EP0611662A2 - Thermosensitive recording material - Google Patents

Thermosensitive recording material Download PDF

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Publication number
EP0611662A2
EP0611662A2 EP94101815A EP94101815A EP0611662A2 EP 0611662 A2 EP0611662 A2 EP 0611662A2 EP 94101815 A EP94101815 A EP 94101815A EP 94101815 A EP94101815 A EP 94101815A EP 0611662 A2 EP0611662 A2 EP 0611662A2
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EP
European Patent Office
Prior art keywords
layer
recording material
catalyst
binder
material according
Prior art date
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Application number
EP94101815A
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German (de)
French (fr)
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EP0611662B1 (en
EP0611662A3 (en
Inventor
Wolfgang Dr. Podszun
Herman Dr. Uytterhoeven
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3372—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—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
    • B41M5/41—Base layers supports or substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate
    • Y10T428/31978—Cellulosic next to another cellulosic
    • Y10T428/31982—Wood or paper

Definitions

  • the invention relates to a transparent thermosensitive recording material based on mono-, oligo- or polysaccharides.
  • Direct thermal recording processes are particularly user-friendly in comparison to other recording processes and have decisive ecological advantages, since apart from the recording material itself no further consumables are required and no waste is generated. These materials can be written on, for example, with a thermal head or a laser beam.
  • Known direct thermal recording materials are based e.g. on the reaction of a leuco dye with a dye developer, this reaction being triggered by the action of heat.
  • the associated materials are simple to set up and handle and are used, for example, in facsimile machines, cash registers or measuring instruments. However, they are out of the question for higher-value applications, since the image stability, in particular the light stability and the maximum achievable density, are inadequate. In addition, it is difficult to produce transparent thermosensitive recording materials based on leuco dyes.
  • US 3 161 770 describes a thermographic copying process using a thermographic recording material which is obtained by treating a carrier material with a mixture of a reducing carbohydrate and a organic acid has been produced. Paper is mainly used as the carrier material; the treatment solution penetrates the paper. Transparent materials cannot be obtained here. But even when using a transparent substrate instead of an opaque paper base, "clear plastic materials, such as Mylar" are also mentioned, only images with insufficient density and stability are obtained. The transparent documents do not absorb the treatment solution. A sticky layer remains. Due to the high stickiness, processing with thermal printers, for example, is impossible.
  • the object of the present invention is to provide a transparent thermosensitive recording material which, with high transparency, provides images with good stability and high optical density and can be processed with conventional thermal printers.
  • thermosensitive recording material which consists of a transparent substrate and one or more binder layers arranged thereon, at least one binder layer containing a mono-, oligo- or polysaccharide and at least one binder layer which can be identical to the first-mentioned binder layer, contains a catalyst.
  • Suitable transparent carrier materials are plastic films made of e.g. Polyethylene terephthalate, cellulose esters such as cellulose acetate, cellulose propionate, cellulose butyrates, furthermore made of polycarbonate or polyimide.
  • the transparent recording material according to the invention contains mono-, oligo- or polysaccharides, hereinafter referred to collectively as saccharide.
  • the monosaccharides galactose, glucose, idose, mannose, fructose, sorbose, ribose and xylose may be mentioned as examples.
  • deoxymonosaccharides can also be used.
  • suitable oligosaccharides are sucrose, maltose, trehalose, lactose and tri- and tetrasaccharides derived from sucrose, such as raffinose and stachiose.
  • Starch from the group of polysaccharides is particularly suitable.
  • (Poly) saccharides containing a keto group or ketal group are particularly suitable.
  • the amount of saccharide is important for the optical density that can be achieved and is generally between 0.5 and 30 g / m2, preferably between 1 and 20 g / m2, particularly preferably between 2 and 15 g / m2.
  • Suitable binders for the saccharide are water-soluble binders which can be processed from aqueous dispersion, for example polyvinyl alcohol, partially hydrolyzed polyvinyl acetates, polyvinyl pyrrolidone, high molecular weight polyethylene oxide, copolymers of polyvinyl pyrrolidone and vinyl acetate, and furthermore latices of acrylate copolymers, polyvinyl chloride and vinyl chloride copolymers.
  • the proportion of binder in the layer or layers containing the saccharide is 5 to 90% by weight, preferably 5 to 70% by weight, particularly preferably 8 to 50% by weight.
  • Metal compounds in particular salts of transition metals, and acids (protonic acids and Lewis acids) are suitable as catalysts.
  • Inorganic and organic protonic acids are particularly effective.
  • Sulfonic acids and phosphonic acids for example benzenesulfonic acid, p-toluenesulfonic acid and o-toluenesulfonic acid, are preferred.
  • the amount of catalyst used is generally 0.1 to 20 g / m2, preferably 0.5 to 10 g / m2.
