EP0138159B1 - Heat-sensitive registration material, preparation thereof, and use of acid-modified polymers in such materials - Google Patents

Heat-sensitive registration material, preparation thereof, and use of acid-modified polymers in such materials Download PDF

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Publication number
EP0138159B1
EP0138159B1 EP84111852A EP84111852A EP0138159B1 EP 0138159 B1 EP0138159 B1 EP 0138159B1 EP 84111852 A EP84111852 A EP 84111852A EP 84111852 A EP84111852 A EP 84111852A EP 0138159 B1 EP0138159 B1 EP 0138159B1
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heat
influence
acid
recording material
reacts under
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EP0138159A2 (en
EP0138159A3 (en
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Hubertus Dr. Psaar
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Bayer AG
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Bayer AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3331—Macromolecular compounds

Definitions

  • Heat-sensitive recording materials are already known in which a colorless dye precursor with an acceptor is applied in one layer to a carrier material, the two components being coated separately with other materials in order to prevent a premature color reaction. During the heat treatment, melting the envelopes and, if applicable, the acceptor material brings both components into contact and triggers a color reaction.
  • Dye precursors from various classes of dyes are known as color formers.
  • materials which can trigger the color reaction mainly organic compounds containing phenolic groups have become known, e.g. B. bisphenol A, which, however, must be mixed with absorbents such as kaolin because of their high rate of migration and volatility. The volatility of the phenols is a major disadvantage of these materials, as they often cause unpleasant smells.
  • acceptors Another disadvantage of these acceptors is their sensitivity to pressure. Applying more pressure to the materials can trigger color reactions. In addition, the influence of moisture can cause the recorded image to disappear.
  • acceptors such as acids, metal salts or acid releasing compounds have also been described.
  • US Pat. No. 3,413,138 acceptors containing carboxylic acids which are prepared by polymerizing ⁇ , ⁇ -unsaturated carboxylic acids with unsaturated compounds such as acrylonitrile and alkyl acrylate. They all have the disadvantage that the dyes formed on them usually have insufficient resistance to light.
  • the glass transition temperature of the polymers can be varied within a wide range and adapted to the desired effect.
  • Acrylates such as methyl acrylate, ethyl ester, n-propyl ester, -n-, -iso- and -tert.-butyl ester, -hexyl ester, -2-ethylhexyl ester and lauryl ester are preferably suitable as comonomers for this purpose.
  • the acid-modified acrylonitrile polymers are prepared by known methods, the sulfo group either being introduced into the end of the polymerization chain by an acid catalyst or by comonomers containing acid groups, e.g. B.
  • the proportion of sulfo groups in the acrylic polymer is preferably 0.5 to 2% by weight.
  • carbinol bases or their derivatives especially carbinol bases or carbinol base ethers of small dye molecules which, due to their low molecular weight, easily penetrate into the polymers and can be bound there in salt form.
  • Examples of such compounds are carbinol bases or carbinol-based derivatives of diaryl and triarylmethane dyes which, for. B. be described in US-A-4 211 436 and fluoranes.
  • the acid-modified acrylonitrile polymers as a powder with binders, e.g. As polyvinyl alcohol, hydroxyethyl cellulose, gum arabic, polyvinyl pyrrolidone, casein or similar substances, ground.
  • binders e.g. As polyvinyl alcohol, hydroxyethyl cellulose, gum arabic, polyvinyl pyrrolidone, casein or similar substances, ground.
  • fatty acids or fatty acid amides, long-chain alkyl sulfates or esters of long-chain alcohols to the polymers, e.g. B. phosphoric acid esters of long-chain alcohols such as mono- and diphosphoric esters of C 8 - to C 22 alcohols, in amounts of 0.1 to 10%, based on the polymer.
  • the polymer can also be treated beforehand with the additives, e.g. B. be ground. The colorants are ground separately with the binders.
  • the dispersions of the acceptor are mixed with the dispersions of the color generator and applied and dried by means of a doctor blade on the carrier material, preferably cellulose paper, so that an application weight of 5 to 8 g per m 2 results.
  • the carrier material preferably cellulose paper
  • bases for example aliphatic amines or carbonates, for. B. mud chalk can be added.
  • a finely powdered polyacrylonitrile polymer prepared from 94% acrylonitrile, 0.5% methallylsulfonic acid and 5.5% methyl acrylate, are ground in a ball mill with 225 g of an 8% aqueous polyvinyl alcohol solution and with the addition of 1.3 g distearyl phosphoric acid ester.
  • a second dispersion is prepared from 1 g of octyl-4,4'-bis (dimethylamino) benzhydryl sulfone and 55 g of an 8% aqueous polyvinyl alcohol solution.
  • the following color former can also be used:
  • a polyacrylic polymer prepared from 86.5% acrylonitrile, 0.5% methallylsulfonic acid, 13% methyl ester, are ground with 1.3 g monostearyl phosphoric acid ester and 425 g water, suction filtered and dried.
  • the dry polymer is ground with 112 g of a 4% aqueous polyvinyl alcohol solution.
  • a second dispersion is made from 2 g of a color former of the formula and 55 g of an 8% aqueous polyvinyl alcohol solution.
  • the two dispersions according to Example 1 are mixed in a ratio of 1/10 and applied to cellulose paper. With a heated pen you get a black lightfast font on the dried paper sheet.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Paper (AREA)
  • Color Printing (AREA)
  • Paints Or Removers (AREA)

