EP0122468B1 - Heat-sensitive registration foil - Google Patents

Heat-sensitive registration foil Download PDF

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Publication number
EP0122468B1
EP0122468B1 EP84102807A EP84102807A EP0122468B1 EP 0122468 B1 EP0122468 B1 EP 0122468B1 EP 84102807 A EP84102807 A EP 84102807A EP 84102807 A EP84102807 A EP 84102807A EP 0122468 B1 EP0122468 B1 EP 0122468B1
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EP
European Patent Office
Prior art keywords
phthalic acid
sensitive recording
heat
recording sheet
heat sensitive
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
Application number
EP84102807A
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German (de)
French (fr)
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EP0122468A2 (en
EP0122468A3 (en
Inventor
Noboru Central Research Laboratory Yamato
Toshimi Central Research Laboratory Satake
Toshiaki Central Research Laboratory Minami
Fumio Central Research Laboratory Fujimura
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Jujo Paper Co Ltd
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Jujo Paper Co Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof

Definitions

  • the invention relates to a heat-sensitive recording sheet which has a high degree of whiteness, which is retained better than before even over a long period of time.
  • a heat-sensitive recording sheet is generally obtained by placing it on the surface of a support, e.g. B. a paper or film, etc., a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, e.g. B. a phenolic substance, mixing the dispersions obtained and adding a binder, filler, sensitizer, lubricant and other auxiliaries has been obtained.
  • a support e.g. B. a paper or film, etc.
  • a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, e.g. B. a phenolic substance, mixing the dispersions obtained and adding a binder, filler, sensitizer, lubricant and other auxiliaries has been obtained.
  • the coating When exposed to heat or heat, the coating immediately undergoes a chemical reaction in which a color is formed. Depending on the choice of special, colorless chromogenic substances, various clear colors can be created.
  • the heat-sensitive recording sheet should still have sufficient color-forming sensitivity for bright recordings with little heat input from the thermal head.
  • a particularly effective and preferred phenol is 4,4'-isopropylidenediphenol (bisphenol A) which is now commonly used, inter alia because of its stability, low cost, availability in trade, etc.
  • 4,4'-isopropylidenediphenol has the disadvantage that it requires a higher color formation temperature. It is therefore not well suited for recordings in which the amount of heat supplied is small and difficulties such as sticking to the thermal head, etc. can easily arise.
  • the color formation temperature of a heat-sensitive sheet must be such that the colorless chromogenic dye or an organic acid such as a phenol is melted or liquid due to the application of heat. If both color forming materials have higher melting points, a substance with a lower melting point is added. The color formation reaction can occur at a lower temperature if one of the farting materials is dissolved due to the melting of this substance.
  • heat-fusible substances with a low melting point e.g. B. various waxes, fatty acid amides, alkylated bisphenols, substituted biphenylalkanes, coumarin compounds or diphenylamines, as sensitizers or melting point depressants.
  • the color formation reaction can only take place when the sensitizer has melted, so that a thermal response sufficient for rapid dynamic recording to the small amount of heat delivered in short time pulses cannot be achieved.
  • the invention is therefore based on the object of providing a heat-sensitive recording sheet which, because of its advantageous thermal responsiveness, enables intensive, clear, high-density recording with rapid recording.
  • the heat-sensitive recording sheet is said to have a high degree of whiteness, which is retained better over a longer period than before.
  • the heat-sensitive recording sheet is said to provide an excellent copy paper for a thermal copying machine of the infrared or strobe type when coated on a thin base paper or a film.
  • the coating amount should be reduced and the productivity should be increased in the production thereof.
  • a heat-sensitive recording sheet which contains a phthalic acid monoester of the general formula as a color developing agent in the color formation layer in the R for -C 6 H 5 , -CH 2 is where X is alkyl, halogen or alkoxy.
  • Color developing agents used to date are phenolic substances such as bisphenol A, p-hydroxybenzoic acid ester, etc.
  • organic carboxylic acids are also described in Japanese Patent Publication 4160/1968, Japanese Patent Laid-Open 39139/1978, etc., but they are described because of the insufficient color developing ability and unstable background whiteness not used in practice.
  • FR-A-2 243 830 describes heat-sensitive recording sheets which contain, in addition to conventional additives, a colorless or slightly colored chromogenic dye in the color formation layer and a phthalic acid monoester as color developing agent.
  • phthalic acid monoesters can include cycloalkyl esters or alkyl esters with at least 4 carbon atoms, the alkyl esters in the alkyl part being unsubstituted or substituted with oxygen functions, such as a hydroxyl, etherified hydroxy or acyloxy group.
  • the phthalic acid monoesters according to the invention have a much better color development capacity and a considerably more stable degree of whiteness of the background than the known organic carboxylic acids.
  • Typical examples of the phthalic acid monoesters according to the invention are phthalic acid monophenyl ester, phthalic acid monobenzyl ester, phthalic acid monomethylphenyl ester, phthalic acid monoethylphenyl ester, phthalic acid monoalkylbenzyl ester, phthalic acid monohalobenzyl ester, phthalic acid monoalkoxybenzyl ester, etc.
  • the phthalic acid monoesters used in the invention can be used alone or in a mixture with organic acids or phenols, such as bisphenol A (4,4'-isopropylidenediphenol), p, p '- (1-methyl-n-hexylidene) diphenol, p-tertiary butylphenol, p-phenylphenol, p-hydroxylbenzoic acid ester, novolactypphenol resin, 4-hydroxy-1-methylsulfonylbenzene, 4-hydroxy-1-butyloxysulfonylbenzene, etc. can be used.
  • organic acids or phenols such as bisphenol A (4,4'-isopropylidenediphenol), p, p '- (1-methyl-n-hexylidene) diphenol, p-tertiary butylphenol, p-phenylphenol, p-hydroxylbenzoic acid ester, novolactypphenol resin, 4-hydroxy-1-methylsulfonylbenzene
  • the amount of the phthalic acid monoesters according to the invention and the type and amount of the other constituents which are chosen depending on the desired effect and the suitability for recording purposes are not particularly limited.
  • phthalic acid monoester 1-20 parts by weight of a filler per 1 part by weight of the chromogenic dye and 10-20% by weight, based on the total solids content, of a binder.
  • Dispersions A and B were separately ground to a particle size of 3 ⁇ m by a ball mill, and then mixed together in the following ratio to produce the heat-sensitive coating colors.
  • working examples 1-a to 1-d according to the invention give a recording sheet with a good whiteness and a less reduction in time compared to the sheet according to comparative experiment 1-e in which bisphenol A was used.
  • the exemplary embodiments according to the invention result in a highly dynamic image density during rapid recording with a facsimile machine.
  • phthalic acid monobenzyl ester has exceptional effects.
  • the dispersions were ground separately into a dispersion by means of an attritor until the particle size was 3 1 1 m. The dispersions were then mixed together in the ratio described below to produce heat sensitive coating colors.
  • Heat-sensitive recording sheets were produced as in Example 1.
  • the heat-sensitive recording sheet of the present invention gives a high whiteness of the background and good durability at high humidity compared to the sheet of Comparative Experiment 2 in which bisphenol A was used together with a sensitizer.
  • the heat-sensitive recording sheet according to the invention has an astonishingly high image density when recorded quickly with a facsimile machine in comparison with the sheet of comparative experiment 2.