  • the saccharide and the catalyst can be in the same layer. However, they are preferably in separate layers.
  • a two-layer structure with a saccharide layer and a catalyst layer is particularly suitable. Higher optical densities can be achieved with a multilayer structure in which several catalyst layers and saccharide layers are alternately one above the other.
  • a polymeric binder with a defined glass transition temperature (Tg) is preferably used in the catalyst layer.
  • the Tg should be between 40 and 150 C, preferably between 60 and 120 C.
  • Binders from different polymer classes such as polyamides, polyesters, polycarbonates, vinyl polymers and cellulose derivatives can be used.
  • Examples include: polyvinyl chloride, poly (vinyl chloride-co-vinyl acetate), poly (vinylidene chloride-co-vinyl acetate), styrene-acrylonitrile copolymers, styrene-acrylonitrile-acrylate terpolymers, polyvinyl butyral, Cellulose acetobutyrate,
  • the content of binder in the catalyst layer is generally 40 to 80 wt .-%.
  • a polymeric barrier layer is located between the saccharide layer and the catalyst layer.
  • This barrier layer increases the stability of the recording material by separating saccharide and catalyst.
  • the polymer of the barrier layer should have a melting and / or softening temperature of more than 40 ° C., preferably more than 50 ° C.
  • Suitable polymers for this barrier layer include the substances specified as binders for the catalyst layer. Polyureas which are produced by reacting di- or triisocyanates and aliphatic diamines are also very suitable.
  • the layer thickness of the barrier layer is 0.05 to 5 ⁇ m, preferably 0.3 to 3 ⁇ m.
  • the recording material according to the invention can contain further layers known for this purpose. It can be beneficial to apply a top coat as the top layer.
  • a common thickness of this cover layer is 0.05 to 2.5 ⁇ m.
  • the cover layer can have non-stick properties, e.g. can be achieved by using polysiloxanes, polysiloxane-polyether block copolymers or fluoropolymers.
  • thermostable cover layer For writing the image material with a thermal head, it has proven to be advantageous to attach a thermostable cover layer.
  • Polymers suitable for this have a softening point above 100 ° C., preferably above 130 ° C.
  • Polycarbonate is particularly suitable, in particular homo- and copolymers of trimethylcyclohexyl bisphenol polycarbonate. The latter polymers result in image materials with a particularly high gloss and good image sharpness. Pollution the thermal head through the image material due to gluing or abrasion does not take place.
  • An additional advantage of these polymers is their ease of processing, for example by casting from an organic solution.
  • the recording materials according to the invention can be produced using known technologies. Production by casting or knife coating is cheap. Particularly good results are achieved if the saccharide layer is poured from water and the catalyst layer from a non-aqueous solvent. Suitable solvents for the production of the catalyst layer are e.g. Acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, dichloromethane, carbon tetrachloride and ethyl acetate.
  • the production of the barrier layer depends on the type of polymer selected for it; it can be made both from organic solution and from aqueous dispersion. To produce barrier layers made of polyureas, the starting components di- or triisocyanate and diamine are cast separately. The conversion to urea then takes place in the barrier layer itself.
  • thermosensitive recording materials according to the invention can e.g. can be written with a thermal head and deliver black and white images with high optical density, good grayscale reproduction, high sharpness and good stability.
  • Writing with an infrared laser is also possible, in which case an infrared absorber is added to the recording material, preferably the catalyst layer and / or the saccharide layer.
  • the recording material according to the invention and the recording method are also particularly advantageous from an ecological point of view.
  • a first layer of sucrose (4.5 g / m2) and polyvinyl alcohol (Moviol® 40-88) (0.5 g / m2) from water is applied to a polyethylene terephthalate base with a thickness of 63 ⁇ m. The layer is dried at 80 C for 5 minutes.
  • a second layer of a mixture of benzenesulfonic acid (3.6 g / m2) and polyvinyl butyral (Butvar® B-79) (0.4 g / m2) of methyl ethyl ketone is poured over it and dried at 35 ° C. in vacuo.
  • a solution of trimethylcyclohexylbisphenol polycarbonate (1.5 g / m2) and polysiloxane-polyether block copolymer (Tegoglide®) (0.1 g / m2) in methyl ethyl ketone is applied to produce a cover layer and then dried in vacuo at 35 C for 10 min.
  • the optical density of the recording materials from Examples 1 and 2 was measured in transmission. Test prints were made using a thermostatted stamp as a test device. The stamp created an image pattern with light and dark areas. The optical density (density measured in transmission) in the dark areas is defined as D-max, that in the light areas as D-min.
  • the D-0 values show that the materials according to the invention are highly transparent.
  • the values after 14 days of storage at 45 ° C demonstrate the good stability.
  • the density values increase significantly with increasing temperature, which makes it possible to set gray levels.
  • the maximum achievable densities are in a technically interesting area.
  • Example II of US 3161770 was reproduced, the following changes being made: Instead of “cellulosic reproduction paper", a hydrophilized polyethylene terephthalate film with a layer thickness of 100 ⁇ m was used (as a transparent base).
  • the optical densities achieved are low.

