protective layer according to the teaching of the second document is between greater than 20 and 40% by weight. , 15 to 30% by weight of bentonite, in particular of an alkaline digested bentonite.
  • a crosslinking aid can be contained in the protective layer, the proportion of which, based on the total weight of the protective layer, is 1 to 2% by weight in the case of the first document and 1 to 5% by weight in the case of the second document is.
  • a protective layer is known from US-A-4,682,192 which serves to protect a heat-sensitive recording layer applied to a substrate.
  • the protective layer contains a colloidal inorganic silicate, which is incorporated either in the absence or in a mixture with a water-soluble or very poorly water-soluble high molecular compound.
  • the colloidal inorganic silicate is selected from colloidal magnesium aluminum silicates and fluorine-containing colloidal magnesium silicates, bentonite, attapulgite and dimonite being disclosed in particular. Further references to special properties of the silicates are not disclosed in the writing.
  • Self-crosslinking acrylic polymers are proposed as poorly water-soluble high-molecular compounds.
  • the mixing ratio of the said silicates and the sparingly water-soluble high molecular weight polymers is generally in the range between 1: 0.1 and 1:10, a ratio between 1: 1 and 1: 5 being given as the preferred range.
  • a protective layer is known from EP-A-0 344 705 , in which 0.5 to 3 parts by weight of pigment are present per part by weight of binder.
  • Suitable binders for the protective layer include polyvinyl alcohol, carboxymethyl cellulose, starch and starch derivatives and copolymer emulsions of styrene-butadiene, vinyl acetate-ethylene, vinyl acetate-vinyl chloride-ethylene and methacrylate-butadiene.
  • Precipitated calcium carbonate, ground calcium carbonate, talc, kaolin, silicon dioxide anhydride, magnesium carbonate, zinc oxide, aluminum oxide and aluminum hydroxide in addition to organic pigments are mentioned as suitable pigments.
  • Protective layers containing pigment, which only contain water-soluble binder, are described as examples.
  • EP-B-0 373 903 relates to a heat-sensitive recording paper with an internal adhesive strength of 2.5 kg.cm or more, which has a protective layer with a smoothness of at least 500 Bekk seconds, preferably from 700 to 1500 Bekk seconds, on a fine particle of a styrene-acrylate polymer and an intermediate layer containing a binder is applied.
  • Suitable binders for the protective layer are both water-soluble and water-insoluble high polymers with sufficient film-forming capacity. Any pigment addition to the protective layer is also disclosed, but there is no indication in the document of the nature of the suitable pigments.
  • the new recording sheet must be distinguished by a high level of environmental resistance, which in the sense of the invention means the outstanding resistance of the heat-sensitive recording sheet to water and to plasticizers.
  • An essential aspect of the new recording sheet must be its cost-effective production method.
  • Another object of the invention is to develop a recording sheet which, in addition to the range of requirements mentioned above, has good validability and good printability in the flexographic and wet offset printing processes, at least on its side provided with the heat-sensitive recording layer.
  • a heat-sensitive recording sheet has good validity in the sense of this invention, if one consisting of coloring pigments, not solvent-based stamping ink immediately after printing, neither dry nor can be wiped completely wet from the recording sheet.
  • water-insoluble binders used in the description and claims means those which are in the form of aqueous dispersions / latices of polymers or copolymers. Crosslinking agents are not included in the binders in the context of the present invention.
  • the basis of the new recording sheet is the highly cleaned alkaline one Bentonite, as an inorganic pigment alone or in the mixing ratio according to the invention with other inorganic pigments in the protective layer.
  • the Self-adhesion of this bentonite requires a completely new composition of the protective layer, which differ in the ratio of binder to pigment and crosslinking agent according to the invention precipitates to binders.
  • the choice of binder comes into play meaning essential to the invention than only by reaching for a self-cross-linking Acrylic polymer as the sole binder and used in a certain ratio with pigment on the one hand and crosslinking agent on the other hand the production of a recording sheet succeeds after its smoothness adjustment according to the invention meets all required technological requirements.
  • acrylic polymer is to be understood as a self-crosslinking binder, selected from the group comprising styrene-acrylic acid ester copolymer Copolymer of styrene / acrylic acid ester containing acrylamide groups and preferred a copolymer based on acrylonitrile, methacrylamide and acrylic ester.
  • the Smoothing the new recording sheet by treating it with a smoothing device, for example, a calender. Due to the fact that the protective layer of the new recording sheet is formed in one layer, the subject of the invention also meet the required economic conditions.
  • the recording sheet according to the invention has a pigment portion in the protective layer which, owing to the choice of the highly purified alkaline bentonite as pigment, makes the new recording sheet relatively protective even with protective layers
  • Area-related mass guarantee both good devaluability and good printability, which can be explained, among other things, by the large inner surface and the large micropore volume of the highly purified alkaline-processed bentonite.
  • a series of experiments showed that natural or precipitated calcium carbonate, kaolin or titanium oxide also make a positive contribution to improving the absorption of printing and stamping ink, but the total proportion of bentonite compared to the other inorganic pigments must not be less than 80% by weight.
  • the positive influence of aluminum oxide and aluminum-modified silica on the printing and stamp ink absorption could also be demonstrated, provided that the total proportion of bentonite compared to the other inorganic pigments does not fall below 80% by weight.
  • Crosslinking agent is more than 5 wt .-% bundling agent furthermore, a high level even with protective layers with a relatively low area-related mass Given the new sheet's environmental resistance.
  • the bentonite in powder form has an area-edge ratio in a range between 15 and 70, in particular in a range between 20 and 50.
  • the crosslinking agent / binder ratio is in a range between 1: 5 and 1:40, preferably in a range between 1: 5 and 1:20 or even better in a range between 1: 5 and 1:10, whereby particularly favorable test results were found with a crosslinking agent / binder ratio in a range between 1: 5 and 1: 7.
  • the protective layer Based on a smoothness of the protective layer of at least 900 Bekk seconds a further increase in barcode readability in the recording sheet according to the invention, if the protective layer becomes smooth in one area due to strong calendering from 1200 to 5500 Bekk seconds.
  • the protective layer is smooth in one Has a range greater than 1500 to 2500 Bekk seconds, as well as excellent Barcode readability and compliance with all other technological and economic Demands also a pleasant and particularly even appearance of the new heat-sensitive recording sheet.
  • the aim is to form the cover layer with the smallest possible area-related mass, but at the same time the contradictory requirements of high environmental resistance as well as good devaluability and good printability in flexo and wet Offset printing processes are to be fulfilled. While the high level of environmental resistance requires a top layer with the largest possible area-related mass and high binding and crosslinking agent content, the demand for good devaluability and printability is aimed at a top layer with the largest possible area-related mass and high pigment content, which above all contradicts good barcode readability.
  • a recording sheet which meets all the requirements ideally has a mass per unit area of the protective layer in a range from 1.0 to 4.0 g / m 2 , preferably in a range from 1.5 to 3.0 g / m 2 and very particularly preferably in a range from 1.8 to 2.5 g / m 2 .
  • the specified protective layers can be heat-sensitive recording layers can be applied directly to the substrate
  • the substrate and the heat-sensitive recording layer can be preferred according to one Embodiment also applied to such heat-sensitive recording sheets in which between the substrate and the heat-sensitive recording layer still an intermediate layer is formed, which is preferably oil-absorbent contains inorganic pigment.
  • an intermediate layer can be a positive one Contribute to the leveling of the substrate surface, which increases the amount necessary coating color for the heat-sensitive recording layer reduced
  • the pigments of this intermediate layer take the wax components of the heat-sensitive recording layer liquefied by the action of heat in the formation of typefaces and thus favor a safe and Fast functioning of the heat-induced recording.
  • the recording sheet according to the invention preferably has a backside coating which is applied to the substrate side which is opposite to the side provided with the heat-sensitive recording layer.
  • a backside coating is proposed, for example, in DE-A-197 48 258 and then serves to improve the printability of the recording sheet on the backside in the offset and flexographic printing process and to improve the blocking effect of the backside against plasticizers, oils and greases.
  • a pigmented intermediate layer which is designed in accordance with a proposal of the as yet unpublished DE 100 21 896 for the formation of authenticity-proofing markings in locally different thicknesses, offers itself as a security feature for the new recording sheet.
  • the protective layer be the metal salt of a long chain fatty acid, especially stearic acid, contains as a lubricant.
  • a zinc stearate is preferably used as a lubricant in the protective layer Amount less than 20, in particular less than 15 parts by weight, based on a total of 100 Parts by weight of the protective layer.
  • the protective layer is produced using an aqueous coating slip, in addition to the pigments, binders, crosslinking agents and Lubricants still contains conventional coating aids and additives, such as. B. dispersants, Defoamers and metal salts to accelerate the crosslinking of the crosslinking agents with a lot of these coating aids of no more than together 10 parts by weight, preferably not more than 7 parts by weight, based on the total 100 parts by weight of the protective layer.
  • a paper web made of bleached and ground hardwood and softwood cellulose with a mass per unit area of 67 g / m 2 is added to the substrate on a Fourdrinier paper machine with the addition of conventional admixtures in customary amounts.
  • a calcined kaolin as a pigment, styrene-butadiene latex as a binder and starch as a cobinder are applied to the front in addition to an additional intermediate layer of 8 g / m 2 .
  • a heat-sensitive recording layer containing color formers and color acceptors and having a mass per unit area of 5.4 g / m 2 is applied to the intermediate layer.
  • a protective layer of 2 g / m 2 is applied to the dried recording layer.
  • the pigment used is a highly purified, alkaline-processed bentonite with a platelet structure, the inherent adhesion of which enables it to be fixed with little need for binding agents, and the specific surface area of which, in the non-dispersed state, is given as 85 m 2 / g with an area-to-edge ratio which is in powder form Bentonite is in a range between 20 and 50.
  • a binder / pigment ratio of 6: 1 and a crosslinking agent / binder ratio of 1: 5 are set.
  • Polyamide-epichlorohydrin resin is used as the crosslinking agent, and the aqueous dispersion of a self-crosslinking copolymer of acrylonitrile, methacrylamide and acrylic ester is used as the binder.
  • the coating slip for the production of the protective layer contains, as further components, a defoamer, stearic acid as a lubricant and various dispersants, on the one hand for the pigment and on the other hand for the lubricant.
  • the applied coating slip is dried and the recording sheet produced so far smoothed using a calender, with a smoothness of 2200 Bekk seconds is achieved.
  • the recording sheet produced in this way which is inexpensive to produce compared to its requirement profile, can be printed well in the flexographic and wet offset printing processes and has good devaluability.
  • the water resistance is recorded as the ratio of two measurements of the dynamic pressure density determined using the Macbeth RD 914 from Karl Schröder KG (Korrillonstrasse 32, D-69469 Weinheim).
  • a sample of the recording sheet according to the invention is provided with a typeface using a TP 3000-300 thermal printer from Charles Richiger AG, Mechanical Engineering (Bernstrasse 81, CH-3613 Steffisburg). After a first measurement of the dynamic printing density, the sample of the recording sheet according to the invention is immersed in water for 60 minutes.
  • the dynamic print density is then measured a second time.
  • the water resistance of the recording sheet according to the invention examined in this way can be described as very good given a quotient of both measured values of 94%.
  • the new recording sheet receives a heat-induced barcode using a 300dpi BOCA printer, type Micro 21 from Boca tickets & printers (Vlietweg 17, NL-2266 KA Leidschendam).
  • the printed image is viewed visually and rated good in terms of sharpness and color density.