Description

Die Erfindung betrifft ein thermoreaktives Aufzeichnungsmaterial, das einen Farbstoffvorläufer und ein durch Sulfogruppen sauermodifiziertes Polymerisat des Acrylnitrils mit mindestens 50 Gew.-% Acrylnitrileinheiten als Akzeptor enthält.The invention relates to a thermoreactive recording material which contains a dye precursor and a polymer of acrylonitrile acid-modified by sulfo groups with at least 50% by weight of acrylonitrile units as acceptor.

Es sind bereits wärmeempfindliche Aufzeichnungsmaterialien bekannt, bei denen ein farbloses Farbstoffvorprodukt mit einem Akzeptor in einer Schicht auf ein Trägermaterial aufgebracht werden, wobei beide Komponenten mit anderen Materialien getrennt umhüllt werden, um eine vorzeitige Farbreaktion zu verhindern. Bei der Wärmebehandlung werden durch Schmelzen der Umhüllungen und gegebenenfalls des Akzeptormaterials beide Komponenten in Kontakt gebracht und eine Farbreaktion ausgelöst. Als Farbbildner sind Farbstoffvorläufer aus verschiedenen Farbstoffklassen bekannt. Als Materialien, die die Farbreaktion auslösen können, sind bisher hauptsächlich phenolische Gruppen enthaltende organische Verbindungen bekannt geworden, z. B. Bisphenol A, die aber wegen ihrer hohen Wanderungsgeschwindigkeit und Flüchtigkeit mit Absorbentien wie Kaolin, vermischt werden müssen. Die Flüchtigkeit der Phenole ist ein großer Nachteil dieser Materialien, da es oft zu Geruchsbelästigungen kommt. Ein weiterer Nachteil dieser Akzeptoren ist ihre Empfindlichkeit gegen Druck. Durch stärkeren Druck auf die Materialien können schon Farbreaktionen ausgelöst werden. Außerdem kann der Einfluß von Feuchtigkeit zum Verschwinden des aufgezeichneten Bildes führen. Es sind auch verschiedene andere Akzeptoren wie Säuren, Metallsalze oder säureabspaltende Verbindungen, beschrieben worden. Beispielsweise sind aus der US-A-3 413 138 Carbonsäuren enthaltende Akzeptoren bekannt, die durch Polymerisation von a, β-ungesättigten Carbonsäuren mit ungesättigten Verbindungen wie Acrylnitril und Acrylsäurealkylester hergestellt werden. Sie alle haben den Nachteil, daß die gebildeten Farbstoffe auf ihnen meist nur ungenügende Lichtbeständigkeit besitzen.Heat-sensitive recording materials are already known in which a colorless dye precursor with an acceptor is applied in one layer to a carrier material, the two components being coated separately with other materials in order to prevent a premature color reaction. During the heat treatment, melting the envelopes and, if applicable, the acceptor material brings both components into contact and triggers a color reaction. Dye precursors from various classes of dyes are known as color formers. As materials which can trigger the color reaction, mainly organic compounds containing phenolic groups have become known, e.g. B. bisphenol A, which, however, must be mixed with absorbents such as kaolin because of their high rate of migration and volatility. The volatility of the phenols is a major disadvantage of these materials, as they often cause unpleasant smells. Another disadvantage of these acceptors is their sensitivity to pressure. Applying more pressure to the materials can trigger color reactions. In addition, the influence of moisture can cause the recorded image to disappear. Various other acceptors such as acids, metal salts or acid releasing compounds have also been described. For example, US Pat. No. 3,413,138 acceptors containing carboxylic acids are known which are prepared by polymerizing α, β-unsaturated carboxylic acids with unsaturated compounds such as acrylonitrile and alkyl acrylate. They all have the disadvantage that the dyes formed on them usually have insufficient resistance to light.