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

Abstract

A thermosensitive recording material contains a monosaccharide, oligosaccharide or polysaccharide and a catalyst in one or more binder layers arranged on a transparent support (substrate, carrier) material. On imagewise warming, for example by means of a thermal head, a black/white image of high optical density, good grey level reproduction, high sharpness and good stability is formed in the recording material.

Description

Die Erfindung betrifft ein transparentes thermoempfindliches Aufzeichnungsmaterial auf Basis von Mono-, Oligo- oder Polysacchariden.The invention relates to a transparent thermosensitive recording material based on mono-, oligo- or polysaccharides.

Direkt thermische Aufzeichnungsverfahren sind im Vergleich zu anderen Aufzeichnungsverfahren besonders benutzerfreundlich und weisen entscheidende ökologische Vorteile auf, da außer dem Aufzeichnungsmaterial selbst keine weiteren Verbrauchsmaterialien benötigt werden und keine Abfälle entstehen. Diese Materialien können beispielsweise mit einem Thermokopf oder einem Laserstrahl beschrieben werden.Direct thermal recording processes are particularly user-friendly in comparison to other recording processes and have decisive ecological advantages, since apart from the recording material itself no further consumables are required and no waste is generated. These materials can be written on, for example, with a thermal head or a laser beam.

Bekannte direkt thermische Aufzeichnungsmaterialien basieren z.B. auf der Reaktion eines Leucofarbstoffs mit einem Farbstoffentwickler, wobei diese Reaktion durch die Einwirkung von Wärme ausgelöst wird. Die zugehörigen Materialien sind einfach in Aufbau und Handhabung und werden beispielsweise in Fernkopierern, Registrierkassen oder Meßinstrumenten eingesetzt. Für höherwertige Anwendungen kommen sie jedoch nicht in Frage, da die Bildstabilität, insbesondere die Lichtstabilität und die maximal erreichbare Dichte unzureichend sind. Darüber hinaus ist es schwierig, transparente thermoempfindliche Aufzeichnungsmaterialien auf Basis von Leucofarbstoffen herzustellen.Known direct thermal recording materials are based e.g. on the reaction of a leuco dye with a dye developer, this reaction being triggered by the action of heat. The associated materials are simple to set up and handle and are used, for example, in facsimile machines, cash registers or measuring instruments. However, they are out of the question for higher-value applications, since the image stability, in particular the light stability and the maximum achievable density, are inadequate. In addition, it is difficult to produce transparent thermosensitive recording materials based on leuco dyes.

In US 3 161 770 ist ein thermografisches Kopierverfahren beschrieben, bei dem ein thermografisches Aufzeichnungsmaterial verwendet wird, das durch Behandeln eines Trägermaterials mit einer Mischung aus einem reduzierenden Kohlenhydrat und einer organischen Säure hergestellt worden ist. Als Trägermaterial wird dabei hauptsächlich Papier verwendet; die Behandlungslösung dringt in das Papier ein. Transparente Materialien können hierbei nicht erhalten werden. Aber auch bei Verwendung eines transparenten Schichtträgers anstelle einer opaken Papierunterlage, erwähnt werden auch "clear plastic materials, such as Mylar", werden nur Bilder mit unzureichender Dichte und Stabilität erhalten. Die transparenten Unterlagen saugen die Behandlungslösung nicht auf. Es bleibt eine klebrige Schicht zurück. Aufgrund der hohen Klebrigkeit ist eine Verarbeitung mit z.B. Thermodruckern unmöglich.US 3 161 770 describes a thermographic copying process using a thermographic recording material which is obtained by treating a carrier material with a mixture of a reducing carbohydrate and a organic acid has been produced. Paper is mainly used as the carrier material; the treatment solution penetrates the paper. Transparent materials cannot be obtained here. But even when using a transparent substrate instead of an opaque paper base, "clear plastic materials, such as Mylar" are also mentioned, only images with insufficient density and stability are obtained. The transparent documents do not absorb the treatment solution. A sticky layer remains. Due to the high stickiness, processing with thermal printers, for example, is impossible.

Die Aufgabe der vorliegenden Erfindung ist, ein transparentes thermoempfindliches Aufzeichnungsmaterial bereitzustellen, das bei hoher Transparenz Bilder mit guter Stabilität und hoher optischer Dichte liefert und mit üblichen Thermodruckern verarbeitet werden kann.The object of the present invention is to provide a transparent thermosensitive recording material which, with high transparency, provides images with good stability and high optical density and can be processed with conventional thermal printers.

Gegenstand der vorliegenden Erfindung ist ein thermoempfindliches Aufzeichnungsmaterial, das aus einem transparenten Trägermaterial und einer oder mehreren darauf angeordneten Bindemittelschichten besteht, wobei mindestens eine Bindemittelschicht ein Mono-, Oligo- oder Polysaccharid enthält und mindestens eine Bindemittelschicht, die mit der erstgenannten Bindemittelschicht identisch sein kann, einen Katalysator enthält.The present invention relates to a thermosensitive recording material which consists of a transparent substrate and one or more binder layers arranged thereon, at least one binder layer containing a mono-, oligo- or polysaccharide and at least one binder layer which can be identical to the first-mentioned binder layer, contains a catalyst.

Geeignete transparente Trägermaterialien sind Kunststoffolien aus z.B. Polyethylenterephthalat, Celluloseester wie Celluloseacetat, Cellulosepropionat, Cellulosebutyrate, desweiteren aus Polycarbonat oder Polyimid.Suitable transparent carrier materials are plastic films made of e.g. Polyethylene terephthalate, cellulose esters such as cellulose acetate, cellulose propionate, cellulose butyrates, furthermore made of polycarbonate or polyimide.

Das erfindungsgemäße transparente Aufzeichnungsmaterial enthält Mono-, Oligo- oder Polysaccharide, nachstehend gemeinsam als Saccharid bezeichnet. Beispielhaft seien die Monosaccharide Galaktose, Glucose, Idose, Mannose, Fructose, Sorbose, Ribose und Xylose genannt. Neben Monosacchariden mit der Formel Cn(H₂O)n können auch Desoxymonosaccharide eingesetzt werden. Beispiele für geeignete Oligosaccharide sind Saccharose, Maltose, Trehalose, Lactose und von der Saccharose abgeleitete Tri- und Tetrasaccharide wie Raffinose und Stachiose. Aus der Gruppe der Polysaccharide ist vor allem Stärke gut geeignet. Besonders gut geeignet sind (Poly)saccharide, die eine Ketogruppe oder Ketalgruppe enthalten.The transparent recording material according to the invention contains mono-, oligo- or polysaccharides, hereinafter referred to collectively as saccharide. The monosaccharides galactose, glucose, idose, mannose, fructose, sorbose, ribose and xylose may be mentioned as examples. In addition to monosaccharides with the formula C n (H₂O) n , deoxymonosaccharides can also be used. Examples of suitable oligosaccharides are sucrose, maltose, trehalose, lactose and tri- and tetrasaccharides derived from sucrose, such as raffinose and stachiose. Starch from the group of polysaccharides is particularly suitable. (Poly) saccharides containing a keto group or ketal group are particularly suitable.

Die Menge an Saccharid ist wichtig für die erreichbare optische Dichte und liegt im allgemeinen zwischen 0,5 und 30 g/m², vorzugsweise zwischen 1 und 20 g/m², besonders bevorzugt zwischen 2 und 15 g/m².The amount of saccharide is important for the optical density that can be achieved and is generally between 0.5 and 30 g / m², preferably between 1 and 20 g / m², particularly preferably between 2 and 15 g / m².