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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)

Description

Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsblatt, das einen hohen Weißgrad hat, der auch über längere Zeit besser als bisher erhalten bleibt.The invention relates to a heat-sensitive recording sheet which has a high degree of whiteness, which is retained better than before even over a long period of time.

Ein wärmeempfindliches Aufzeichnungsblatt erhält man im allgemeinen dadurch, daß man auf die Oberfläche eines Trägers, z. B. ein Papier oder einen Film usw. eine Beschichtungsmasse aufbringt, die durch Feinvermahlen und Dispergieren eines farblosen chromogenen Stoffs und eines Farbentwicklungsmaterials, z. B. eine phenolische Substanz, Vermischen der erhaltenen Dispersionen miteinander und Zugeben eines Bindemittels, Füllstoffs, Sensibilisierungsmittels, Gleitmittels und anderer Hilfsmittel erhalten worden ist.A heat-sensitive recording sheet is generally obtained by placing it on the surface of a support, e.g. B. a paper or film, etc., a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, e.g. B. a phenolic substance, mixing the dispersions obtained and adding a binder, filler, sensitizer, lubricant and other auxiliaries has been obtained.

Bei Wärme- oder Hitzeeinwirkung erfolgt in der Beschichtung augenblicklich eine chemische Umsetzung bei der eine Farbe gebildet wird. Je nach Wahl der speziellen, farblosen chromogenen Stoffe lassen sich verschiedene klare Farben erzeugen.When exposed to heat or heat, the coating immediately undergoes a chemical reaction in which a color is formed. Depending on the choice of special, colorless chromogenic substances, various clear colors can be created.

Mit zunehmender Verbreitung der wärmeempfindlichen Aufzeichnungstechnik wurden die schnelle Aufzeichnung und die Verbesserung der Bildqualität, d.h. die Erhöhung der Bildauflösung erforderlich.With the proliferation of heat-sensitive recording technology, rapid recording and improvement in image quality, i.e. the increase in image resolution is required.

Wenn zum Beispiel die von einem Thermokopf in einer Aufzeichnungsvorrichtung abgegebene Wärmeenergie geringer ist, soll das wärmeempfindliche Aufzeichnungsblatt trotzdem eine ausreichende farbbildende Empfindlichkeit für helle Aufzeichnungen bei geringer Wärmezufuhr vom Thermokopf haben.For example, if the thermal energy given off by a thermal head in a recording apparatus is lower, the heat-sensitive recording sheet should still have sufficient color-forming sensitivity for bright recordings with little heat input from the thermal head.