Es wurde nun gefunden, daß durch Sulfogruppen sauermodifiziertes Polyacrylnitril, wie es auch für die Faserherstellung benutzt wird, ein Akzeptormaterial ist, welches die obengenannten Nachteile nicht aufweist. Neben den Polymeren des Acrylnitrils kommen auch Mischpolymerisate des Acrylnitrils mit anderen Vinylverbindungen wie Vinylidencyanid, Vinylfluorid, Vinylacetat, Vinylpropionat, Vinylpyridin, Vinylimidazol, Vinylpyrrolidon, Vinylethanol, Acryl- oder Methacrylsäureester sowie deren Hydroxyalkylester, Acryl- oder Methacrylsäureamide oder deren Dialkylamide in Betracht, wobei diese Mischpolymerisate mindestens 50 Gew.-%, vorzugsweise mindestens 85 Gew.-% Acrylnitrileinheiten aufweisen. Durch Verwendung bestimmter Comonomerer läßt sich die Glastemperatur der Polymeren in weiten Bereichen variieren und dem gewünschten Effekt anpassen. Als Comonomere sind hierzu vorzugsweise Acrylate wie Acrylsäuremethylester, -ethylester, -n-propylester, -n-, -iso- und -tert.-butylester, -hexylester, -2-ethylhexylester und -laurylester geeignet. Die Herstellung der sauermodifizierten Acrylnitrilpolymerisate erfolgt nach bekannten Methoden, wobei die Sulfogruppe entweder durch einen sauren Katalysator in das Ende der Polymerisationskette eingeführt wird oder durch Säuregruppen enthaltende Comonomere, z. B. Vinylsulfonsäure, Styrolsulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Vinyloxyarensulfonsäure, Allyloxyarensulfonsäure, Methallyloxyarensulfonsäure, Acryloxyalkoxyarensulfonsäure, einpolymerisiert wird. Diese Herstellungen werden beispielsweise in DT-C-654 989, US-A-2 601 256 und US-A-2 913 438 sowie in F. Krczil "Kurzes Handbuch der Polymerisationstechnik" (1940) Bd. I, S. 722-725, und in Houben-Weyl, "Methoden der organischen Chemie" (1961), Bd. XIV/1 S. 998 bis 1009 beschrieben.It has now been found that polyacrylonitrile acid-modified by sulfo groups, as is also used for fiber production, is an acceptor material which does not have the disadvantages mentioned above. In addition to the polymers of acrylonitrile, there are also copolymers of acrylonitrile with other vinyl compounds such as vinylidene cyanide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl ethanol, acrylic or methacrylic acid esters and their hydroxyalkyl esters, acrylic or methacrylic acid amides or their dialkyl amides or their dialkyl amides, or these dialkyl amides, or these dialkyl amides, or their dialkyl amides, or these dialkyl amides, or their dialkyl amides, or their dialkyl amides or these dialkyl amides, Copolymers have at least 50% by weight, preferably at least 85% by weight, of acrylonitrile units. By using certain comonomers, the glass transition temperature of the polymers can be varied within a wide range and adapted to the desired effect. Acrylates such as methyl acrylate, ethyl ester, n-propyl ester, -n-, -iso- and -tert.-butyl ester, -hexyl ester, -2-ethylhexyl ester and lauryl ester are preferably suitable as comonomers for this purpose. The acid-modified acrylonitrile polymers are prepared by known methods, the sulfo group either being introduced into the end of the polymerization chain by an acid catalyst or by comonomers containing acid groups, e.g. B. vinyl sulfonic acid, styrene sulfonic acid, allylsulfonic acid, methallylsulfonic acid, vinyloxyarenesulfonic acid, allyloxyarenesulfonic acid, methallyloxyarenesulfonic acid, acryloxyalkoxyarenesulfonic acid. These preparations are described, for example, in DT-C-654 989, US-A-2 601 256 and US-A-2 913 438 and in F. Krczil "Kurzes Handbuch der Polymerisationstechnik" (1940) Vol. I, pp. 722-725 , and in Houben-Weyl, "Methods of Organic Chemistry" (1961), Vol. XIV / 1 pp. 998 to 1009.

Der Anteil der Sulfogruppen im Acrylpolymerisat beträgt vorzugweise 0,5 bis 2 Gew.-%.The proportion of sulfo groups in the acrylic polymer is preferably 0.5 to 2% by weight.