Abstract

The invention relates to a heat-sensitive recording sheet comprising a substrate, a heat-sensitive recording layer and a protective layer which is provided on the recording layer and which contains pigment. At least 80 wt. % of the pigment of the protective layer is formed from a highly purified bentonite treated with alkaline, the bonding agent of the protective layer consists of a water-insoluble, self-crosslinking acryl polymer, the bonding agent/pigment ratio is between 7:1 and 9:1, the crosslinking agent/bonding agent ratio is higher than 1:5, and the protective layer comprises Bekk smoothness of at least 900 seconds.

Description

Die Erfindung betrifft einen wärmeempfindlichen Aufzeichnungsbogen mit einem Substrat, einer Farbbildner und Farbakzeptoren enthaltenden wärmeempfindlichen Aufzeichnungsschicht und einer auf der Aufzeichnungsschicht ausgebildeten Schutzschicht, die als Bindemittel ein wasserunlösliches, selbstvernetzendes Acrylpolymer, ein Vernetzungsmittel und als Pigment einen alkalisch aufbereiteten Bentonit enthält, sowie seine Verwendung als Ticket.The invention relates to a heat-sensitive recording sheet with a Substrate, a heat-sensitive recording layer containing color formers and color acceptors and a protective layer formed on the recording layer, which as a binder is a water-insoluble, self-crosslinking acrylic polymer, a crosslinking agent and contains as a pigment an alkaline bentonite, as well as its Use as a ticket.

Ein Wärmeaufzeichnungsbogen der eingangs genannten Art ist aus der WO 97-18091 A 1 und genauso aus der WO 98-43824 A 1 bekannt. Entsprechend beider Schriften enthält die Schutzschicht des bekannten Wärmeaufzeichnungsbogens jeweils neben wasserunlöslichem auch wasserlösliches Bindemittel. Während gemäß der Lehre der ersten Schrift ein Pigmentanteil von 12 bis 20 Gew.-% vorzusehen ist, der überwiegend aus alkalisch aufgeschlossenem Bentonit bestehen kann, liegt der Pigmentanteil der Schutzschicht gemäß der Lehre der zweiten Schrift insgesamt zwischen größer 20 und 40 Gew.-%, wobei 15 bis 30 Gew.-% aus Bentonit, insbesondere aus einem alkalisch aufgeschlossenen Bentonit, bestehen. Gegebenenfalls kann entsprechend der Lehre beider Schriften in der Schutzschicht ein Vernetzungshilfsmittel enthalten sein, dessen Anteil - bezogen auf das Gesamtgewicht der Schutzschicht - im Fall der ersten Schrift 1 bis 2 Gew.-% und im Fall der zweiten Schrift 1 bis 5 Gew.-% beträgt.A heat recording sheet of the type mentioned is known from WO 97-18091 A 1 and also from WO 98-43824 A 1 . According to both documents, the protective layer of the known heat recording sheet contains not only water-insoluble but also water-soluble binder. While according to the teaching of the first document, a pigment content of 12 to 20% by weight is to be provided, which can consist predominantly of alkaline digested bentonite, the pigment content of the protective layer according to the teaching of the second document is between greater than 20 and 40% by weight. , 15 to 30% by weight of bentonite, in particular of an alkaline digested bentonite. If appropriate, according to the teaching of both documents, a crosslinking aid can be contained in the protective layer, the proportion of which, based on the total weight of the protective layer, is 1 to 2% by weight in the case of the first document and 1 to 5% by weight in the case of the second document is.

Aus der US-A-4,682,192 ist eine Schutzschicht bekannt, die zum Schutz einer auf ein Substrat aufgetragenen wärmeempfindlichen Aufzeichnungsschicht dient. Die Schutzschicht enthält ein kolloidales anorganisches Silikat, das entweder in Abwesenheit oder in Mischung mit einer wasserlöslichen oder sehr schwer wasserlöslichen hochmolekularen Verbindung eingebunden ist. Das kolloidale anorganische Silikat ist ausgewählt aus kolloidalen Magnesiumaluminiumsilikaten sowie fluorhaltigen kolloidalen Magnesiumsilikaten, wobei insbesondere Bentonit, Attapulgit und Dimonit offenbart werden. Weitergehende Hinweise zu speziellen Eigenschaften der Silikate werden in der Schrift nicht offenbart. Als schwer wasserlösliche hochmolekulare Verbindungen werden selbstvernetzende Acrylpolymere vorgeschlagen. Das Abmischungsverhältnis der besagten Silikate und der schwer wasserlöslichen hochmolekularen Polymere liegt allgemein im Bereich zwischen 1 : 0,1 und 1 : 10, wobei als bevorzugter Bereich ein Verhältnis zwischen 1 : 1 und 1 : 5 angegeben ist. A protective layer is known from US-A-4,682,192 which serves to protect a heat-sensitive recording layer applied to a substrate. The protective layer contains a colloidal inorganic silicate, which is incorporated either in the absence or in a mixture with a water-soluble or very poorly water-soluble high molecular compound. The colloidal inorganic silicate is selected from colloidal magnesium aluminum silicates and fluorine-containing colloidal magnesium silicates, bentonite, attapulgite and dimonite being disclosed in particular. Further references to special properties of the silicates are not disclosed in the writing. Self-crosslinking acrylic polymers are proposed as poorly water-soluble high-molecular compounds. The mixing ratio of the said silicates and the sparingly water-soluble high molecular weight polymers is generally in the range between 1: 0.1 and 1:10, a ratio between 1: 1 and 1: 5 being given as the preferred range.