In der japanischen Patentpublikation Nr. 14039/1970 und in anderen Veröffentlichungen sind viele Farbentwicklungsmittel beschrieben. Ein besonders wirksames und bevorzugtes Phenol ist 4,4'- lsopropylidendiphenol (Bisphenol A), das unter anderem wegen seiner Stabilität, niedrigen Kosten, Erhältlichkeit im Handel, usw. jetzt üblicherweise verwendet wird. 4,4'-Isopropylidendiphenol hat jedoch den Nachteil, daß es eine höhere Farbbildungstemperatur benötigt. Es eignet sich daher nicht gut für Aufzeichnungen, bei denen die gelieferte Wärmemenge gering ist und es können dabei leicht Schwierigkeiten wie Anhaften am Thermokopf, usw. entstehen.Many color developing agents are described in Japanese Patent Publication No. 14039/1970 and other publications. A particularly effective and preferred phenol is 4,4'-isopropylidenediphenol (bisphenol A) which is now commonly used, inter alia because of its stability, low cost, availability in trade, etc. However, 4,4'-isopropylidenediphenol has the disadvantage that it requires a higher color formation temperature. It is therefore not well suited for recordings in which the amount of heat supplied is small and difficulties such as sticking to the thermal head, etc. can easily arise.

Die Farbbildungstemperatur eines wärmeempfindlichen Blattes muß so beschaffen sein, daß der farblose chromogene Farbstoff oder eine organiche Säure, wie ein Phenol, aufgrund der Wärmezufuhr geschmolzen oder flüssig wird. Falls beide Farbbildungsmaterialien höhere Schmelzpunkte haben, wird eine Substanz mit einem niedrigeren Schmelzpunkt zugegeben. Dabei kann die Farbbildungsreaktion bei einer tieferen Temperatur auftreten, wenn eines der Fartbildungsmaterialien infolge des Schmelzens dieser Substanz gelöst wird.The color formation temperature of a heat-sensitive sheet must be such that the colorless chromogenic dye or an organic acid such as a phenol is melted or liquid due to the application of heat. If both color forming materials have higher melting points, a substance with a lower melting point is added. The color formation reaction can occur at a lower temperature if one of the farting materials is dissolved due to the melting of this substance.

Deshalb ist in den japanischen Offenlegungsschriften Nr. 39139/1978, 26139/1978, 5636/1978, 11036/1978 usw. vorgesehen, daß hitzenschmelzbare Substanzen mit einem niedrigen Schmelzpunkt, z. B. verschiedene Wachse, fettsäureamide, alkylierte Bisphenole, substituierte Biphenylalkane, Cumarinverbindungen oder Diphenylamine, als Sensibilisatoren oder Schmelzpunkterniedrigungsmittel zugegeben werden.Therefore, in Japanese Patent Laid-Open Nos. 39139/1978, 26139/1978, 5636/1978, 11036/1978, etc., it is provided that heat-fusible substances with a low melting point, e.g. B. various waxes, fatty acid amides, alkylated bisphenols, substituted biphenylalkanes, coumarin compounds or diphenylamines, as sensitizers or melting point depressants.

Wenn ein Sensibilisator vorhanden ist, kann die Farbbildungsreaktion erst stattfinden, wenn der Sensibilisator geschmolzen ist, so daß eine zur raschen dynamischen Aufzeichnung ausreichende thermische Ansprechbarkeit auf die geringe, in kurzen Zeitimpulsen gelieferte Wärmemenge, nicht erzielbar ist.If a sensitizer is present, the color formation reaction can only take place when the sensitizer has melted, so that a thermal response sufficient for rapid dynamic recording to the small amount of heat delivered in short time pulses cannot be achieved.

Der Erfindung liegt daher die Aufgabe zugrunde, ein wärmeempfindliches Aufzeichnungsblatt zu schaffen, das aufgrund einer vorteilhaften thermischen Ansprechbarkeit eine intensive, klare Aufzeichnung mit hoher Dichte bei rascher Aufzeichnung ermöglicht.The invention is therefore based on the object of providing a heat-sensitive recording sheet which, because of its advantageous thermal responsiveness, enables intensive, clear, high-density recording with rapid recording.

Außerdem soll das wärmeempfindliche Aufzeichnungsblatt einen hohen Weißgrad haben, der auch über längere Zeit besser als bisher erhalten bleibt.In addition, the heat-sensitive recording sheet is said to have a high degree of whiteness, which is retained better over a longer period than before.