Als Farbstoffvorläufer sind die üblicherweise für Druck- und Thermokopierzwecke verwendbaren Farbstoffbildner zu verwenden mit Ausnahme derjenigen, die nur durch Luftoxidation in Farbstoffe überführt werden können. Geeignete Farbbildner werden z. B. in den folgenden Publikationen beschrieben:

  • US-A-3 193404, US-A-3 489 800, DT-A-2 001 864.
  • DT-A-2 363 453, GB-A-1 160 940, JP-A-53 9127,
  • JP-A-46 29550, JP-A-43 2119, JP-A-52 148 099,
  • J P-A-48 3695, JP-A-51 23204, J P-A-56 52729.
The dye precursors to be used are the dye formers which can usually be used for printing and thermocopying purposes, with the exception of those which can only be converted into dyes by air oxidation. Suitable color formers are e.g. B. described in the following publications:
  • US-A-3 193404, US-A-3 489 800, DT-A-2 001 864.
  • DT-A-2 363 453, GB-A-1 160 940, JP-A-53 9127,
  • JP-A-46 29550, JP-A-43 2119, JP-A-52 148 099,
  • J PA-48 3695, JP-A-51 23204, J PA-56 52729.

Besonders geeignet sind Carbinolbasen oder deren Derivate, speziell Carbinolbasen oder Carbinolbasenether kleiner Farbstoffmoleküle, die aufgrund ihres niederen Molekulargewichtes leicht in die Polymerisate eindringen und dort salzartig gebunden werden können.Particularly suitable are carbinol bases or their derivatives, especially carbinol bases or carbinol base ethers of small dye molecules which, due to their low molecular weight, easily penetrate into the polymers and can be bound there in salt form.

Beispiele für solche Verbindungen sind Carbinolbasen bzw. Carbinolbasenderivate von Diaryl- und Triarylmethanfarbstoffen, die z. B. in der US-A-4 211 436 beschrieben werden und Fluorane.Examples of such compounds are carbinol bases or carbinol-based derivatives of diaryl and triarylmethane dyes which, for. B. be described in US-A-4 211 436 and fluoranes.

Zur Herstellung der wärmeempfindlichen Materialien, z. B. Papier, werden die sauer modifizierten Acrylnitrilpolymerisate . als Pulver mit Bindemitteln, z. B. Polyvinylalkohol, Hydroxyethylcellulose, Gummiarabicum, Polyvinylpyrrolidon, Casein oder ähnlichen Substanzen, vermahlen.To produce the heat-sensitive materials, e.g. B. paper, the acid-modified acrylonitrile polymers. as a powder with binders, e.g. As polyvinyl alcohol, hydroxyethyl cellulose, gum arabic, polyvinyl pyrrolidone, casein or similar substances, ground.

Zur besseren Farbstoffbildung ist es zweckmäßig, den Polymerisaten Fettsäuren oder Fettsäureamide, langkettige Alkylsulfate oder Ester von Langkettigen Alkoholen z. B. Phosphorsäureester langkettiger Alkohole wie Mono- und Diphosphorsäureester von C8- bis C22-Alkoholen, in Mengen von 0,1 bis 10 %, bezogen auf das Polymerisat, zuzusetzen. Das Polymerisat kann auch vorher mit den Zusätzen behandelt, z. B. vermahlen werden. Die Farbgeber werden getrennt mit den Bindemitteln vermahlen. Die Dispersionen des Akzeptors werden mit den Dispersionen des Farbgebers vermischt und mittels einer Rakel auf das Trägermaterial, vorzugsweise Cellulosepapier, so aufgetragen und getrocknet, daß dabei ein Auftragsgewicht von 5 bis 8 g pro m2 resultiert. Je nach Reaktivität des Farbgebers ist es auch möglich, Polymerisat und Farbgeber zusammen mit dem Bindemittel zu vermahlen und wie beschrieben aufzutragen. Außerdem können zur Stabilisierung der Farbbildner Basen, beispielsweise aliphatische Amine oder Carbonate, z. B. Schlammkreide, zugesetzt werden. In einer anderen Verfahrensweise ist es auch möglich das Akzeptorpapier aus einer Mischung eines Acrylnitrilpolymerisat mit dem oben beschriebenen Zusätzen mit Zellstoff, Leimungsmittel und Aluminiumsulfat in einem Blattbildner zu erzeugen und mit dem Farbbildner zu beschichten.For better dye formation, it is advisable to add fatty acids or fatty acid amides, long-chain alkyl sulfates or esters of long-chain alcohols to the polymers, e.g. B. phosphoric acid esters of long-chain alcohols such as mono- and diphosphoric esters of C 8 - to C 22 alcohols, in amounts of 0.1 to 10%, based on the polymer. The polymer can also be treated beforehand with the additives, e.g. B. be ground. The colorants are ground separately with the binders. The dispersions of the acceptor are mixed with the dispersions of the color generator and applied and dried by means of a doctor blade on the carrier material, preferably cellulose paper, so that an application weight of 5 to 8 g per m 2 results. Depending on the reactivity of the color donor, it is also possible to grind the polymer and color donor together with the binder and apply it as described. In addition, bases, for example aliphatic amines or carbonates, for. B. mud chalk can be added. In another procedure, it is also possible to produce the acceptor paper from a mixture of an acrylonitrile polymer with the additives described above with cellulose, sizing agent and aluminum sulfate in a sheet former and to coat it with the color former.