Aus der EP-A-0 344 705 ist eine Schutzschicht bekannt, in der je Gew.-Teil Bindemittel 0,5 bis 3 Gew.-Teile Pigment vorliegen. Als geeignete Bindemittel werden für die Schutzschicht u. a. Polyvinylalkohol, Carboxymethylzellulose, Stärke und Stärkederivate sowie Copolymeremulsionen von Styrol-Butadien, Vinylacetat-Ethylen, Vinylacetat-Vinylchlorid-Ethylen und Methacrylat-Butadien offenbart. Als geeignete Pigmente werden gefälltes Calciumcarbonat, gemahlenes Calciumcarbonat, Talkum, Kaolin, Siliziumdioxidanhydrid, Magnesiumkarbonat, Zinkoxid, Alumiumoxid und Aluminiumhydroxid neben organischen Pigmenten genannt. Beispielhaft sind pigmenthaltige Schutzschichten beschrieben, die nur wasserlösliches Bindemittel enthalten. A protective layer is known from EP-A-0 344 705 , in which 0.5 to 3 parts by weight of pigment are present per part by weight of binder. Suitable binders for the protective layer include polyvinyl alcohol, carboxymethyl cellulose, starch and starch derivatives and copolymer emulsions of styrene-butadiene, vinyl acetate-ethylene, vinyl acetate-vinyl chloride-ethylene and methacrylate-butadiene. Precipitated calcium carbonate, ground calcium carbonate, talc, kaolin, silicon dioxide anhydride, magnesium carbonate, zinc oxide, aluminum oxide and aluminum hydroxide in addition to organic pigments are mentioned as suitable pigments. Protective layers containing pigment, which only contain water-soluble binder, are described as examples.

Die EP-B-0 373 903 betrifft ein wärmeempfindliches Aufzeichnungspapier mit einer inneren Haftfestigkeit von 2,5 kg·cm oder mehr, das eine Schutzschicht mit einer Glätte von mindestens 500 Bekk-Sekunden, vorzugsweise von 700 bis1500 Bekk-Sekunden aufweist, die auf eine feine Teilchen eines Styrol-Acrylatpolymeren und ein Bindemittel enthaltende Zwischenschicht aufgetragen ist. Als für die Schutzschicht geeignete Bindemittel werden sowohl wasserlösliche als auch wasserunlösliche Hochpolymere mit ausreichendem Filmbildevermögen bezeichnet. Eine gegebenenfalls erfolgende Pigmentzugabe zur Schutzschicht wird ebenfalls offenbart, es lassen sich jedoch der Schrift keine Hinweise auf die Art der geeigneten Pigmente entnehmen. EP-B-0 373 903 relates to a heat-sensitive recording paper with an internal adhesive strength of 2.5 kg.cm or more, which has a protective layer with a smoothness of at least 500 Bekk seconds, preferably from 700 to 1500 Bekk seconds, on a fine particle of a styrene-acrylate polymer and an intermediate layer containing a binder is applied. Suitable binders for the protective layer are both water-soluble and water-insoluble high polymers with sufficient film-forming capacity. Any pigment addition to the protective layer is also disclosed, but there is no indication in the document of the nature of the suitable pigments.

Die bekannten wärmeempfindlichen Aufzeichnungspapiere haben sich in zahlreichen Anwendungsbereichen als Büropapiere wie auch als Tickets und Labels bewährt, jedoch ergeben sich immer wieder neue Einsatzgebiete, die an die zum Einsatz kommenden Aufzeichnungspapiere neue Anforderungen stellen.
Mit der bereits bekannten Verwendung wärmeempfindlicher Aufzeichnungspapiere als Lotteriescheine wuchs der Bedarf an solchen Papieren, die unter dem Einfluß von auf sie einwirkender Wärme ein Schriftbild erzeugen können, das Barcodes umfaßt, die so scharfkantig und farbdicht abgebildet werden, daß sie mittels Laser fehlerfrei erkenn- und analysierbar sind. Damit ein solches Aufzeichnungspapier als Lotterieschein eingesetzt werden kann, muß die oben definierte Barcode-Lesbarkeit auch noch dann gegeben sein, wenn der Lotterieschein versehentlich naß geworden ist. Da häufig Lotteriescheine in Einsteckhüllen aufbewahrt werden, um sie vor mechanischer Zerstörung zu schützen, ist es ferner notwendig, daß die so genutzten wärmeempfindlichen Aufzeichnungspapiere eine hohe Beständigkeit gegenüber Weichmachern aufweisen, wie sie üblicherweise in Einsteckhüllen verwendet werden. Nicht zu unterschätzen ist die Notwendigkeit, daß ein für den Einsatz als Lotterieschein geeignetes Aufzeichnungspapier preisgünstig herzustellen sein muß.
Keinem der bekannten wärmeempfindlichen Aufzeichnungspapiere gelang es, dieses Anforderungsspektrum vollständig zu erfüllen.
Da Lotteriescheine gewöhnlich mittels Flexo- oder insbesondere mittels Naß-Offset-Druckverfahren aufgebrachte Aufdrucke aufweisen, ist die Bedruckbarkeit des neuen Aufzeichnungsbogens eine weitere Forderung, die möglichst noch ergänzt wird um seine Entwertbarkeit.The known heat-sensitive recording papers have proven themselves in numerous areas of application as office papers as well as tickets and labels, but there are always new areas of application which place new demands on the recording papers used.
With the already known use of heat-sensitive recording papers as lottery tickets, the need for such papers grew which, under the influence of heat acting on them, can produce a typeface comprising barcodes which are so sharp-edged and color-tight that they can be recognized by laser without errors and are analyzable. In order that such a recording paper can be used as a lottery ticket, the barcode legibility defined above must also be given if the lottery ticket has accidentally got wet. Since lottery tickets are often stored in insertion sleeves to protect them from mechanical destruction, it is also necessary that the heat-sensitive recording papers used in this way have a high resistance to plasticizers, as are usually used in insertion sleeves. Not to be underestimated is the need for recording paper suitable for use as a lottery ticket to be inexpensive to manufacture.
None of the known heat-sensitive recording papers was able to fully meet this range of requirements.
Since lottery tickets usually have imprints applied by means of flexographic printing or, in particular, by means of wet offset printing processes, the printability of the new recording sheet is a further requirement which, if possible, is supplemented by its validity.

So ist es Aufgabe der vorliegenden Erfindung, einen wärmeempfindlichen Aufzeichnungsbogen zur Verfügung zu stellen, der als Ticket und hier speziell als Lotterieschein eine hervorragende Barcode-Lesbarkeit garantiert. Der neue Aufzeichnungsbogen muß sich durch eine hohe Umweltresistenz auszeichnen, worunter im Sinne der Erfindung die herausragende Beständigkeit des wärmeempfindlichen Aufzeichnungsbogens gegenüber Wasser und gegenüber Weichmachern zu verstehen ist. Wesentlich an dem neuen Aufzeichnungsbogen muß seine kostengünstige Herstellungsweise sein.
Die Erfindung sieht eine weitere Aufgabe darin, einen Aufzeichnungsbogen zu entwickeln, der neben dem oben aufgeführten Anforderungsspektrum mindestens auf seiner mit der wärmeempfindlichen Aufzeichnungsschicht versehenen Seite eine gute Entwertbarkeit sowie eine gute Bedruckbarkeit im Flexo- und Naß-Offset-Druckverfahren aufweist.It is an object of the present invention to provide a heat-sensitive recording sheet which, as a ticket and here in particular as a lottery ticket, guarantees excellent barcode readability. The new recording sheet must be distinguished by a high level of environmental resistance, which in the sense of the invention means the outstanding resistance of the heat-sensitive recording sheet to water and to plasticizers. An essential aspect of the new recording sheet must be its cost-effective production method.
Another object of the invention is to develop a recording sheet which, in addition to the range of requirements mentioned above, has good validability and good printability in the flexographic and wet offset printing processes, at least on its side provided with the heat-sensitive recording layer.