Darüberhinaus soll das wärmeempfindliche Aufzeichnungsblatt bei Beschichtung eines dünnen Rohpapiers oder eines Films ein ausgezeichnetes Kopierpapier für eine thermische Kopiermaschine vom Infrarot- oder Stroboflasch-Typ ergeben.In addition, the heat-sensitive recording sheet is said to provide an excellent copy paper for a thermal copying machine of the infrared or strobe type when coated on a thin base paper or a film.

Schließlich soll bei dem wärmeempfindlichen Aufzeichnungsblatt der Erfindung die Beschichtungsmenge erniedrigt und bei dessen Herstellung die Produktivität erhöht werden können.Finally, in the heat-sensitive recording sheet of the invention, the coating amount should be reduced and the productivity should be increased in the production thereof.

Gelöst wird diese Aufgabe durch ein wärmeempfindliches Aufzeichnungsblatt, das als Farbentwicklungsmittel in der Farbbildungsschicht einen Phthalsäuremonoester der allgemeinen Formel

Figure imgb0001
in der R für -C6H5, -CH2
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
steht, wobei X Alkyl-, Halogen oder Alkoxy bedeutet, enthält.This object is achieved by a heat-sensitive recording sheet which contains a phthalic acid monoester of the general formula as a color developing agent in the color formation layer
Figure imgb0001
 in the R for -C 6 H 5 , -CH 2
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
 is where X is alkyl, halogen or alkoxy.

Bisher verwendete Farbentwicklungsmittel sind phenolische Substanzen, wie Bisphenol A, p-Hydroxybenzoesäureester, usw. Als Farbentwicklungsmittel sind auch organische Carbonsäuren in der japanischen Patentpublikation 4160/1968, der japanischen Offenlegungsschrift 39139/1978, usw beschrieben, sie werden aber wegen der ungenügenden Farbentwicklungsfähigkeit und des unstabilen Weißgrades des Hintergrundes nicht in der Praxis verwendet.Color developing agents used to date are phenolic substances such as bisphenol A, p-hydroxybenzoic acid ester, etc. As the color developing agent, organic carboxylic acids are also described in Japanese Patent Publication 4160/1968, Japanese Patent Laid-Open 39139/1978, etc., but they are described because of the insufficient color developing ability and unstable background whiteness not used in practice.

In der FR-A-2 243 830 werden wärmeempfindliche Aufzeichnungsblätter beschrieben, die in der Farbbildungsschicht neben üblichen Additiven einen farblosen oder schwachfarbigen chromogenen Farbstoff und als Farbentwicklungsmittel einen Phthalsäuremonoester enthalten. Derartige Phthalsäuremonoester können unter anderem Cycloalkylester oder Alkylester mit mindestens 4 Kohlenstoffatomen sein, wobei die Alkylester im Alkylteil unsubstituiert oder mit Sauerstoffunktionen, wie einer Hydroxy-, verätherten Hydroxy-oder Acyloxygruppe substituiert ist.FR-A-2 243 830 describes heat-sensitive recording sheets which contain, in addition to conventional additives, a colorless or slightly colored chromogenic dye in the color formation layer and a phthalic acid monoester as color developing agent. Such phthalic acid monoesters can include cycloalkyl esters or alkyl esters with at least 4 carbon atoms, the alkyl esters in the alkyl part being unsubstituted or substituted with oxygen functions, such as a hydroxyl, etherified hydroxy or acyloxy group.

Die erfindungsgemäßen Phthalsäuremonoester haben ein viel besseres Farbentwicklungsvermögen und einen erheblich stabileren Weißgrad des Hintergrundes als die bekannten organischen Carbonsäuren.The phthalic acid monoesters according to the invention have a much better color development capacity and a considerably more stable degree of whiteness of the background than the known organic carboxylic acids.

Die Ursache für die besseren Effekte ist vielleicht darin zu sehen, daß eine von zwei Carboxylgruppen der Phthalsäure mit bestimmten Gruppen verestert ist, so daß eine wasser-unlösliche, sublimierbare Verbindung mit einem geeigneten Schmelzpunkt (90 - 130°C) gebildet wird, und daß diese Ester-Gruppe die Acidität der benachbarten Carbonsäure so beeinflusst, daß geeignete Bedingungen für eine stabile und dichte Farbentwicklung des farblosen chromogenen Farbstoffs gegeben sind.The reason for the better effects may be seen in the fact that one of two carboxyl groups of phthalic acid is esterified with certain groups, so that a water-insoluble, sublimable compound with a suitable melting point (90-130 ° C.) is formed, and that this ester group influences the acidity of the neighboring carboxylic acid in such a way that suitable conditions for stable and dense color development of the colorless chromogenic dye are given.