Beispiel 1example 1

In einer Kugelmühle werden 40 g eines feinpulvrigen Polyacrylnitrilpolymerisats, hergestellt aus 94 % Acrylnitril, 0,5 % Methallylsulfonsäure und 5,5 % Acrylsäuremethylester, mit 225 g einer 8 %-igen wäßrigen Polyvinylalkohollösung und unter Zusatz von 1,3 g Distearylphosphorsäureester vermahlen. Eine zweite Dispersion wird aus 1 g Octyl-4,4'-bis-(dimethylamino)-benzhydrylsulfon und 55 g einer 8 %-igen wäßrigen Polyvinylalkohollösung hergestellt. Man mischt die Dispersion des Farbbildners mit der des Akzeptors im Verhältnis 1/10 und trägt die Mischung auf Cellulosepapier mittels einer Rakel auf und trocknet sie, so daß man ein Auftragsgewicht von 6 bis 7 g/m2 erhält. Das Papier ist mit Schreibmitteln, wie z. B. einem Kugelschreiber, beschriftbar. Es ist gegen starken Druck unempfindlich. Bei Berührung des Papiers mit einem beheizten Stift erhält man eine klare, scharfe, schattenfreie, blaue Schrift. Die Lichtechtheit der Färbung ist ausgezeichnet.40 g of a finely powdered polyacrylonitrile polymer, prepared from 94% acrylonitrile, 0.5% methallylsulfonic acid and 5.5% methyl acrylate, are ground in a ball mill with 225 g of an 8% aqueous polyvinyl alcohol solution and with the addition of 1.3 g distearyl phosphoric acid ester. A second dispersion is prepared from 1 g of octyl-4,4'-bis (dimethylamino) benzhydryl sulfone and 55 g of an 8% aqueous polyvinyl alcohol solution. The dispersion of the color former is mixed with that of the acceptor in a ratio of 1/10 and the mixture is applied to cellulose paper by means of a doctor blade and dried so that an application weight of 6 to 7 g / m 2 is obtained. The paper is covered with writing materials such as B. a ballpoint pen, can be labeled. It is insensitive to strong pressure. When you touch the paper with a heated pen, you get clear, sharp, shadow-free, blue writing. The lightfastness of the coloring is excellent.

Anstelle des obengenannten Farbbildners kann man auch folgende Farbbildner einsetzen:Instead of the color former mentioned, the following color former can also be used:

Phenyl-4,4'-bis-(dimethylamino)benzhydryl-sulfon, Phenyl-4,4'-bis-(dimethylamino)-benzhydryl-sulfonamid, p-Tolyl-4,4'-bis-(dimethylamino)-benzhydryl-sulfonamid, p-Tolyl-3,3'-bismethyl-4,4'-bis-(dimethylamino)-benzhydryl-sulfon, p-Tolyl-4,4'-bis-(diethylamino)-benzhydryl-sulfon, Dodecyl-4,4'-bis-(dimethylamino)-benzhydryl-sulfon, p-Dodecyl-phenyl-4,4'-bis(dimethylamino)-benzhydryl-sulfon.Phenyl-4,4'-bis (dimethylamino) benzhydryl sulfone, phenyl 4,4'-bis (dimethylamino) benzhydryl sulfonamide, p-tolyl 4,4'-bis (dimethylamino) benzhydryl- sulfonamide, p-tolyl-3,3'-bismethyl-4,4'-bis (dimethylamino) benzhydryl sulfone, p-tolyl-4,4'-bis (diethylamino) benzhydryl sulfone, dodecyl-4 , 4'-bis (dimethylamino) benzhydryl sulfone, p-dodecylphenyl-4,4'-bis (dimethylamino) benzhydryl sulfone.