Dabei verfügt ein wärmeempfindlicher Aufzeichnungsbogen über eine gute Entwertbarkeit im Sinne dieser Erfindung, wenn eine aus farbgebenden Pigmenten bestehende, nicht lösemittelhaltige Entwerterstempelfarbe sofort nach ihrem Aufdruck weder trocken noch naß vollständig von dem Aufzeichnungsbogen weggewischt werden kann.A heat-sensitive recording sheet has good validity in the sense of this invention, if one consisting of coloring pigments, not solvent-based stamping ink immediately after printing, neither dry nor can be wiped completely wet from the recording sheet.

Die Erfinder haben nach intensiven Forschungsarbeiten erkannt, daß eine solche Vielzahl von sich teilweise widersprechenden Anforderungen idealerweise durch einen wärmeempfindlichen Aufzeichnungsbogen erfüllt werden kann, der

  • ein Substrat,
  • eine Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht sowie
  • eine auf der Aufzeichnungsschicht ausgebildete Schutzschicht, die als Bindemittel ein wasserunlösliches, selbstvernetzendes Acrylpolymer, ein Vernetzungsmittel und als Pigment überwiegend einen alkalisch aufbereiteten Bentonit enthält,
aufweist, wobei
  • das Pigment der Schutzschicht aus einem oder mehreren anorganischen Pigmenten besteht und mindestens 80 Gew.-% aus einem hoch gereinigten alkalisch aufbereiteten Bentonit gebildet sind,
  • das Bindemittel der Schutzschicht aus einem oder aus mehreren wasserunlöslichen, selbstvernetzenden Acrylpolymeren besteht,
  • das Bindemittel-/Pigmentverhältnis in einem Bereich zwischen 7 : 1 und 9 : 1 liegt,
  • das Vernetzungsmittel-/Bindemittelverhältnis größer als 1 : 5 ist und
  • die Schutzschicht eine Glätte von mindestens 900 Bekk-Sekunden aufweist.
After intensive research, the inventors have recognized that such a multitude of partially contradicting requirements can ideally be met by a heat-sensitive recording sheet which
  • a substrate,
  • a heat-sensitive recording layer containing color formers and color acceptors and
  • a protective layer formed on the recording layer which contains a water-insoluble, self-crosslinking acrylic polymer, a crosslinking agent and, as a pigment, predominantly an bentonite which has been prepared in an alkaline manner,
has, wherein
  • the pigment of the protective layer consists of one or more inorganic pigments and at least 80% by weight is formed from a highly purified alkaline bentonite,
  • the binder of the protective layer consists of one or more water-insoluble, self-crosslinking acrylic polymers,
  • the binder / pigment ratio is in a range between 7: 1 and 9: 1,
  • the crosslinking agent / binder ratio is greater than 1: 5 and
  • the protective layer has a smoothness of at least 900 Bekk seconds.

Dabei beziehen sich die in Beschreibung und Patentansprüchen offenbarten Zahlenangaben zum Bindemittel-/Pigmentverhältnis und zum Vernetzungsmittel-/Bindemittelverhältnis auf die jeweiligen Gew.-% bzgl. der Schutzschicht.The figures disclosed in the description and claims relate on the binder / pigment ratio and on the crosslinking agent / binder ratio to the respective% by weight with respect to the protective layer.

Die in Beschreibung und Patentansprüchen gemachten Angaben zur flächenbezogenen Masse, zu Gew.-% (Gewichts-%) und zu Gew.-Teilen (Gewichts-Teilen) beziehen sich jeweils auf das "atro"-Gewicht, d.h. absolut trockene Gewichtsteile.
Unter dem in Beschreibung und Patentansprüchen verwendeten Begriff "wasserunlösliche Bindemittel" sind solche zu verstehen, die in Form wässeriger Dispersionen/Latizes von Polymeren oder Copolymeren vorliegen. Vernetzungsmittel werden im Rahmen der vorliegenden Erfindung den Bindemitteln nicht zugerechnet.The information given in the description and patent claims on the area-related mass, on% by weight (% by weight) and on parts by weight (parts by weight) in each case relate to the “atro” weight, ie absolutely dry parts by weight.
The term “water-insoluble binders” used in the description and claims means those which are in the form of aqueous dispersions / latices of polymers or copolymers. Crosslinking agents are not included in the binders in the context of the present invention.

Grundlage des neuen Aufzeichnungsbogens ist der hoch gereinigte alkalisch aufbereitete Bentonit, der als anorganisches Pigment allein oder im erfindungsgemäßen Mischungsverhältnis mit anderen anorganischen Pigmenten in der Schutzschicht enthalten ist. Die Eigenadhäsion dieses Bentonits erfordert eine völlig neue Komposition der Schutzschicht, die sich in dem erfindungsgemäßen Verhältnis von Bindemittel zu Pigment und Vernetzungsmittel zu Bindemittel niederschlägt. Der Wahl des Bindemittels kommt insofern eine erfindungswesentliche Bedeutung zu, als erst durch den Griff zu einem selbstvernetzenden Acrylpolymer als alleiniges Bindemittel und eingesetzt in einem bestimmten Verhältnis mit Pigment einerseits und Vernetzungsmittel andererseits die Herstellung eines Aufzeichnungsbogens gelingt, der nach seiner erfindungsgemäßen Einstellung der Glätte allen geforderten technologischen Anforderungen gerecht wird. Als selbstvernetzendes Acrylpolymer im Sinne dieser Erfindung ist ein selbstvernetzendes Bindemittel zu verstehen, ausgewählt aus der Gruppe umfassend Styrol-Acrylsäureester-Copolymerisat, ein Acrylamidgruppen enthaltendes Copolymerisat aus Styrol/Acrylsäureester sowie bevorzugt ein Copolymer auf Basis von Acrylnitril, Methacrylamid und Acrylester. Dabei wird die Glätte des neuen Aufzeichnungsbogens durch seine Behandlung mit einer Glättvorrichtung, beispielsweise einem Kalander, erzielt. Aufgrund der Tatsache, daß die Schutzschicht des neuen Aufzeichnungsbogens einlagig ausgebildet ist, kann der Erfindungsgegenstand auch die geforderten wirtschaftlichen Bedingungen erfüllen.The basis of the new recording sheet is the highly cleaned alkaline one Bentonite, as an inorganic pigment alone or in the mixing ratio according to the invention with other inorganic pigments in the protective layer. The Self-adhesion of this bentonite requires a completely new composition of the protective layer, which differ in the ratio of binder to pigment and crosslinking agent according to the invention precipitates to binders. In this respect, the choice of binder comes into play meaning essential to the invention than only by reaching for a self-cross-linking Acrylic polymer as the sole binder and used in a certain ratio with pigment on the one hand and crosslinking agent on the other hand the production of a recording sheet succeeds after its smoothness adjustment according to the invention meets all required technological requirements. As a self-networking For the purposes of this invention, acrylic polymer is to be understood as a self-crosslinking binder, selected from the group comprising styrene-acrylic acid ester copolymer Copolymer of styrene / acrylic acid ester containing acrylamide groups and preferred a copolymer based on acrylonitrile, methacrylamide and acrylic ester. The Smoothing the new recording sheet by treating it with a smoothing device, for example, a calender. Due to the fact that the protective layer of the new recording sheet is formed in one layer, the subject of the invention also meet the required economic conditions.