Als Bindemittel für das Saccharid eignen sich wasserlösliche und aus wäßriger Dispersion verarbeitbare Bindemittel, beispielsweise Polyvinylalkohol, teilverseifte Polyvinylacetate, Polyvinylpyrrolidon, hochmolekulares Polyethylenoxid, Copolymerisate aus Polyvinylpyrrolidon und Vinylacetat, desweiteren Latices von Acrylatcopolymerisaten, Polyvinylchlorid und Vinylchloridcopolymerisaten. Der Bindemittelanteil in der oder den das Saccharid enthaltenden Schichten beträgt 5 bis 90 Gew.-%, vorzugsweise 5 bis 70 Gew.-%, besonders bevorzugt 8 bis 50 Gew.-%.Suitable binders for the saccharide are water-soluble binders which can be processed from aqueous dispersion, for example polyvinyl alcohol, partially hydrolyzed polyvinyl acetates, polyvinyl pyrrolidone, high molecular weight polyethylene oxide, copolymers of polyvinyl pyrrolidone and vinyl acetate, and furthermore latices of acrylate copolymers, polyvinyl chloride and vinyl chloride copolymers. The proportion of binder in the layer or layers containing the saccharide is 5 to 90% by weight, preferably 5 to 70% by weight, particularly preferably 8 to 50% by weight.

Als Katalysatoren sind Metallverbindungen, insbesondere Salze von Übergangsmetallen, und Säuren (Protonsäuren und Lewissäuren) geeignet. Besonders wirksam sind anorganische und organische Protonsäuren. Bevorzugt werden Sulfonsäuren und Phosphonsäuren, beispielsweise Benzolsulfonsäure, p-Toluolsulfonsäure und o-Toluolsulfonsäure. Die Einsatzmenge an Katalysator beträgt im allgemeinen 0,1 bis 20 g/m², vorzugsweise 0,5 bis 10 g/m².Metal compounds, in particular salts of transition metals, and acids (protonic acids and Lewis acids) are suitable as catalysts. Inorganic and organic protonic acids are particularly effective. Sulfonic acids and phosphonic acids, for example benzenesulfonic acid, p-toluenesulfonic acid and o-toluenesulfonic acid, are preferred. The amount of catalyst used is generally 0.1 to 20 g / m², preferably 0.5 to 10 g / m².

Das Saccharid und der Katalysator können sich in der gleichen Schicht befinden. Bevorzugt befinden sie sich jedoch in separaten Schichten. Gut geeignet ist ein Zweischichtenaufbau mit einer Saccharidschicht und einer Katalysatorschicht. Höhere optische Dichten lassen sich mit einem Mehrschichtenaufbau realisieren, bei dem mehrere Katalysatorschichten und Saccharidschichten übereinander im Wechsel vorliegen.The saccharide and the catalyst can be in the same layer. However, they are preferably in separate layers. A two-layer structure with a saccharide layer and a catalyst layer is particularly suitable. Higher optical densities can be achieved with a multilayer structure in which several catalyst layers and saccharide layers are alternately one above the other.

In der Katalysatorschicht wird bevorzugt ein polymeres Bindemittel mit einer definierten Glasübergangstemperatur (Tg) verwendet. Die Tg soll zwischen 40 und 150 C, vorzugsweise zwischen 60 und 120 C liegen. Es können Bindemittel aus unterschiedlichen Polymerklassen wie z.B. Polyamide, Polyester, Polycarbonate, Vinylpolymerisate und Cellulosederivate eingesetzt werden. Beispielhaft seien genannt: Polyvinylchloid, Poly(vinylchlorid-co-vinylacetat), Poly(vinylidenchlorid-co-vinylacetat), Styrol-Acrylnitril-Copolymerisate, Styrol-Acrylnitril-Acrylat-Terpolymere, Polyvinylbutyral, Celluloseacetobutyrat, Der Gehalt an Bindemittel in der Katalysatorschicht liegt im allgemeinen bei 40 bis 80 Gew.-%.A polymeric binder with a defined glass transition temperature (Tg) is preferably used in the catalyst layer. The Tg should be between 40 and 150 C, preferably between 60 and 120 C. Binders from different polymer classes such as polyamides, polyesters, polycarbonates, vinyl polymers and cellulose derivatives can be used. Examples include: polyvinyl chloride, poly (vinyl chloride-co-vinyl acetate), poly (vinylidene chloride-co-vinyl acetate), styrene-acrylonitrile copolymers, styrene-acrylonitrile-acrylate terpolymers, polyvinyl butyral, Cellulose acetobutyrate, The content of binder in the catalyst layer is generally 40 to 80 wt .-%.

Besonders günstig ist es, in der Katalysatorschicht oder einer angrenzenden Schicht ein Bindemittel zu verwenden, das sich bei Erwärmung, insbesondere in Gegenwart des Katalysators, exotherm zersetzt, z.B. Cellulosenitrat oder nitrierte Stärke. In diesem Fall werden Aufzeichnungsmaterialien mit besonders hoher thermischer Empfindlichkeit erhalten.It is particularly favorable to use in the catalyst layer or in an adjacent layer a binder which decomposes exothermically when heated, in particular in the presence of the catalyst, e.g. Cellulose nitrate or nitrated starch. In this case, recording materials with particularly high thermal sensitivity are obtained.