Man erhält beim Berühren des so behandelten Papieres mit einem beheizten Stift ebenfalls eine lichtechte blaue Schrift.When the paper treated in this way is touched with a heated pen, light-fast blue writing is also obtained.

Beispiel 2Example 2

40 g eines Polyacrylpolymerisats, hergestellt aus 86,5 % Acrylnitril, 0,5 % Methallylsulfonsäure, 13 % Acrylsäuremethylester werden mit 1,3 g Monostearylphosphorsäureester und 425 g Wasser vermahlen, abgesaugt und getrocknet. Das trockene Polymerisat wird mit 112 g einer 4 %-igen wäßrigen Polyvinylalkohollösung vermahlen. Eine zweite Dispersion wird aus 2 g eines Farbbildners der Formel

Figure imgb0001
und 55 g einer 8 %-igen wäßrigen Polyvinylalkohollösung hergestellt. Man mischt beide Dispersionen gemäß Beispiel 1 im Verhältnis 1/10 und trägt sie auf Cellulosepapier auf. Mit einem beheizten Stift erhält man auf dem getrockneten Papierblatt eine schwarze lichtechte Schrift.40 g of a polyacrylic polymer, prepared from 86.5% acrylonitrile, 0.5% methallylsulfonic acid, 13% methyl ester, are ground with 1.3 g monostearyl phosphoric acid ester and 425 g water, suction filtered and dried. The dry polymer is ground with 112 g of a 4% aqueous polyvinyl alcohol solution. A second dispersion is made from 2 g of a color former of the formula
Figure imgb0001
 and 55 g of an 8% aqueous polyvinyl alcohol solution. The two dispersions according to Example 1 are mixed in a ratio of 1/10 and applied to cellulose paper. With a heated pen you get a black lightfast font on the dried paper sheet.

Setzt man anstelle des obengenannten Farbbildners eine Verbindung der Formel

Figure imgb0002
(Beispiel 2 der US-A-4 211 436) ein, so erhält man bei der Berührung mit einem beheizten Stift eine lichtechte schwarzblaue Schrift.If a compound of the formula is used instead of the color former mentioned above
Figure imgb0002
 (Example 2 of US-A-4 211 436), you get a lightfast black and blue font when touched with a heated pen.

Beispiel 3Example 3

40 g eines Acrylnitrilpolymerisats, hergestellt aus 92,2 % Acrylnitril, 2 % Methallylsulfonsäure, 5,8 % Acrylsäuremethylester, werden mit 1,3 g des Ethanolaminsalzes vom Distearylphosphorsäureester wie im Beispiel 2 behandelt und in einer Polyvinylalkohollösung dispergiert. Die Dispersion wird mit einer zweiten Dispersion aus 2 g des Farbbildners der Formel

Figure imgb0003
(Beispiel 3 der US-A-4 211 436) und 55 g einer wäßrigen 8 %-igen Polyvinylalkohollösung im Verhältnis 1/10 gemischt und auf Cellulosepapier gemäß Beispiel 1 aufgetragen. Bei der Beschriftung mit einem beheizten Stift erhält man eine rote lichtechte Schrift.40 g of an acrylonitrile polymer, prepared from 92.2% acrylonitrile, 2% methallylsulfonic acid, 5.8% methyl acrylate, are treated with 1.3 g of the ethanolamine salt of the distearylphosphate as in Example 2 and dispersed in a polyvinyl alcohol solution. The dispersion is mixed with a second dispersion of 2 g of the color former of the formula
Figure imgb0003
 (Example 3 of US-A-4 211 436) and 55 g of an aqueous 8% polyvinyl alcohol solution mixed in a ratio of 1/10 and applied to cellulose paper according to Example 1. When labeling with a heated pen, you get a red, lightfast font.

Ersetzt man das Polymerisat durch ein Polyacrylnitrilpolymerisat mit einem Gehalt von 22 % Acrylsäuremethylester und den Farbbildner durch einen der Formel

Figure imgb0004
so erhält man bei der Hitzebeschriftung ein lichtechtes schwarzblaues Schriftbild.If the polymer is replaced by a polyacrylonitrile polymer containing 22% of methyl acrylate and the color former by one of the formula
Figure imgb0004
 so you get a lightfast black and blue typeface with the heat inscription.

Ersetzt man den Farbbildner durch einen Farbbildner der US-A-4 211 436, Tabelle der Spalten 9 - 16, so erhält man bei der Hitzebeschriftung Schriftbilder mit den in der Tabelle angegebenen Farbtönen.If the color former is replaced by a color former from US Pat. No. 4,211,436, table in columns 9-16, the inscriptions obtained with the heat inscription have the hues indicated in the table.