Der erfindungsgemäße Aufzeichnungsbogen weist mit seinem Bindemittel-/Pigmentverhältnis in einem Bereich zwischen 7 : 1 und 9 : 1 einen Pigmentanteil in der Schutzschicht auf, der u.a. aufgrund der Wahl des hoch gereinigten alkalisch aufbereiteten Bentonits als Pigment dem neuen Aufzeichnungsbogen schon bei Schutzschichten mit relativ geringer flächenbezogener Masse sowohl eine gute Entwertbarkeit wie auch eine gute Bedruckbarkeit garantieren, was u.a. mit der großen inneren Oberfläche und dem großen Mikroporenvolumen des hoch gereinigten alkalisch aufbereiteten Bentonits zu erklären ist.
In Versuchsreihen zeigte sich, daß auch natürliches oder gefälltes Calciumcarbonat, Kaolin oder Titanoxid einen positiven Beitrag zur Verbesserung der Druck- und Stempelfarbenabsorption beitragen, jedoch darf der Gesamtanteil des Bentonits gegenüber den anderen anorganischen Pigmenten 80 Gew.-% nicht unterschreiten. In weitergehenden Versuchsreihen konnte ferner der positive Einfluß von Aluminiumoxid sowie von Aluminiummodifiziertem Silica auf die Druck- und Stempelfarbenabsorption nachgewiesen werden, sofern auch hier der Gesamtanteil des Bentonits gegenüber den anderen anorganischen Pigmenten 80 Gew.-% nicht unterschreitet.The recording sheet according to the invention, with its binder / pigment ratio in a range between 7: 1 and 9: 1, has a pigment portion in the protective layer which, owing to the choice of the highly purified alkaline bentonite as pigment, makes the new recording sheet relatively protective even with protective layers Area-related mass guarantee both good devaluability and good printability, which can be explained, among other things, by the large inner surface and the large micropore volume of the highly purified alkaline-processed bentonite.
A series of experiments showed that natural or precipitated calcium carbonate, kaolin or titanium oxide also make a positive contribution to improving the absorption of printing and stamping ink, but the total proportion of bentonite compared to the other inorganic pigments must not be less than 80% by weight. In further series of tests, the positive influence of aluminum oxide and aluminum-modified silica on the printing and stamp ink absorption could also be demonstrated, provided that the total proportion of bentonite compared to the other inorganic pigments does not fall below 80% by weight.

Durch die Wahl eines wasserunlöslichen, selbstvernetzenden Acrylpolymers als Bindemittel und dessen erfindungsgemäßes Verhältnis einerseits zum Pigment in einem Bereich zwischen 7 : 1 und 9 : 1, und andererseits durch das Verhättnis von 1 Gew.-% Vernetzungsmittel zu mehr als 5 Gew.-% Bündemittel ist ferner schon bei Schutzschichten mit relativ geringer flächenbezogener Masse eine hohe Umweltresistenz des neuen Aufzeichnungsbogens gegeben.By choosing a water-insoluble, self-crosslinking acrylic polymer as a binder and its ratio according to the invention on the one hand to the pigment in one area between 7: 1 and 9: 1, and on the other hand by the ratio of 1% by weight Crosslinking agent is more than 5 wt .-% bundling agent furthermore, a high level even with protective layers with a relatively low area-related mass Given the new sheet's environmental resistance.

Entscheidendes Ergebnis der intensiven Forschungsarbeiten ist es jedoch, daß der erfindungsgemäße Aufzeichnungsbogen neben den oben erläuterten Eigenschaften auch noch die geforderte hervorragende Barcode-Lesbarkeit garantiert, was zum einen durch die hohe Glätte größer 900 Bekk-Sekunden bewirkt, zum anderen durch die relativ geringe flächenbezogene Masse der Schutzschicht begünstigt wird. Zusammengefaßt kann festgehalten werden, daß erst durch die Kombination aller in Anspruch 1 wiedergegebenen Merkmale des erfindungsgemäßen Aufzeichnungsbogens das gesamte Anforderungsspektrum erfüllt werden kann.The decisive result of the intensive research work, however, is that the invention Recording sheet in addition to the properties explained above the required excellent barcode readability still guarantees, on the one hand, by the high smoothness of more than 900 Bekk seconds causes, on the other hand, the relatively low area-related mass of the protective layer is favored. To summarize be noted that only by the combination of all reproduced in claim 1 Features of the recording sheet according to the invention the entire range of requirements can be fulfilled.

Es hat sich gezeigt, daß besonders gute Ergebnisse hinsichtlich der dieser Erfindung zugrunde liegenden Aufgabenstellung zu erzielen sind, sofern der Bentonit in Pulverform ein Flächen-Kanten-Verhältnis in einem Bereich zwischen 15 und 70, insbesondere in einem Bereich zwischen 20 bis 50 aufweist.
Im Rahmen der umfangreichen Versuchsreihen zeichnete sich ab, daß eine überzeugende Barcode-Lesbarkeit in Kombination mit hoher Umweltresistenz dann gegeben ist, wenn das Vernetzungsmittel-/Bindemittelverhältnis in einem Bereich zwischen 1 : 5 und 1 : 40, bevorzugt in einem Bereich zwischen 1 : 5 und 1 : 20 oder noch besser in einem Bereich zwischen 1 : 5 und 1 : 10 liegt, wobei ganz besonders günstige Versuchsergebnisse festzustellen waren bei einem Vernetzungsmittel-/Bindemittelverhältnis in einem Bereich zwischen 1 : 5 und 1 : 7.It has been shown that particularly good results can be achieved with regard to the object on which this invention is based, provided that the bentonite in powder form has an area-edge ratio in a range between 15 and 70, in particular in a range between 20 and 50.
Within the scope of the extensive test series, it became apparent that there is convincing barcode readability in combination with high environmental resistance if the crosslinking agent / binder ratio is in a range between 1: 5 and 1:40, preferably in a range between 1: 5 and 1:20 or even better in a range between 1: 5 and 1:10, whereby particularly favorable test results were found with a crosslinking agent / binder ratio in a range between 1: 5 and 1: 7.

Grundsätzlich kommt der Wahl des Vernetzungsmittel keine erfindungswesentliche Bedeutung zu, sofern sich Vernetzungsmittel und Bindemittel in der Schutzschicht hinsichtlich ihrer Wirkungen nicht negativ beeinflussen. In den dieser Erfindung zugrundeliegenden Versuchsarbeiten kamen insbesondere solche Vernetzungsmittel zum Einsatz, die ausgewählt sind aus der Gruppe umfassend

  • zyklischen Harnstoff,
  • Methylolharnstoff,
  • Amoniumzirkoniumkarbonat und
  • bevorzugt Polyamidepichlorhydrinharz.
In principle, the choice of the crosslinking agent is of no importance to the invention, provided that the crosslinking agent and binder in the protective layer do not adversely affect their effects. In the experimental work on which this invention is based, use was made in particular of those crosslinking agents which are selected from the group comprising
  • cyclic urea,
  • methylol,
  • Ammonium zirconium carbonate and
  • preferably polyamide epichlorohydrin resin.

Ausgehend von einer Glätte der Schutzschicht von mindestens 900 Bekk-Sekunden ergibt sich bei dem erfindungsgemäßen Aufzeichnungsbogen eine weiter gesteigerte Barcode-Lesbarkeit, wenn die Schutzschicht durch starke Kalandrierung eine Glätte in einem Bereich von 1200 bis 5500 Bekk-Sekunden aufweist. Als bevorzugte Ausführungsform des Erfindungsgegenstandes ist es aufzuführen, wenn die Schutzschicht eine Glätte in einem Bereich größer 1500 bis 2500 Bekk-Sekunden aufweist, da hier neben hervorragender Barcode-Lesbarkeit und der Erfüllung aller anderen technologischen und wirtschaftlichen Forderungen auch ein angenehmes und besonders gleichmäßiges Erscheinungsbild des neuen wärmeempfindlichen Aufzeichnungsbogens auffällt. Based on a smoothness of the protective layer of at least 900 Bekk seconds a further increase in barcode readability in the recording sheet according to the invention, if the protective layer becomes smooth in one area due to strong calendering from 1200 to 5500 Bekk seconds. As a preferred embodiment of the The object of the invention is to be listed if the protective layer is smooth in one Has a range greater than 1500 to 2500 Bekk seconds, as well as excellent Barcode readability and compliance with all other technological and economic Demands also a pleasant and particularly even appearance of the new heat-sensitive recording sheet.