In einer besonderen Ausführungsform der vorliegenden Erfindung befindet sich zwischen der Saccharidschicht und der Katalysatorschicht eine polymere Sperrschicht. Diese Sperrschicht erhöht die Stabilität des Aufzeichnungsmaterials durch Trennung von Saccharid und Katalysator. Das Polymer der Sperrschicht soll eine Schmelz- und/oder Erweichungstemperatur von mehr als 40 C, bevorzugt von mehr als 50 C haben. Geeignete Polymere für diese Sperrschicht sind u.a. die als Bindemittel für die Katalysatorschicht angegebenen Substanzen. Gut geeignet sind auch Polyharnstoffe, die durch Umsetzung von Di- oder Triisocyanaten und aliphatischen Diaminen erzeugt werden. Die Schichtdicke der Sperrschicht beträgt 0,05 bis 5 µm, vorzugsweise 0,3 bis 3 µm.In a particular embodiment of the present invention, a polymeric barrier layer is located between the saccharide layer and the catalyst layer. This barrier layer increases the stability of the recording material by separating saccharide and catalyst. The polymer of the barrier layer should have a melting and / or softening temperature of more than 40 ° C., preferably more than 50 ° C. Suitable polymers for this barrier layer include the substances specified as binders for the catalyst layer. Polyureas which are produced by reacting di- or triisocyanates and aliphatic diamines are also very suitable. The layer thickness of the barrier layer is 0.05 to 5 μm, preferably 0.3 to 3 μm.

Selbstverständlich kann das erfindungsgemäße Aufzeichnungsmaterial weitere für diesen Einsatzzweck bekannte Schichten enthalten. So kann es günstig sein, als oberste Schicht eine Abdeckschicht (topcoat) anzubringen. Eine übliche Dicke dieser Abdeckschicht beträgt 0,05 bis 2,5 µm.Of course, the recording material according to the invention can contain further layers known for this purpose. It can be beneficial to apply a top coat as the top layer. A common thickness of this cover layer is 0.05 to 2.5 µm.

Die Abdeckschicht kann Antihafteigenschaften haben, was sich z.B. durch die Verwendung von Polysiloxanen, Polysiloxan-Polyether-Blockcopolymerisaten oder Fluorpolymeren erreichen läßt.The cover layer can have non-stick properties, e.g. can be achieved by using polysiloxanes, polysiloxane-polyether block copolymers or fluoropolymers.

Für das Beschreiben des Bildmaterials mit einem Thermokopf hat es sich als günstig erwiesen, eine thermostabile Abdeckschicht anzubringen. Hierfür geeignete Polymere haben einen Erweichungspunkt oberhalb von 100 C, vorzugsweise oberhalb von 130 C. Gut geeignet ist Polycarbonat, insbesondere Homo- und Copolymere des Trimethylcyclohexylbisphenolpolycarbonats. Die letztgenannten Polymere führen zu Bildmaterialien mit besonders hohem Glanz und guter Bildschärfe. Eine Verschmutzung des Thermokopfes durch das Bildmaterial infolge von Verklebung oder Abrieb findet nicht statt. Ein zusätzlicher Vorteil dieser Polymere besteht in ihrer einfachen Verarbeitbarkeit, z.B. durch Gießen aus organischer Lösung.For writing the image material with a thermal head, it has proven to be advantageous to attach a thermostable cover layer. Polymers suitable for this have a softening point above 100 ° C., preferably above 130 ° C. Polycarbonate is particularly suitable, in particular homo- and copolymers of trimethylcyclohexyl bisphenol polycarbonate. The latter polymers result in image materials with a particularly high gloss and good image sharpness. Pollution the thermal head through the image material due to gluing or abrasion does not take place. An additional advantage of these polymers is their ease of processing, for example by casting from an organic solution.

Die Herstellung der erfindungsgemäßen Aufzeichnungsmaterialien kann mit bekannten Technologien erfolgen. Günstig ist die Herstellung durch Gießen oder Rakeln. Besonders gute Ergebnisse werden erzielt, wenn die Saccharidschicht aus Wasser und die Katalysatorschicht aus einem nichtwäßrigen Lösungsmittel gegossen wird. Geeignete Lösemittel zur Herstellung der Katalysatorschicht sind z.B. Aceton, Methylethylketon, Tetrahydrofuran, Dioxan, Dichlormethan, Tetrachlormethan und Ethylacetat. Die Herstellung der Sperrschicht richtet sich nach der Art des dafür ausgesuchten Polymers, sie kann sowohl aus organischer Lösung als auch aus wäßriger Dispersion erfolgen. Zur Herstellung von Sperrschichten aus Polyharnstoffen werden die Ausgangskomponenten Di- oder Triisocyanat und Diamin separat gegossen. Die Umsetzung zum Harnstoff findet dann in der Sperrschicht selbst statt.The recording materials according to the invention can be produced using known technologies. Production by casting or knife coating is cheap. Particularly good results are achieved if the saccharide layer is poured from water and the catalyst layer from a non-aqueous solvent. Suitable solvents for the production of the catalyst layer are e.g. Acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, dichloromethane, carbon tetrachloride and ethyl acetate. The production of the barrier layer depends on the type of polymer selected for it; it can be made both from organic solution and from aqueous dispersion. To produce barrier layers made of polyureas, the starting components di- or triisocyanate and diamine are cast separately. The conversion to urea then takes place in the barrier layer itself.

Die erfindungsgemäßen thermoempfindlichen Aufzeichnungsmaterialien können z.B. mit einem Thermokopf beschrieben werden und liefern Schwarz-Weiß-Bilder mit hoher optischer Dichte, guter Graustufenwiedergabe, hoher Schärfe und guter Stabilität. Auch das Einschreiben mit einem Infrarot-Laser ist möglich, in diesem Falle wird dem Aufzeichnungsmaterial, vorzugsweise der Katalysatorschicht und/oder der Saccharidschicht, ein Infrarotabsorber zugesetzt.The thermosensitive recording materials according to the invention can e.g. can be written with a thermal head and deliver black and white images with high optical density, good grayscale reproduction, high sharpness and good stability. Writing with an infrared laser is also possible, in which case an infrared absorber is added to the recording material, preferably the catalyst layer and / or the saccharide layer.