Typische Beispiele für die erfindungsgemäßen Phthalsäuremonoester sind Phthalsäuremonophenylester, Phthalsäuremonobenzylester, Phthalsäuremonomethylphenylester, Phthalsäuremonoethylphenylester, Phthalsäuremonoalkylbenzylester, Phthalsäuremonohalogenbenzylester, Phthalsäuremonoalkoxybenzylester usw.Typical examples of the phthalic acid monoesters according to the invention are phthalic acid monophenyl ester, phthalic acid monobenzyl ester, phthalic acid monomethylphenyl ester, phthalic acid monoethylphenyl ester, phthalic acid monoalkylbenzyl ester, phthalic acid monohalobenzyl ester, phthalic acid monoalkoxybenzyl ester, etc.

Die bei der Erfindung verwendeten Phthalsäuremonester können je nach Anwendungszweck und benötigten Eigenschaften allein oder in einer Mischung mit organischen Säuren oder Phenolen, wie Bisphenol A (4,4'-Isopropylidendiphenol), p,p'-(1-Methyl-n-hexyliden) diphenol, p-Tertiärbutylphenol, p-Phenylphenol, p-Hydroxylbenzoesäureester, Novolaktypphenolharz, 4-Hydroxy-1-methylsulfonylbenzol, 4-Hydroxy-1-butyloxysulfonylbenzol usw. verwendet werden.Depending on the intended use and the properties required, the phthalic acid monoesters used in the invention can be used alone or in a mixture with organic acids or phenols, such as bisphenol A (4,4'-isopropylidenediphenol), p, p '- (1-methyl-n-hexylidene) diphenol, p-tertiary butylphenol, p-phenylphenol, p-hydroxylbenzoic acid ester, novolactypphenol resin, 4-hydroxy-1-methylsulfonylbenzene, 4-hydroxy-1-butyloxysulfonylbenzene, etc. can be used.

Die Wahl der erfindunggemäßen farblosen chromogenen Farbstoffe unterliegt keinen besonderen Einschränkungen, man kan z. B. Folgende verwenden:

  • 3-Diäthylamino-6-methyl-7-anilinofluoran (schwarz), 3-(N-Äthyl-p-toluidino)-6-methyl-7-anilinofluoran (schwarz), 3-(N-Äthyl-N-isoamyl)amino-6-methyl-7-anilinofluoran (schwarz), 3-Diäthylamino-6-methyl-7(ortho- paradimethylanilino)-fluoran (schwarz), 3-Pyrrolidino-6-methyl-7-anilinofluoran (schwarz), 3-Piperidino-6-methyl-7-anilino-fluoran (schwarz), 3-(N-Cyclohexyl-N-methylamino)-6-methyl-7-anilinfluoran (schwarz), 3-Diäthylamino-7-(meta-tri-fluor-methylanilino)fluoran (schwarz), 3-dibutylamino-7-(ortho-cchloranilino)-fluorran (schwarz), 3-Diäthylamino-6-ämethylchlor-fluoran (rot), 3-Diäthylamino-6-methylfluoran (rot), 3-Cyclohexylamino-6-chlorfluoran (orange), Kristallviolettlacton (blau), 3-(4-Diäthylamino-2-äthoxyphenyl)-3-(1- äthyl-2-methylindol-3-yl)4-azaphthalid (blau), 3-(4-Diäthylamino-2-äthoxyphenyl)-3-(1-äthytl-2-methylindol-3-yl)-7-azaphthalid (blau).
The choice of colorless chromogenic dyes according to the invention is not subject to any particular restrictions. B. Use the following:
  • 3-diethylamino-6-methyl-7-anilinofluoran (black), 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluoran (black), 3- (N-ethyl-N-isoamyl) amino -6-methyl-7-anilinofluorane (black), 3-diethylamino-6-methyl-7 (orthoparadimethylanilino) -fluorane (black), 3-pyrrolidino-6-methyl-7-anilinofluorane (black), 3-piperidino -6-methyl-7-anilino-fluoran (black), 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-aniline fluoran (black), 3-diethylamino-7- (meta-tri-fluoro- methylanilino) fluoran (black), 3-dibutylamino-7- (ortho-chloroanilino) -fluorane (black), 3-diethylamino-6-eamethylchlorofluorane (red), 3-diethylamino-6-methylfluorane (red), 3- Cyclohexylamino-6-chlorofluorane (orange), crystal violet lactone (blue), 3- (4-diethylamino-2-ethoxyphenyl) -3- (1- ethyl-2-methylindol-3-yl) 4-azaphthalide (blue), 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethytl-2-methylindol-3-yl) -7-azaphthalide (blue).