Um eine gute Barcode-Lesbarkeit bei dem neuen Aufzeichnungsbogen zu erreichen, ist die Ausbildung der Deckschicht mit einer möglichst geringen flächenbezogenen Masse anzustreben, wobei jedoch gleichzeitig auch die sich widersprechenden Forderungen einer hohen Umweltresistenz sowie einer guten Entwertbarkeit und guten Bedruckbarkeit im Flexo- und Naß-Offset-Druckverfahren zu erfüllen sind. Während die hohe Umweltresistenz eine Deckschicht mit möglichst großer flächenbezogener Masse und hohem Bindeund Vernetzungsmittelanteil erfordert, zielt die Forderung nach guter Entwertbarkeit und Bedruckbarkeit auf eine Deckschicht mit möglichst großer flächenbezogener Masse und hohem Pigmentanteil, der vor allem einer guten Barcode-Lesbarkeit widerspricht. Die Erfinder stellten fest, daß ein alle gestellten Forderungen erfüllender Aufzeichnungsbogen idealerweise eine flächenbezogene Masse der Schutzschicht in einem Bereich von 1,0 bis 4,0 g/m2, bevorzugt in einem Bereich von 1,5 bis 3,0 g/m2 und ganz besonders bevorzugt in einem Bereich von 1,8 bis 2,5 g/m2 aufweist.In order to achieve good barcode legibility with the new recording sheet, the aim is to form the cover layer with the smallest possible area-related mass, but at the same time the contradictory requirements of high environmental resistance as well as good devaluability and good printability in flexo and wet Offset printing processes are to be fulfilled. While the high level of environmental resistance requires a top layer with the largest possible area-related mass and high binding and crosslinking agent content, the demand for good devaluability and printability is aimed at a top layer with the largest possible area-related mass and high pigment content, which above all contradicts good barcode readability. The inventors have found that a recording sheet which meets all the requirements ideally has a mass per unit area of the protective layer in a range from 1.0 to 4.0 g / m 2 , preferably in a range from 1.5 to 3.0 g / m 2 and very particularly preferably in a range from 1.8 to 2.5 g / m 2 .

Im Rahmen der vorliegenden Erfindung können die angegebenen Schutzschichten auf wärmeempfindliche Aufzeichnungsschichten aufgetragen sein, die direkt auf das Substrat beispielsweise aus Papier aufgebracht sind, sie können jedoch gemäß einer vorzugsweisen Ausführungsform auch bei solchen wärmeempfindlichen Aufzeichnungsbögen angewendet werden, bei denen zwischen dem Substrat und der wärmeempfindlichen Aufzeichnungsschicht noch eine Zwischenschicht ausgebildet ist, die bevorzugt ölabsorptives anorganisches Pigment enthält. Eine solche Zwischenschicht kann zum einen einen positiven Beitrag zur Egalisierung der Substratoberfläche leisten, womit sich die Menge an notwendigerweise aufzubringender Streichfarbe für die wärmeempfindliche Aufzeichnungsschicht reduziert, zum anderen nehmen die Pigmente dieser Zwischenschicht die durch Hitzeeinwirkung verflüssigten Wachsbestandteile der wärmeempfindlichen Aufzeichnungsschicht bei der Schriftbildausbildung auf und begünstigen so eine sichere und schnelle Funktionsweise der wärmeinduzierten Aufzeichnung.In the context of the present invention, the specified protective layers can be heat-sensitive recording layers can be applied directly to the substrate For example, are applied from paper, but they can be preferred according to one Embodiment also applied to such heat-sensitive recording sheets in which between the substrate and the heat-sensitive recording layer still an intermediate layer is formed, which is preferably oil-absorbent contains inorganic pigment. On the one hand, such an intermediate layer can be a positive one Contribute to the leveling of the substrate surface, which increases the amount necessary coating color for the heat-sensitive recording layer reduced, on the other hand the pigments of this intermediate layer take the wax components of the heat-sensitive recording layer liquefied by the action of heat in the formation of typefaces and thus favor a safe and Fast functioning of the heat-induced recording.

Der erfindungsgemäße Aufzeichnungsbogen weist bevorzugt eine Rückseitenbeschichtung auf, die auf der Substratseite aufgetragen ist, die der mit der wärmeempfindlichen Aufzeichnungsschicht versehenen Seite gegenüberliegt. Eine solche Rückseitenbeschichtung wird beispielsweise in der DE-A-197 48 258 vorgeschlagen und dient dann einer verbesserten rückseitigen Bedruckbarkeit des Aufzeichnungsbogens im Offset- und Flexodruckverfahren sowie einer verbesserten Sperrwirkung der Rückseite gegenüber Weichmachern, Ölen und Fetten. The recording sheet according to the invention preferably has a backside coating which is applied to the substrate side which is opposite to the side provided with the heat-sensitive recording layer. Such a backside coating is proposed, for example, in DE-A-197 48 258 and then serves to improve the printability of the recording sheet on the backside in the offset and flexographic printing process and to improve the blocking effect of the backside against plasticizers, oils and greases.

Der neue wärmeempfindliche Aufzeichnungsbogen ist insbesondere zur Verwendung als Ticket und hier speziell zur Verwendung als Lotterieschein konzipiert. Häufig wird an so verwendete Aufzeichnungsbögen die Anforderung gestellt, daß deren Authentizität einfach und möglichst ohne Verwendung aufwendiger Hilfsmittel nachweisbar ist. In einer dieser Anforderung gerecht werdenden Ausführungsform weist der neue Aufzeichnungsbogen ein Sicherheitsmerkmal oder eine Kombination mehrerer Sicherheitsmerkmale auf. Als Sicherheitsmerkmale bieten sich dabei insbesondere folgende, auch in der noch nicht veröffentlichten DE 199 36 030 offenbarte authentizitätsnachweisende Komponenten an, ohne dabei weder in Art noch in zu kombinierender Anzahl beschränkt oder festgelegt zu sein:

  • ein mit bloßem Auge unsichtbarer, in das Substrat eingearbeiteter wasserunlöslicher Farbstoff (A), der bei einer Oberflächenbenetzung mit einem organischen Lösungsmittel oder einer Säure eine auffällige Färbung zumindest auf der Seite, die der mit der wärmeempfindlichen Aufzeichnungsschicht versehenen Seite gegenüberliegt, bewirkt;
  • ein im sauren oder neutralen pH-Bereich bei Tageslicht nur schwach sichtbarer Farbstoff (B), der im regelmäßigen oder unregelmäßigen Muster auf die gesamte Fläche der Seite, die der mit der wärmeempfindlichen Aufzeichnungsschicht versehenen Seite gegenüberliegt, aufgebracht ist und der im Kontakt mit einer alkalischen Substanz eine Farbreaktion eingeht, die zu einer bei Tageslicht fluoreszierenden beständigen Farbe führt;
  • ein in das Substrat eingearbeitetes oder aufgedrucktes Wasserzeichen;
  • ein in das Substrat eingebrachter mit einem Farbstoff (C) eingefärbter und/oder mit einem optischen Aufheller behandelter Zellstoff, der unter UV-Bestrahlung fluoreszierend ist;
  • eine SC-Schicht, die auf die Seite aufgebracht ist, die der mit der wärmeempfindlichen Aufzeichnungsschicht versehenen Seite gegenüberliegt, und in der Akzeptoren und Mikrokapseln mit darin eingekapselten Farbbildnern vorliegen, wobei die Farbbilder mit den Akzeptoren auf Druck eine farbbildende Reaktion eingehen.
The new heat-sensitive recording sheet is especially designed for use as a ticket and here specifically for use as a lottery ticket. Frequently, the requirement for recording sheets used in this way is that their authenticity can be demonstrated simply and as far as possible without the use of complex aids. In an embodiment which meets this requirement, the new recording sheet has a security feature or a combination of several security features. The following security features in particular are suitable as security features, which are also disclosed in DE 199 36 030 , which has not yet been published, without being restricted or defined neither in terms of type nor in number to be combined:
  • a water-insoluble dye (A) which is invisible to the naked eye and which is incorporated into the substrate and which, when surface-wetted with an organic solvent or an acid, causes a striking coloration at least on the side opposite to the side provided with the heat-sensitive recording layer;
  • a dye (B) which is only slightly visible in daylight in the acidic or neutral pH range and which is applied in a regular or irregular pattern to the entire surface of the side opposite the side provided with the heat-sensitive recording layer and which is in contact with an alkaline Substance undergoes a color reaction which leads to a stable color fluorescent in daylight;
  • a watermark incorporated or printed on the substrate;
  • a cellulose introduced into the substrate with a dye (C) and / or treated with an optical brightener, which is fluorescent under UV radiation;
  • an SC layer which is applied to the side opposite the side provided with the heat-sensitive recording layer and in which acceptors and microcapsules with color formers encapsulated therein are present, the color images having a color-forming reaction with the acceptors when printed.