Das erfindungsgemäße Aufzeichnungsmaterial und das Aufzeichnungsverfahren sind auch aus ökologischer Sicht besonders vorteilhaft.The recording material according to the invention and the recording method are also particularly advantageous from an ecological point of view.

Die chemischen Reaktionen, die zur Ausbildung der optischen Dichte führen, sind im einzelnen nicht bekannt.The chemical reactions that lead to the formation of the optical density are not known in detail.

BeispieleExamples Beispiel 1example 1 Thermoempfindliches AufzeichnungsmaterialThermosensitive recording material

Auf einer Polyethylenterephthalat-Unterlage mit einer Dicke von 63 µm wird eine erste Schicht aus Saccharose (4,5 g/m²) und Polyvinylalkohol (Moviol® 40-88) (0,5 g/m²) aus Wasser aufgetragen. Die Schicht wird 5 Minuten bei 80 C getrocknet. Darüber wird eine zweite Schicht aus einer Mischung aus Benzolsulfonsäure (3,6 g/m²) und Polyvinylbutyral (Butvar® B-79) (0,4 g/m²) aus Methylethylketon gegossen und bei 35 C im Vakuum getrocknet. Darüber wird zur Herstellung einer Abdeckschicht eine Lösung aus Trimethylcyclohexylbisphenolpolycarbonat (1,5 g/m²) und Polysiloxan-Polyether-Blockcopolymerisat (Tegoglide®) (0,1 g/m²) in Methylethylketon aufgetragen und anschließend 10 min bei 35 C im Vakuum getrocknet.A first layer of sucrose (4.5 g / m²) and polyvinyl alcohol (Moviol® 40-88) (0.5 g / m²) from water is applied to a polyethylene terephthalate base with a thickness of 63 µm. The layer is dried at 80 C for 5 minutes. A second layer of a mixture of benzenesulfonic acid (3.6 g / m²) and polyvinyl butyral (Butvar® B-79) (0.4 g / m²) of methyl ethyl ketone is poured over it and dried at 35 ° C. in vacuo. A solution of trimethylcyclohexylbisphenol polycarbonate (1.5 g / m²) and polysiloxane-polyether block copolymer (Tegoglide®) (0.1 g / m²) in methyl ethyl ketone is applied to produce a cover layer and then dried in vacuo at 35 C for 10 min.

Beispiel 2Example 2 Thermoempfindliche AufzeichnungsmaterialienThermosensitive recording materials

Entsprechend der in Beispiel 1 beschriebenen Arbeitsweise wurden Aufzeichnungsmaterialien mit der in der nachfolgenden Tabelle beschriebenen Zusammensetzung hergestellt. Anstelle von Benzolsulfonsäure wurde p-Toluolsulfonsäure verwendet. Nr. 1. Schicht 2. Schicht 3. Schicht Abdeckschicht 2A 4,5 g/m² Glucose 0,5 g/m² PVA 4,0 g/m² p-TSS 6,0 g/m² SAN-Acr. --- 0,15 g/m² Tegoglide 2B 3,6 g/m² Glucose 0,4 g/m² PVA 3,2 g/m² p-TSS 2,8 g/m² SAN-Acr. --- 0,15 g/m² Tegoglide 2C 9,0 g/m² Glucose 1,0 g/m² PVA 1,6 g/m² p-TSS 2,4 g/m² SAN-Acr. 1,5 g/m² Nitrocellulose 0,15 g/m² Tegoglide 2D 9,0 g/m² Glucose 1,0 g/m² PVA 1,6 g/m² p-TSS 2,4 g/m² SAN-Acr. 3,5 g/m² Nitrocellulose 0,15 g/m² Tegoglide 2E 9,0 g/m² Glucose 1,0 g/m² PVA 1,6 g/m² p-TSS 2,4 g/m² Butvar --- 1,0 g/m² TMC-PC 2F 1,6 g/m² p-TSS 2,4 g/m² Butvar 9,0 g/m² Glucose 1,0 g/m² PVA --- 1,0 g/m² TMC-PC 2G 1,6 g/m² p-TSS 2,4 g/m² Butvar 9,0 g/m² Glucose 1,0 g/m² PVA 1,6 g/m² p-TSS 2,4 g/m² Butvar 1,0 g/m² TMC-PC Erläuterung der Einsatzstoffe: p-TSS p-Toluolsulfonsäure SAN-Acr. Terpolymer aus 56,5 Gew.-% Styrol, 22,5 Gew.-% Ethylhexylacrylat und 18 Gew.-% Acrylnitril Butvar® Polyvinylbutyral PVA Polyvinylalkohol, Moviol® 40-88 Tegoglide® Polysiloxan-Polyethylenoxid-Blockcopolymer TMC-PC Trimethylolcyclohexylbisphenolpolycarbonat Recording materials with the composition described in the table below were produced in accordance with the procedure described in Example 1. Instead of benzenesulfonic acid, p-toluenesulfonic acid was used. No. 1st layer 2 layer 3 layer Cover layer 2A 4.5 g / m² glucose 0.5 g / m² PVA 4.0 g / m² p-TSS 6.0 g / m² SAN-Acr. --- 0.15 g / m² tegoglide 2 B 3.6 g / m² glucose 0.4 g / m² PVA 3.2 g / m² p-TSS 2.8 g / m² SAN-Acr. --- 0.15 g / m² tegoglide 2C 9.0 g / m² glucose 1.0 g / m² PVA 1.6 g / m² p-TSS 2.4 g / m² SAN-Acr. 1.5 g / m² nitrocellulose 0.15 g / m² tegoglide 2D 9.0 g / m² glucose 1.0 g / m² PVA 1.6 g / m² p-TSS 2.4 g / m² SAN-Acr. 3.5 g / m² nitrocellulose 0.15 g / m² tegoglide 2E 9.0 g / m² glucose 1.0 g / m² PVA 1.6 g / m² p-TSS 2.4 g / m² Butvar --- 1.0 g / m² TMC-PC 2F 1.6 g / m² p-TSS 2.4 g / m² Butvar 9.0 g / m² glucose 1.0 g / m² PVA --- 1.0 g / m² TMC-PC 2G 1.6 g / m² p-TSS 2.4 g / m² Butvar 9.0 g / m² glucose 1.0 g / m² PVA 1.6 g / m² p-TSS 2.4 g / m² Butvar 1.0 g / m² TMC-PC Explanation of the input materials: p-TSS p-toluenesulfonic acid SAN Acr. Terpolymer of 56.5% by weight styrene, 22.5% by weight ethylhexyl acrylate and 18% by weight acrylonitrile Butvar® Polyvinyl butyral PVA Polyvinyl alcohol, Moviol® 40-88 Tegoglide® Polysiloxane-polyethylene oxide block copolymer TMC-PC Trimethylolcyclohexylbisphenol polycarbonate