Das oben erwähnte Farbentwicklungsmittel und der basische farblose chromogene Farbstoff werden mittels einer Mahlvorrichtung, wie Kugelmühle, Reibungsmühle, Sandschleifmaschine usw. oder mittels einer geeigneten Emulgiermaschine bis zu einer Teilchengröße von mehreren Mikron oder kleiner zermahlen. Hierzu gibt man verschiedene Additive, je nach Zweckbestimmung, um die Beschichtungsfarbe zu erzeugen. Die Additive, die erfindungsgemäß verwendet werden können, sind z. B. folgende:

  • Bindemittel, wie Polyvinylalkohol, modifizierter Polyvinylalkohol, Hydroxyäthylzellulose, Methylzellulose, Stärke, Styrol-Maleinsäureanhydrid-Copolymere, Vinylacetat-Maleinsäureanhydrid-Copolymere, StyrolButadien-Copolymere usw., anorganische oder organische Füllstoffe, wie Kaolin, gebranntes Kaolin, Diatomeenerde, Talk, Titandioxyd, Kalziumcarbonat, Magnesiumcarbonat, Aluminiumhydroxyd, usw.; Trennmittel, wie Metallsalze von Fettsäuren; Gleitmittel wie Wachse, UV-Absorptionsmittel der Benzophenon-und Triazolreihe, wasserfest machende Mittel, wie Glyoxal usw., Dispergiermittel, Antischaummittel usw. Das gewünschte wärmeepfindliche Blatt wird erhalten, indem man diese Beschichtungsfarbe auf ein Papier oder auf verschiedene Filme aufträgt.
The above-mentioned color developing agent and the basic colorless chromogenic dye are ground to a particle size of several microns or smaller by means of a grinding device such as a ball mill, attritor, sand grinder, etc. or by means of a suitable emulsifying machine. Various additives are added to this, depending on the intended use, in order to produce the coating color. The additives that can be used according to the invention are e.g. B. the following:
  • Binders, such as polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, starch, styrene-maleic anhydride copolymers, vinyl acetate-maleic anhydride copolymers, styrene-butadiene copolymers, etc., inorganic or organic fillers, such as kaolin, baked kaolin, diatomaceous earth, talc , Magnesium carbonate, aluminum hydroxide, etc .; Release agents, such as metal salts of fatty acids; Lubricants such as waxes, UV absorbers of the benzophenone and triazole series, waterproofing agents such as glyoxal etc., dispersants, anti-foaming agents etc. The desired heat-sensitive sheet is obtained by applying this coating color to a paper or on different films.

Die Menge der erfindungsgemäßen Phthalsäuremonoester sowie Art und Menge der anderen Bestandteile, die je nach dem gewünschten Effekt und der Eignung für Aufzeichnungszwecke gewählt werden, sind nicht besonders beschränkt.The amount of the phthalic acid monoesters according to the invention and the type and amount of the other constituents which are chosen depending on the desired effect and the suitability for recording purposes are not particularly limited.

Im allgemeinen ist es vorteilhaft, 3-10 Gewichtsteile Phthalsäuremonoester, 1-20 Gewichtsteile eines Füllstoffs pro 1 Gewichtsteil des chromogenen Farbstoffs und 10-20 Gew.%, bezogen auf den Gesamtfeststoffgehalt, eines Bindemittels zu verwenden.In general, it is advantageous to use 3-10 parts by weight of phthalic acid monoester, 1-20 parts by weight of a filler per 1 part by weight of the chromogenic dye and 10-20% by weight, based on the total solids content, of a binder.

Anhand der nachfolgenden Beispiele, die Ausführungsbeispiele und Vergleichsversuche darstellen, wird die Erfindung naher erläutert.The invention is explained in more detail with reference to the following examples, which represent exemplary embodiments and comparative experiments.

Beispiel 1example 1

Figure imgb0009
Figure imgb0009

Die Dispersionen A und B wurden getrennt zu einer Teilchengröße der festen Bestandteile von 3 µm mittels einer Kugelmühle zermahlen und dann im folgenden Verhältnis miteinander vermischt, um die wärmeempfindlichen Beschichtungsfarben zu erzeugen.

Figure imgb0010
Dispersions A and B were separately ground to a particle size of 3 µm by a ball mill, and then mixed together in the following ratio to produce the heat-sensitive coating colors.
Figure imgb0010

Diese Beschichtungsfarben wurden in einer Beschichtungsmenge von 6,0,g/m2 auf ein Basispapier mit einem Gewicht von 50 g/m2 aufgetragen, getrocknet und superkalandriert, um eine Glätte von 200-300 Sekunden einzustellen. Die erhaltenen, eine schwarze Farbe bildenden, wärmeempfindlichen Aufzeichnungsblätter wurden hinsichtlich ihrer Qualität und ihres Verhaltens geprüft. Die Ergebnisse sind in Tabelle 1 angegeben.