Auch eine pigmentierte Zwischenschicht, die entsprechend eines Vorschlags der noch nicht veröffentlichten DE 100 21 896 zur Ausbildung von authentizitätsnachweisenden Markierungen in lokal unterschiedlicher Dicke ausgeführt ist, bietet sich als Sicherheitsmerkmal für den neuen Aufzeichnungsbogen an. A pigmented intermediate layer, which is designed in accordance with a proposal of the as yet unpublished DE 100 21 896 for the formation of authenticity-proofing markings in locally different thicknesses, offers itself as a security feature for the new recording sheet.

Es wird weiterhin bevorzugt, daß die Schutzschicht das Metallsalz einer langkettigen Fettsäure, insbesondere Stearinsäure, als Schmiermittel (engl.: lubricant) enthält. Ganz besonders wird als Schmiermittel in der Schutzschicht ein Zinkstearat bevorzugt in einer Menge kleiner 20, insbesondere kleiner 15 Gew.-Teilen, bezogen auf insgesamt 100 Gew.-Teile der Schutzschicht.It is further preferred that the protective layer be the metal salt of a long chain fatty acid, especially stearic acid, contains as a lubricant. Most notably a zinc stearate is preferably used as a lubricant in the protective layer Amount less than 20, in particular less than 15 parts by weight, based on a total of 100 Parts by weight of the protective layer.

Die Herstellung der Schutzschicht erfolgt unter Verwendung einer wässerigen Streichmasse, die außer den genannten Pigmenten, Bindemitteln, Vernetzungsmitteln und Schmiermitteln noch übliche Streichfarbenhilfsmittel und Zusätze enthält, wie z. B. Dispergiermittel, Entschäumer und Metallsalze zur Vernetzungsbeschleunigung der Vernetzungsmittel bei einer Menge dieser Streichfarbenhilfsmittel von nicht mehr als zusammen 10 Gew.-Teilen, vorzugsweise von nicht mehr als 7 Gew.-Teilen, bezogen auf insgesamt 100 Gew.-Teile der Schutzschicht.The protective layer is produced using an aqueous coating slip, in addition to the pigments, binders, crosslinking agents and Lubricants still contains conventional coating aids and additives, such as. B. dispersants, Defoamers and metal salts to accelerate the crosslinking of the crosslinking agents with a lot of these coating aids of no more than together 10 parts by weight, preferably not more than 7 parts by weight, based on the total 100 parts by weight of the protective layer.

Das nachfolgende Beispiel wird die Erfindung weiter verdeutlichen:The following example will further illustrate the invention:

Auf einer Langsieb-Papiermaschine wird als Substrat eine Papierbahn aus gebleichten und gemahlenen Laub- und Nadelholzzellstoffen mit einer flächenbezogenen Masse von 67 g/m2 unter Zusatz üblicher Beischlagstoffe in üblichen Mengen hergestellt. Frontseitig wird eine kalziniertes Kaolin als Pigment, Styrol-Butadien-Latex als Bindemittel und Stärke als Cobinder neben weiteren Hilfsmitteln aufweisende Zwischenschicht von 8 g/m2 aufgebracht.A paper web made of bleached and ground hardwood and softwood cellulose with a mass per unit area of 67 g / m 2 is added to the substrate on a Fourdrinier paper machine with the addition of conventional admixtures in customary amounts. A calcined kaolin as a pigment, styrene-butadiene latex as a binder and starch as a cobinder are applied to the front in addition to an additional intermediate layer of 8 g / m 2 .

Auf die Zwischenschicht wird eine Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht mit einer flächenbezogenen Masse von 5,4 g/m2 aufgetragen.A heat-sensitive recording layer containing color formers and color acceptors and having a mass per unit area of 5.4 g / m 2 is applied to the intermediate layer.

Auf die getrocknete Aufzeichnungsschicht wird eine Schutzschicht von 2 g/m2 aufgebracht. Als Pigment wird ein hoch gereinigter alkalisch aufbereiteter Bentonit mit Plättchenstruktur eingesetzt, dessen Eigenadhäsion seine Fixierung mit geringem Bindemittelbedarf ermöglicht und dessen spezifische Oberfläche im nicht dispergierten Zustand mit 85 m2/g angegeben wird bei einem Flächen-Kanten-Verhältnis, das bei dem in Pulverform vorliegenden Bentonit in einem Schwankungsbereich zwischen 20 und 50 liegt. Es wird ein Bindemittel-/Pigmentverhältnis von 6 : 1 sowie ein Vernetzungsmittel-/Bindemittelverhältnis von 1 : 5 eingestellt. Als Vernetzungsmittel wird Polyamid-epichlorhydrinharz, als Bindemittel die wässerige Dispersion eines selbstvernetzenden Copolymers aus Acrylnitril, Methacrylamid und Acrylester benutzt. Die Streichmasse zur Herstellung der Schutzschicht enthält als weitere Komponenten einen Entschäumer, als Schmiermittel Stearinsäure sowie verschiedene Dispergiermittel zum einen für das Pigment und zum anderen für das Schmiermittel.A protective layer of 2 g / m 2 is applied to the dried recording layer. The pigment used is a highly purified, alkaline-processed bentonite with a platelet structure, the inherent adhesion of which enables it to be fixed with little need for binding agents, and the specific surface area of which, in the non-dispersed state, is given as 85 m 2 / g with an area-to-edge ratio which is in powder form Bentonite is in a range between 20 and 50. A binder / pigment ratio of 6: 1 and a crosslinking agent / binder ratio of 1: 5 are set. Polyamide-epichlorohydrin resin is used as the crosslinking agent, and the aqueous dispersion of a self-crosslinking copolymer of acrylonitrile, methacrylamide and acrylic ester is used as the binder. The coating slip for the production of the protective layer contains, as further components, a defoamer, stearic acid as a lubricant and various dispersants, on the one hand for the pigment and on the other hand for the lubricant.

Die aufgetragene Streichmasse wird getrocknet und der soweit hergestellte Aufzeichnungsbogen mittels eines Kalanders geglättet, wobei eine Glätte von 2200 Bekk-Sekunden erzielt wird.The applied coating slip is dried and the recording sheet produced so far smoothed using a calender, with a smoothness of 2200 Bekk seconds is achieved.

Der so hergestellte, verglichen mit seinem Anforderungsprofil kostengünstig hergestellte Aufzeichnungsbogen läßt sich im Flexo- wie im Naß-Offset-Druckverfahren gut bedrucken und weist eine gute Entwertbarkeit auf.
Die Wasserbeständigkeit wird als Verhältnis zweier Messungen der mit Hilfe des Macbeth RD 914 der Firma Karl Schröder KG (Korrillonstraße 32, D-69469 Weinheim) bestimmten dynamischen Druckdichte erfaßt. Dazu wird ein Muster des erfindungsgemäßen Aufzeichnungsbogens unter Benutzung eines Thermodruckers vom Typ TP 3000-300 der Firma Charles Richiger AG, Maschinenbau (Bernstrasse 81, CH-3613 Steffisburg) mit einem Schriftbild versehen. Nach einer ersten Bemessung der dynamischen Druckdichte wird das Muster des erfindungsgemäßen Aufzeichnungsbogens über 60 Minuten in Wasser getaucht. Anschließend wird die dynamischen Druckdichte ein zweites Mal bemessen. Die so untersuchte Wasserbeständigkeit des erfindungsgemäßen Aufzeichnungsbogens ist bei einem Quotienten aus beiden Meßwerten von 94 % als sehr gut zu bezeichnen. Der neue Aufzeichnungsbogen erhält einen durch Hitze induzierten Barcode unter Benutzung eines 300dpi-BOCA-Druckers, Typ Micro 21 der Firma Boca tickets & printers (Vlietweg 17, NL-2266 KA Leidschendam). Das Druckbild wird visuell betrachtet und hinsichtlich seiner Scharfkantigkeit und Farbdichte mit gut bewertet.The recording sheet produced in this way, which is inexpensive to produce compared to its requirement profile, can be printed well in the flexographic and wet offset printing processes and has good devaluability.
The water resistance is recorded as the ratio of two measurements of the dynamic pressure density determined using the Macbeth RD 914 from Karl Schröder KG (Korrillonstrasse 32, D-69469 Weinheim). For this purpose, a sample of the recording sheet according to the invention is provided with a typeface using a TP 3000-300 thermal printer from Charles Richiger AG, Mechanical Engineering (Bernstrasse 81, CH-3613 Steffisburg). After a first measurement of the dynamic printing density, the sample of the recording sheet according to the invention is immersed in water for 60 minutes. The dynamic print density is then measured a second time. The water resistance of the recording sheet according to the invention examined in this way can be described as very good given a quotient of both measured values of 94%. The new recording sheet receives a heat-induced barcode using a 300dpi BOCA printer, type Micro 21 from Boca tickets & printers (Vlietweg 17, NL-2266 KA Leidschendam). The printed image is viewed visually and rated good in terms of sharpness and color density.