Beispiel 4Example 4

40 g eines Acrylnitrilpolymerisates aus 89 % Acrylnitril, 1,9 % Styrolsulfonsäure, 9 % Acrylsäuremethylester werden mit 3 g des Ethanolaminsalzes vom Distearylphosphorsäureester und 225 g einer 2 %-igen wäßrigen Polyvinylalkohollösung vermahlen. Eine 2. Dispersion wird aus 2 g p-Tolyl-4,4'-bis-(dimethylamino)-benzhydrylsulfon und 55 g einer 8 %-igen wäßrigen Polyvinylalkohollösung hergestellt.40 g of an acrylonitrile polymer composed of 89% acrylonitrile, 1.9% styrene sulfonic acid, 9% methyl ester are ground with 3 g of the ethanolamine salt of the distearyl phosphoric acid ester and 225 g of a 2% aqueous polyvinyl alcohol solution. A second dispersion is prepared from 2 g of p-tolyl-4,4'-bis (dimethylamino) benzhydryl sulfone and 55 g of an 8% aqueous polyvinyl alcohol solution.

Beide Dispersionen werden vermischt und gemäß Beispiel 1 im Verhältnis 1/10 auf Papier aufgetragen. Mit einem beheizten Stift erhält man eine lichtechte blaue Schrift.Both dispersions are mixed and applied according to Example 1 in a ratio of 1/10 to paper. With a heated pen you get a lightfast blue font.

Man erhält ebenfalls blaue lichtechte Drucke, wenn man anstelle des obengenannten Polymerisates Acrylpolymere folgender Zusammensetzung verwendet:

  • 80 % Acrylnitril, 4,5 % Styrolsulfonsäure, 14,5 % Acrylsäurebutylester;
  • 78,5 % Acrylnitril, 1,5 % Methallylsulfonsäure, 20 % Acrylsäureethylester;
  • 54 % Acrylnitril, % Methallylsulfonsäure, 45 % Acrylsäuremethylester;
  • 78,5 % Acrylnitril, 14 % Styrolsulfonsäure, 7 % Acrylsäuremethylester;
  • 89,5 % Acrylnitril, 0,8 % Methallylsulfonsäure, 9,5 % N-Phenyl-maleinimid;
  • 73 % Acrylnitril, 2,5 % 2-Acrylamido-2-methylpropansulfonsäure, 24,5 % Acrylsäurebutylester;
  • 84 % Acrylnitril, 1,7 % 2-Acrylamido-2-methylpropansulfonsäure, 14 % Ethylhexylacrylat;
  • 88 % Acrylnitril, 1,8 % 2-Acrylamido-2-methylpropansulfonsäure, 13,5 % Stearylmethacrylat.
Blue lightfast prints are also obtained if, instead of the polymer mentioned above, acrylic polymers of the following composition are used:
  • 80% acrylonitrile, 4.5% styrene sulfonic acid, 14.5% butyl acrylate;
  • 78.5% acrylonitrile, 1.5% methallylsulfonic acid, 20% ethyl acrylate;
  • 54% acrylonitrile,% methallylsulfonic acid, 45% methyl acrylate;
  • 78.5% acrylonitrile, 14% styrene sulfonic acid, 7% methyl acid ester;
  • 89.5% acrylonitrile, 0.8% methallylsulfonic acid, 9.5% N-phenyl-maleimide;
  • 73% acrylonitrile, 2.5% 2-acrylamido-2-methylpropanesulfonic acid, 24.5% butyl acrylate;
  • 84% acrylonitrile, 1.7% 2-acrylamido-2-methylpropanesulfonic acid, 14% ethylhexyl acrylate;
  • 88% acrylonitrile, 1.8% 2-acrylamido-2-methylpropanesulfonic acid, 13.5% stearyl methacrylate.

Claims (9)