Figure imgb0011
These coating colors were applied in a coating amount of 6.0 g / m 2 on a base paper with a weight of 50 g / m 2 , dried and supercalendered to adjust a smoothness of 200-300 seconds. The obtained heat-sensitive recording sheets forming black color were tested for their quality and behavior. The results are shown in Table 1.
Figure imgb0011

Anmerkungen zu Tabelle 1:

  • (1) Die optische Dichte des Hintergrundes wurde mit einem Macbeth-Dichtemesser vom Typ RD-104 gemessen, wobei kleine Werte einem hohen Weißgrad entsprechen.
  • (2) Die wärmeempfindlichen Aufzeichnungsblätter wurden 5 Sekunden unter einem Druck von 10 g/cm2 gegen eine auf 105°C erhitzte Platte gepreßt. Die optische Dichte des statischen Bildes wurde mit einem Macbeth-Dichtemesser vom Typ RD-104 gemessen, wobei größere Werte einer dunkleren Farbe entsprechen.
  • (3) Die wärmeempfindlichen Aufzeichnungsblätter wurden bei einer Pulsbreite von 0,7 Millisekunden unter Bedingung der Mode G 111 mit Hilfe einer Thermofaksimiliermaschine vom Typ CP-4800A, hergestellt von der Firma Toshiba Corporation, mit Aufzeichnungsbildern versehen, deren optische Dichten mit einem Macbeth-Dichtemesser vom Typ RD-104 bestimmt wurden.
Notes on Table 1:
  • (1) The optical density of the background was measured with a Macbeth RD-104 density meter, with small values corresponding to a high degree of whiteness.
  • (2) The heat-sensitive recording sheets were pressed for 5 seconds under a pressure of 10 g / cm 2 against a plate heated to 105 ° C. The optical density of the static image was measured with a Macbeth RD-104 density meter, with larger values corresponding to a darker color.
  • (3) The heat-sensitive recording sheets were provided with recording images at a pulse width of 0.7 millisecond under the condition of Mode G 111 using a CP-4800A thermal facsimile machine manufactured by Toshiba Corporation, the optical densities of which were measured with a Macbeth density meter RD-104 were determined.

Wie aus Tabelle 1 ersichtlich ist, ergeben die erfindungsgemäßen Ausführungsbeispiele 1-a bis 1-d ein Aufzeichnungsblatt mit einem guten Weißgrad und einer geringeren Verminderung des der Zeit, im Vergleich zum Blatt gemäß dem Vergleichsversuch 1-e, bei dem Bisphenol A verwendet wurde.As can be seen from Table 1, working examples 1-a to 1-d according to the invention give a recording sheet with a good whiteness and a less reduction in time compared to the sheet according to comparative experiment 1-e in which bisphenol A was used.

Die erfindungsgemäßen Ausführungsbeispiele ergeben eine hohedynamische Bilddichte bei der schnellen Aufzeichnung mit einer Faksimiliermaschine.The exemplary embodiments according to the invention result in a highly dynamic image density during rapid recording with a facsimile machine.

Von der erfindungsgemäßen Phthalsäuremonoestern hat Phthalsäuremonobenzylester außergewähnliche Effekte.Of the phthalic acid monoesters according to the invention, phthalic acid monobenzyl ester has exceptional effects.

Beispiel 2Example 2

Figure imgb0012
Figure imgb0012

Die Dispersionen wurden getrennt mittels einer Reibungsmühle zu einer Dispersion vermahlen, bis die Teilchengröße 3 11m betrug. Dann wurden die Dispersionen im unten beschriebenen Verhältnis miteinander vermischt, um wärmeempfindliche Beschichtungsfarben zu erzeugen.The dispersions were ground separately into a dispersion by means of an attritor until the particle size was 3 1 1 m. The dispersions were then mixed together in the ratio described below to produce heat sensitive coating colors.

Wärmeempfindliche Aufzeichnungsblätter wurden wie im Beispiel 1 hergestellt.

Figure imgb0013
Heat-sensitive recording sheets were produced as in Example 1.
Figure imgb0013

Die erhaltenen, eine schwarze Farbe bildenden, wärmempfindlichen Blätter wurden hinsichtlich ihrer Qualität und ihres Verhaltens wie im Beispiel 1 geprüft. Die Ergebnisse sind in Tabelle 2 angegeben.

Figure imgb0014

  • (1) Die wärmeempfindlichen Aufzeichnungsblätter wurden 24 Stunden bei 40°C und 90 % relativer Luftfeuchtigkeit gelagert und die optische Dichte des Hintergrundes wurde unter Verwendung eines Macbeth-Dichtemessers vom Typ RD-104 gemessen.
  • (2) Die wärmeempfindlichen Aufzeichnungsblätter wurden bei einer Pulsbreite von 1,0 Millisekunden und einer Spannung von 17,66 V unter Verwendung einer Thermofaksimiliermaschine vom Typ FR-H, hergestellt von der Firma Matsushita Graphic Communication Systems, Inc., mit Aufzeichnungen versehen. Die aufgezeichnete Bilddichte wurde unter Verwendung eines Macbeth-Dichtemessers vom Typ RD-104 gemessen.
The obtained heat-sensitive sheets forming a black color were tested for quality and behavior as in Example 1. The results are shown in Table 2.
Figure imgb0014
  • (1) The heat sensitive recording sheets were stored at 40 ° C and 90% RH for 24 hours, and the optical density of the background was measured using a Macbeth RD-104 density meter.
  • (2) The heat-sensitive recording sheets were recorded at a pulse width of 1.0 millisecond and a voltage of 17.66 V using a FR-H thermal facsimile machine manufactured by Matsushita Graphic Communication Systems, Inc. The recorded image density was measured using a RD-104 Macbeth density meter.