Claims (14)

  1. Heat-sensitive recording sheet having
    a substrate,
    a heat-sensitive recording layer comprising colour formers and colour acceptors and
    a protective layer which is formed on top of the recording layer and which comprises a water-insoluble self-crosslinking acrylic polymer as binder, a crosslinking agent and, as pigment, predominantly an alkali-treated bentonite,
    characterised in that
    the pigment of the protective layer consists of one or more inorganic pigments, at least 80 % by weight being formed by a highly purified alkali-treated bentonite,
    the binder of the protective layer consists of one or more water-insoluble self-crosslinking acrylic polymer(s),
    the binder/pigment ratio is 6:1 or is in a range between 7:1 and 9:1,
    the crosslinking agent/binder ratio is 1 : >5 and
    the protective layer has a Bekk smoothness of at least 900 seconds.
  2. Recording sheet according to claim 1, characterised in that the pigment mixture comprises further inorganic pigments selected from the group comprising natural or precipitated calcium carbonate, kaolin, titanium oxide, aluminium oxide and aluminium-modified silica.
  3. Recording sheet according to either of claims 1 and 2, characterised in that the bentonite in powder form has a surface-to-edge ratio in a range between 15 and 70.
  4. Recording sheet according to any one of claims 1 to 3, characterised in that the crosslinking agent/binder ratio is in a range between 1:5 and 1:40.
  5. Recording sheet according to any one of claims 1 to 4; characterised in that the crosslinking agent/binder ratio is in a range between 1:5 and 1:10.
  6. Recording sheet according to any one of claims 1 to 3, characterised in that the crosslinking agent/binder ratio is in a range between 1:5 and 1:7.
  7. Recording sheet according to any one of claims 1 to 6, characterised in that the crosslinking agent is selected from the group comprising cyclic urea, methylol urea, polyamide-epichlorohydrin resin and ammonium zirconium carbonate.
  8. Recording sheet according to any one of claims 1 to 7, characterised in that the protective layer has a Bekk smoothness in a range from 1200 to 5500 seconds.
  9. Recording sheet according to any one of claims 1 to 8, characterised in that the protective layer has a Bekk smoothness in a range from > 1500 to 2500 seconds.
  10. Recording sheet according to any one of claims 1 to 9, characterised in that the weight per unit area of the protective layer is in a range from 1.5 to 3.0 g/m2.
  11. Recording sheet according to any one of claims 1 to 10, characterised in that a pigment-containing intermediate layer is formed between the substrate and the heat-sensitive recording layer.
  12. Recording sheet according to any one of claims 1 to 11, characterised in that the substrate has a reverse side coating on that side which is located opposite the heat-sensitive recording layer.
  13. Recording sheet according to any one of claims 1 to 12, characterised in that the recording sheet has a security feature or a combination of a plurality of security features.
  14. Use of a recording sheet according to any one of claims 1 to 13 as a ticket.
EP01983538A 2000-10-16 2001-10-09 Heat-sensitive recording sheet and use of the same Expired - Lifetime EP1333991B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10051294A DE10051294C1 (en) 2000-10-16 2000-10-16 Thermographic material useful for ticket, especially lottery ticket, has protective coating of water-insoluble, self-crosslinking acrylic polymer and crosslinker pigmented (mainly) with highly purified, alkali-treated bentonite
DE10051294 2000-10-16
PCT/EP2001/011677 WO2002032688A1 (en) 2000-10-16 2001-10-09 Heat-sensitive recording sheet and use of the same

Publications (2)

Publication Number Publication Date
EP1333991A1 EP1333991A1 (en) 2003-08-13
EP1333991B1 true EP1333991B1 (en) 2004-08-18

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP01983538A Expired - Lifetime EP1333991B1 (en) 2000-10-16 2001-10-09 Heat-sensitive recording sheet and use of the same

Country Status (8)

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US (2) US20060154819A1 (en)
EP (1) EP1333991B1 (en)
JP (1) JP2004526586A (en)
CN (1) CN1211217C (en)
AT (1) ATE273800T1 (en)
DE (2) DE10051294C1 (en)
ES (1) ES2227302T3 (en)
WO (1) WO2002032688A1 (en)

Cited By (1)

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EP1925459A2 (en) 2006-11-24 2008-05-28 Mitsubishi Hitec Paper Flensburg GmbH Heat-sensitive recording material with authentification feature

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DE10343273A1 (en) * 2003-09-17 2005-04-21 Voith Paper Patent Gmbh Coating machine for applying at least one color with a high solids content
DE202004019989U1 (en) * 2004-12-27 2005-03-17 Siemens Ag Security paper for thermal printing has a multi layer construction incorporating a surface protection layer and a backing layer
DE102008007596B4 (en) 2008-02-06 2010-08-05 Kanzan Spezialpapiere Gmbh Process for the preparation of thermal recording materials, in particular thermal papers and recording materials
CN101952508B (en) * 2008-03-31 2013-01-23 日本制纸株式会社 Additive for papermaking and paper containing the same
CN101417563B (en) * 2008-10-21 2010-09-22 莫文生 Environmental protection carbonless copying paper developer preparation method using low acid method
DE102011114129A1 (en) 2011-09-23 2013-03-28 Mitsubishi Hitec Paper Europe Gmbh Recording material for offset printing
CN103757979B (en) * 2013-12-31 2016-02-03 金华盛纸业（苏州工业园区）有限公司 Heat-sensitive paper and preparation method thereof
EP2910384B1 (en) 2014-02-21 2016-09-21 Mitsubishi HiTec Paper Europe GmbH Heat-sensitive recording material with a novel dye-acceptor combination

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US4682192A (en) * 1984-07-31 1987-07-21 Nippon Kayaku Kabushiki Kaisha Heat-sensitive recording sheet
JPH01301368A (en) * 1988-05-31 1989-12-05 Kanzaki Paper Mfg Co Ltd Thermal recording material
DE68921164T2 (en) * 1988-12-12 1995-06-14 Tomoegawa Paper Mfg Co Ltd Heat-sensitive recording paper for labels.
JPH02274589A (en) * 1989-04-18 1990-11-08 Nippon Kayaku Co Ltd Thermal recording sheet
DE19542598A1 (en) * 1995-11-15 1997-05-22 Feldmuehle Ag Stora Heat-sensitive recording sheet
DE19713590C1 (en) * 1997-04-02 1998-10-29 Stora Publication Paper Ag Heat-sensitive recording sheet
DE19806433B4 (en) * 1998-02-17 2004-11-11 Mitsubishi Hitec Paper Flensburg Gmbh Use of a heat-sensitive recording material as a label

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EP1925459A2 (en) 2006-11-24 2008-05-28 Mitsubishi Hitec Paper Flensburg GmbH Heat-sensitive recording material with authentification feature

Also Published As

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CN1211217C (en) 2005-07-20
DE50103351D1 (en) 2004-09-23
ATE273800T1 (en) 2004-09-15
US20080081764A1 (en) 2008-04-03
CN1474751A (en) 2004-02-11
US20060154819A1 (en) 2006-07-13
DE10051294C1 (en) 2002-04-18
EP1333991A1 (en) 2003-08-13
ES2227302T3 (en) 2005-04-01
JP2004526586A (en) 2004-09-02
WO2002032688A1 (en) 2002-04-25

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