Beispiel 3Example 3 Anwendungstechnische PrüfungenApplication tests

Die optische Dichte der Aufzeichnungsmaterialien aus den Beispielen 1 und 2 wurde in Transmission gemessen. Mit Hilfe eines thermostatisierbaren Stempels als Testgerät wurden Probedrucke angefertigt. Der Stempel erzeugte dabei ein Bildmuster mit hellen und dunkeln Stellen. Die optische Dichte (Densität gemessen in Transmission) an den dunklen Stellen wird als D-max definiert, die an den hellen Stellen als D-min. Definition der Meßgrößen: D-0 Densität nach Herstellung D-45-14d Densität nach 14-tägiger Lagerung bei 45°C D-max-130 Densität an den dunklen Stellen eines bei 130°C gedruckten Testbildes D-min-130 Densität an den hellen Stellen eines bei 130°C gedruckten Testbildes D-max-150 Densität an den dunklen Stellen eines bei 150°C gedruckten Testbildes D-min-150 Densität an den hellen Stellen eines bei 150°C gedruckten Testbildes D-max-180 Densität an den dunkein Stellen eines bei 180°C gedruckten Testbildes D-min-180 Densität an den hellen Stellen eines bei 180°C gedruckten Testbildes Meßergebnisse: Bsp.-Nr. D-0 D-45-14d D-max-130 D-min-130 D-max-150 D-min-150 D-max-180 D-min-180 1 0,03 0,03 0,46 0,04 0,66 0,05 0,98 0,06 2A 0,03 0,03 0,38 0,05 0,67 0,05 0,86 0,05 2B 0,03 0,04 0,45 0,05 0,73 0,05 0,78 0,06 2C 0,03 0,07 1,05 0,09 1,53 0,14 1,98 0,42 2D 0,04 0,11 1,35 0,16 1,74 0,29 2,45 0,46 2E 0,03 0,03 0,92 0,07 1,45 0,16 1,85 0,16 2F 0,03 0,03 0,83 0,06 1,28 0,12 1,49 0,15 2G 0,05 0,06 1,08 0,08 1,67 0,23 3,24 0,26 The optical density of the recording materials from Examples 1 and 2 was measured in transmission. Test prints were made using a thermostatted stamp as a test device. The stamp created an image pattern with light and dark areas. The optical density (density measured in transmission) in the dark areas is defined as D-max, that in the light areas as D-min. Definition of the measurands: D-0 Density after manufacture D-45-14d Density after 14 days of storage at 45 ° C D-max-130 Density in the dark areas of a test image printed at 130 ° C D-min-130 Density in the light areas of a test image printed at 130 ° C D-max-150 Density in the dark areas of a test image printed at 150 ° C D-min-150 Density in the light areas of a test image printed at 150 ° C D-max-180 Density in the dark areas of a test image printed at 180 ° C D-min-180 Density in the light areas of a test image printed at 180 ° C Measurement results: E.g. no. D-0 D-45-14d D-max-130 D-min-130 D-max-150 D-min-150 D-max-180 D-min-180 1 0.03 0.03 0.46 0.04 0.66 0.05 0.98 0.06 2A 0.03 0.03 0.38 0.05 0.67 0.05 0.86 0.05 2 B 0.03 0.04 0.45 0.05 0.73 0.05 0.78 0.06 2C 0.03 0.07 1.05 0.09 1.53 0.14 1.98 0.42 2D 0.04 0.11 1.35 0.16 1.74 0.29 2.45 0.46 2E 0.03 0.03 0.92 0.07 1.45 0.16 1.85 0.16 2F 0.03 0.03 0.83 0.06 1.28 0.12 1.49 0.15 2G 0.05 0.06 1.08 0.08 1.67 0.23 3.24 0.26

Die D-0-Werte zeigen, daß die erfindungsgemäßen Materialien hoch transparent sind. Die Werte nach 14-tägiger Lagerung bei 45°C belegen die gute Stabilität. Die Densitätswerte nehmen mit steigender Temperatur deutlich zu, wodurch die Einstellung von Graustufen möglich wird. Die maximal erreichbaren Densitäten liegen in einem technisch interessanten Bereich.The D-0 values show that the materials according to the invention are highly transparent. The values after 14 days of storage at 45 ° C demonstrate the good stability. The density values increase significantly with increasing temperature, which makes it possible to set gray levels. The maximum achievable densities are in a technically interesting area.