Wie aus Tabelle 2 ersichtlich, ergibt das erfindungsgemäße, wärmeempfindliche Aufzeichnungsblatt einen hohen Weißgrad des Hintergrunds und gute Haltbarkeit bei hoher Luftfeuchtigkeit im Vergleich mit dem Blatt des Vergleichsversuchs 2, bei dem Bisphenol A zusammen mit einem Sensibilisator eingesetzt wurde.As can be seen from Table 2, the heat-sensitive recording sheet of the present invention gives a high whiteness of the background and good durability at high humidity compared to the sheet of Comparative Experiment 2 in which bisphenol A was used together with a sensitizer.

Das erfindungsgemäße, wärmeempfindliche Aufzeichnungsblatt weist eine erstaunlich hohe Bilddichte bei rascher Aufzeichnung mit einer Faksimiliermaschine im Vergleich zu dem Blatt des Vergleichsversuchs 2 auf.The heat-sensitive recording sheet according to the invention has an astonishingly high image density when recorded quickly with a facsimile machine in comparison with the sheet of comparative experiment 2.

Claims (6)

1. Heat sensitive recording sheet which in the color-forming layer besides usual additives comprises a colorless or pale colored chromogemic dye and a phthalic acid monoester as color developing agent,
characterized in that
the phthalic acid monoester is a compound of the gemeral formula
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
and X is alkyl, halogen or alkoxy.
2. The heat sensitive recording sheet of claim 1, characterized in that the phthalic acid monoester is phthalic acid monobenzyl ester.
3. The heat sensitive recording sheet of claim 1, characterized in that the phthalic acid monoester is at least one compound selected from: phthalic acid monophenylester, phthalic acid monomethylphenylester, phthalic acid monoethylphenylester, phthalic acid monoalkylbenzylester, phthalic acid monohalogenbenzylester and phthalic acid monoalkoxybenzylester.
4. The heat sensitive recording sheet of anyone of claims 1 to 3, characterized in that the color developing layer further comprises as color developing agent at least one compound selected from phenols and organic carboxylic acids.
5. The heat sensitive recording sheet of anyone of claims 1 to 4, characterized in that the color developing layer contains 3 to 10 parts by weight phthalic acid monoester, 1 to 20 parts by weight of a filling material per 1 part by weight of chromogenic dye and 10 to 20 percent by weight of a binder, based on the content of total solids.
6. The use of phthalic acid monoesters of claim 1 as color developing agent for heat sensitive recording material.
EP84102807A 1983-03-15 1984-03-14 Heat-sensitive registration foil Expired EP0122468B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP41436/83 1983-03-15
JP58041436A JPS59167294A (en) 1983-03-15 1983-03-15 Thermal recording sheet

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EP0122468A2 EP0122468A2 (en) 1984-10-24
EP0122468A3 EP0122468A3 (en) 1984-12-27
EP0122468B1 true EP0122468B1 (en) 1987-07-01

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Publication number Priority date Publication date Assignee Title
JPS6046293A (en) * 1983-08-24 1985-03-13 Jujo Paper Co Ltd Thermal recording paper
JPS60122191A (en) * 1983-12-06 1985-06-29 Ricoh Co Ltd Thermal recording material
JPS62148288A (en) * 1985-12-24 1987-07-02 Kanzaki Paper Mfg Co Ltd Thermal recording material
JPS6317081A (en) * 1986-07-10 1988-01-25 Kanzaki Paper Mfg Co Ltd Thermal recording medium
DE69309886T2 (en) * 1993-01-29 1997-11-20 Agfa Gevaert Nv Heat and light sensitive recording element

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Publication number Priority date Publication date Assignee Title
US3965282A (en) * 1973-09-14 1976-06-22 Agfa-Gevaert N.V. Thermographic recording material
US3911171A (en) * 1973-09-14 1975-10-07 Agfa Gevaert A Naamloze Vennoo Thermographic recording process

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EP0122468A2 (en) 1984-10-24
JPS59167294A (en) 1984-09-20
DE3464474D1 (en) 1987-08-06
US4498091A (en) 1985-02-05
EP0122468A3 (en) 1984-12-27
JPH0211439B2 (en) 1990-03-14

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