1. Recording material which reacts under the influence of heat and contains a dyestuff precursor and an acceptor material, where the acceptor material is a polymer of acrylonitrile which is acid modified by sulpho groups and contains at least 50 % by weight of acrylonitrile units.
2. Recording material which reacts under the influence of heat, according to Claim 1, characterised in that the acrylic polymer contains 0.5 to 2 % by weight of a sulpho group.
3. Recording material which reacts under the influence of heat, according to Claim 1, characterised in that the acrylic polymer contains acrylate or methacrylate as further comonomers.
4. Recording material which reacts under the influence of heat, according to Claim 1, characterised in that it contains carbinol bases or carbinol base derivatives of di- or triarylmethane dyestuffs or fluoranes as the dyestuff precursors.
5. Recording material which reacts under the influence of heat, according to Claim 1, characterised in that it contains 4,4'-tetraalkyl-diaminodiarylmethanealkyl-sulphinates as the dyestuff precursors.
6. Recording material which reacts under the influence of heat, according to Claims 1 to 5, characterised in that the material contains phosphoric acid esters of long-chain alcohols.
7. Recording material which reacts under the influence of heat, according to Claims 1 to 6, characterised in that the material preferably contains mono- and diphosphoric acid esters of C8 to C22-alcohols.
8. Process for the preparation of the recording material of Claim 1, which reacts under the influence of heat, by coating carrier materials with formulations containing dyestuff precursors and acceptors.
9. Use of acid-modified polymers of acrylonitrile as acceptors in recording materials which react under the influence of heat.
EP84111852A 1983-10-13 1984-10-04 Heat-sensitive registration material, preparation thereof, and use of acid-modified polymers in such materials Expired EP0138159B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3337296 1983-10-13
DE19833337296 DE3337296A1 (en) 1983-10-13 1983-10-13 THERMOREACTIVE RECORDING MATERIAL, ITS PRODUCTION AND THE USE OF ACID-MODIFIED POLYMERISATS AS ACCEPTORS IN THIS RECORDING MATERIAL

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EP0138159A2 EP0138159A2 (en) 1985-04-24
EP0138159A3 EP0138159A3 (en) 1986-05-21
EP0138159B1 true EP0138159B1 (en) 1988-08-31

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EP84111852A Expired EP0138159B1 (en) 1983-10-13 1984-10-04 Heat-sensitive registration material, preparation thereof, and use of acid-modified polymers in such materials

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US (1) US4600930A (en)
EP (1) EP0138159B1 (en)
JP (1) JPS60132788A (en)
CA (1) CA1230739A (en)
DE (2) DE3337296A1 (en)
FI (1) FI79976C (en)
HK (1) HK51289A (en)

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Publication number Priority date Publication date Assignee Title
AT399126B (en) * 1987-03-31 1995-03-27 Ruetgerswerke Ag COLOR DEVELOPER DIMENSIONS FOR COLOR REACTION SYSTEMS
DE3715724A1 (en) * 1987-05-12 1988-11-24 Bayer Ag THERMOREACTIVE RECORDING MATERIAL
US4877767A (en) * 1987-08-14 1989-10-31 The Mead Corporation Vinyl developer resins
DE3922766A1 (en) * 1989-07-11 1991-01-17 Bayer Ag THERMOREACTIVE RECORDING MATERIAL
DE3940480A1 (en) * 1989-12-07 1991-06-13 Bayer Ag CHROMOGENIC ENAMINE COMPOUNDS, THEIR PRODUCTION AND USE AS A COLOR IMAGE
JP2596271Y2 (en) * 1991-10-02 1999-06-07 株式会社アマダ Laser processing machine

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3413138A (en) * 1965-10-13 1968-11-26 Interchem Corp Thermosensitive copy sheet
BE790932A (en) * 1971-11-01 1973-03-01 Fuji Photo Film Co Ltd RECORD SHEET
JPS5833838B2 (en) * 1978-03-28 1983-07-22 神崎製紙株式会社 heat sensitive recording material
DE2820486A1 (en) * 1978-05-10 1979-11-15 Bayer Ag PROCESS FOR THE PRODUCTION OF SULFINATES OF 4,4'DIAMINOBENZHYDROL AND ITS SUBSTITUTIONAL PRODUCTS
JPS5553592A (en) * 1978-10-16 1980-04-19 Fuji Photo Film Co Ltd Recording material
JPS56148588A (en) * 1980-04-22 1981-11-18 Mitsubishi Paper Mills Ltd Heat-sensitive paper
JPS57167380A (en) * 1981-04-08 1982-10-15 Pilot Ink Co Ltd Thermochromic material
JPS59106995A (en) * 1982-12-11 1984-06-20 Kanzaki Paper Mfg Co Ltd Thermal recording body

Also Published As

Publication number Publication date
FI843998A0 (en) 1984-10-11
DE3473747D1 (en) 1988-10-06
FI843998L (en) 1985-04-14
DE3337296A1 (en) 1985-04-25
FI79976C (en) 1990-04-10
US4600930A (en) 1986-07-15
JPS60132788A (en) 1985-07-15
EP0138159A2 (en) 1985-04-24
CA1230739A (en) 1987-12-29
FI79976B (en) 1989-12-29
HK51289A (en) 1989-07-07
EP0138159A3 (en) 1986-05-21

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