Beispiel 4Example 4 Vergleichsbeispiel in Anlehnung an Beispiel II von US 3161770Comparative example based on Example II of US 3161770

Das Beispiel II von US 3161770 wurde nachgestellt, wobei folgende Änderungen vorgenommen wurden:
Anstelle von "cellulosic reproduction paper" wurde (als transparente Unterlage) eine hydrophilierte Polyethylenterephthalatfolie mit 100 µm Schichtdicke eingesetzt.Example II of US 3161770 was reproduced, the following changes being made:
Instead of "cellulosic reproduction paper", a hydrophilized polyethylene terephthalate film with a layer thickness of 100 µm was used (as a transparent base).

Die Lösungen wurden nicht mit einem "solution-wet roller" sondern mit einer Rakel aufgetragen. (Diese Art der Auftragung wird in US 3161770, Spalte 4, Zeile 32 ebenfalls empfohlen und ist für nicht saugfähige Unterlagen besser geeignet als ein "solution-wet roller").The solutions were not applied with a "solution-wet roller" but with a squeegee. (This type of application is also recommended in US 3161770, column 4, line 32 and is more suitable for non-absorbent substrates than a "solution-wet roller").

Folgende Lösungen wurden verwendet: Wasser m-Benzoldisulfonsäure Harnstoff Saccharose 4 A 100 g 28,5 14,4 g 0 g 4 B 100 g 28,5 g 14,4 g 2 g 4 C 100 g 28,5 g 14,4 g 5 g 4 D 100 g 28,5 g 14,4 g 10 g The following solutions were used: water m-benzene disulfonic acid urea Sucrose 4 A 100 g 28.5 14.4 g 0 g 4 B 100 g 28.5 g 14.4 g 2 g 4 C 100 g 28.5 g 14.4 g 5 g 4 D 100 g 28.5 g 14.4 g 10 g

Die Lösungen wurden mit einer Naßschichtdicke von 15 µm aufgetragen, die Schichten wurden anschließend bei 70 C gründlich getrocknet. Die erhaltenen Aufzeichnungsmaterialien waren so klebrig, daß sie nicht mit einem Thermoprinter oder einem Thermostempel bedruckt werden konnten. Die Materialien sind damit für technische Anwendungen ungeeignet. Um dennoch eine Aussage zur Thermoempfindlichkeit zu bekommen, wurden die Materialien für kurze Zeit (ca. 15 s) in einem Ofen einer Temperatur von 181 C (360 F) ausgesetzt. Anschließend wurden die optischen Dichten in Transmission bestimmt (D-max): D-min D-max 4 A 0,06 0,12 4 B 0,07 0,15 4 C 0,06 0,20 4 D 0,08 0,22 The solutions were applied with a wet layer thickness of 15 μm, the layers were then dried thoroughly at 70 ° C. The recording materials obtained were so sticky that they could not be printed with a thermal printer or a thermal stamp. The materials are therefore unsuitable for technical applications . In order to get a conclusion about the thermal sensitivity, the materials were exposed to a temperature of 181 C (360 F) for a short time (approx. 15 s). The optical densities in transmission were then determined (D-max): D-min D-max 4 A 0.06 0.12 4 B 0.07 0.15 4 C 0.06 0.20 4 D 0.08 0.22

Die erreichten optischen Dichten sind gering.The optical densities achieved are low.

Claims (7)

Thermoempfindliches Aufzeichnungsmaterial, bestehend aus einem transparenten Trägermaterial und einer oder mehreren darauf angeordneten Bindemittelschichten, dadurch gekennzeichnet, daß mindestens eine Bindemittelschicht ein Mono-, Oligo- oder Polysaccharid enthält und mindestens eine Bindemittelschicht, die mit der erstgenannten Bindemittelschicht identisch sein kann, einen Katalysator enthält.Thermosensitive recording material, consisting of a transparent support material and one or more binder layers arranged thereon, characterized in that at least one binder layer contains a mono-, oligosaccharide or polysaccharide and at least one binder layer, which can be identical to the first-mentioned binder layer, contains a catalyst. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß das Mono-, Oligo- oder Polysaccharid und der Katalysator in verschiedenen Bindemittelschichten vorliegen.Recording material according to claim 1, characterized in that the mono-, oligo- or polysaccharide and the catalyst are present in different binder layers. Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß der Katalysator eine Sulfonsäure ist.Recording material according to one of claims 1 and 2, characterized in that the catalyst is a sulfonic acid. Aufzeichnungsmaterial nach Anspruch 2, dadurch gekennzeichnet, daß die Bindemittelschicht, in der der Katalysator vorliegt, ein Bindemittel mit einer Glasübergangstemperatur von 40 bis 150 C enthält.Recording material according to claim 2, characterized in that the binder layer in which the catalyst is present contains a binder with a glass transition temperature of 40 to 150 ° C. Aufzeichnungsmaterial nach Anspruch 2, dadurch gekennzeichnet, daß die Bindemittelschicht, in der der Katalysator vorliegt, oder eine daran angrenzende Schicht ein Bindemittel enthält, das sich bei der Erwärmung in Gegenwart des Katalysators exotherm zersetzt.Recording material according to Claim 2, characterized in that the binder layer in which the catalyst is present or an adjacent layer contains a binder which decomposes exothermically when heated in the presence of the catalyst. Aufzeichnungsmaterial nach Anspruch 2, dadurch gekennzeichnet, daß zwischen der Saccharidschicht und der Katalysatorschicht eine Sperrschicht angebracht ist.Recording material according to claim 2, characterized in that a barrier layer is provided between the saccharide layer and the catalyst layer. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es eine Abdeckschicht aus einem Polymeren mit einer Erweichungstemperatur >100 C enthält.Recording material according to one of Claims 1 to 6, characterized in that it contains a cover layer made of a polymer with a softening temperature> 100 ° C.
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DE4305165A1 (en) 1994-08-25
US5472930A (en) 1995-12-05
DE59402265D1 (en) 1997-05-07
EP0611662B1 (en) 1997-04-02
JPH06247057A (en) 1994-09-06
EP0611662A3 (en) 1995-01-18

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