EP0262569A2 - Pressure-sensitive recording material - Google Patents

Pressure-sensitive recording material Download PDF

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Publication number
EP0262569A2
EP0262569A2 EP87113877A EP87113877A EP0262569A2 EP 0262569 A2 EP0262569 A2 EP 0262569A2 EP 87113877 A EP87113877 A EP 87113877A EP 87113877 A EP87113877 A EP 87113877A EP 0262569 A2 EP0262569 A2 EP 0262569A2
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EP
European Patent Office
Prior art keywords
pressure
recording material
oil
sensitive recording
formula
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EP87113877A
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German (de)
French (fr)
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EP0262569B2 (en
EP0262569B1 (en
EP0262569A3 (en
Inventor
Bodo Dr. Dipl.-Chem. Hilterhaus
Günther Dr. Dipl.-Chem. Hunger
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Stora Feldmuehle AG
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Feldmuehle AG
Stora Feldmuehle 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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/1366—Organic colour formers, e.g. leuco dyes characterised solely by tri (aryl or hetaryl)methane derivatives
    • 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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
    • B41M5/1655—Solvents
    • 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
    • Y10S428/914—Transfer or decalcomania

Definitions

  • the invention is based on an object according to the preamble of claim 1.
  • Color formers based on triphenylmethane leuco dyes have been described in DE-A-2750283. These color formers produce excellent color formation when in contact with acidic reactants. In order to be able to use this class of color formers in pressure-sensitive recording materials, these substances are dissolved in suitable solvents, of which DE-A-2750283 names partially hydrogenated terphenyl, alkylated naphthalenes or dibuthyl phthalate. The dissolved color formers are then enclosed in microcapsules in accordance with known methods. The solvents mentioned have been suspected on various occasions of causing skin irritation when using the carbonless paper produced therewith.
  • EP-A-24898 proposes a solvent mixture of aromatic hydrocarbon and ester components in a specific ratio, this solvent mixture advantageously at least 50% by weight and only in exceptional cases with higher proportions of inert diluent, such as e.g. Mineral or vegetable oils can be blended.
  • inert diluent such as e.g. Mineral or vegetable oils
  • EP-A-86636 in which aromatic hydrocarbons are preferred to oils of animal or vegetable origin and mineral oils among a large number of high-boiling solvents, expresses the generally prevailing view that the naturally occurring oils are based on mineral, animal or Vegetable-based are less suitable because, despite their known physiological harmlessness, they are known as a bad solvent for the usual color formers and their use in significant amounts would result in a lower color-forming capacity, in particular a lower color intensity.
  • the present invention has for its object to provide a pressure-sensitive recording material in which the in microcapsules included color formers are dissolved in a physiologically largely harmless solvent.
  • the present invention succeeds in that a color former based on a triphenylmethane leuco dye is used which is soluble in the solvents mentioned above.
  • the solvent for the color former consists entirely of e.g. vegetable oils. To achieve the greatest possible harmlessness, however, it has proven sufficient if at least 80% by weight of the solvent used consists of the oils proposed according to the invention.
  • the solvents known per se for color formers such as alkylated naphthalenes, hydrogenated terphenyls, alkylated biphenyls, diphenylethanes, alkylbenzenes, chlorinated paraffins, or mixtures of these compounds can be used as residual solvents. If more than 20% by weight of such solvents is added, there are increased concerns about the safety.
  • capsule wall material which must be present in the dissolved state for the production of the microcapsules, is also of considerable importance in the context of the present invention.
  • water-soluble polymers or water-dispersible hydrocolloids but also dispersible plastics for the production of capsule wall materials have proven to be suitable in the context of the present invention.
  • the invention also provides mixtures of the color formers mentioned, which are particularly advantageous for achieving a specific color tone.
  • mineral oils white oil and spindle oil in particular, and also paraffinum liquidum known from the medical field according to DAB 8 (German Pharmaceutical Book, 8th edition) have proven to be particularly suitable.
  • microcapsules are produced by processes known per se, such as, for example, the coacervation processes described in DE-B-1122495 and DE-A-2225274.
  • suitable water-soluble polymeric substances such as pig skin gelatin, gum arabic, cellulose compounds and polyvinyl alcohol are also described there.
  • the production of microcapsules from urea-formaldehyde resins is specified in US Pat. No. 3,516,941. However, it should be emphasized that the invention is not restricted to the use of the encapsulation methods and capsule wall materials described in the above documents.
  • the recording material according to the invention can be produced with all microcapsules, the walls of which are formed from a material initially dissolved or dispersed in water, additional hardening steps possibly being used to form a dense and stable capsule wall, or such substances being added that add another Can cause hardening of the capsule walls.
  • solutions of color formers were prepared at temperatures of 25 to 40 ° C. and the solutions prepared were encapsulated in a melamine-formaldehyde precondensate.
  • the finished microcapsules were applied to the back of a wood-free paper.
  • a good color reaction and an excellent color intensity were observed on pressure contact with a receiver paper coated with acidic color reactants, in particular in Examples 1 to 4.
  • Examples 5 to 9 also showed good results with regard to color intensity, whereas Example 10 had a slightly lower color intensity. Satisfactory results were obtained with Examples 11 to 18.

Abstract

A pressure-sensitive recording material is disclosed, having microcapsules containing a triphenylmethane leuco-dye dissolved in a solvent composed at least 80% of plant, animal or paraffin oils, the microcapsule walls being formed of a wall material which is water-soluble or water-dispersible before the formation of the microcapsules. Preferably, the color former is of the formula <IMAGE>

Description

Die Erfindung geht aus von einem Gegenstand nach dem Oberbegriff des Anspruchs 1.The invention is based on an object according to the preamble of claim 1.

Farbbildner auf Basis von Triphenylmethanleukofarbstoffen wurden in der DE-A-­2750283 beschrieben. Diese Farbbildner bewirken bei Kontakt mit sauren Reaktanten eine ausgezeichnete Farbbildung. Um diese Klasse von Farbbildnern in druckempfindlichen Aufzeichnungsmaterialien einsetzen zu können, werden diese Substanzen in geeigneten Lösungsmitteln aufgelöst, von denen die DE-A- 2750283 partiell hydriertes Terphenyl, alkylierte Naphtaline oder Dibuthylphthalat nennt. Anschließend werden die aufgelösten Farbbildner entsprechend bekannten Verfahren in Mikrokapseln eingeschlossen. Die genannten Lösungsmittel sind verschiedentlich in Verdacht geraten, beim Gebrauch der damit hergestellten Durchschreibepapiere Hautreizungen auszulösen. Andererseits bestehen auch Bedenken bei der Entsorgung, insbesondere auch bei der Wiederaufbereitung von Mikrokapseln enthaltendem Ausschuß in der Papierfabrik. Es entstand somit das Bedürfnis, diese Lösungsmittel durch solche Lösungsmittel zu substituieren, die in dieser Beziehung weniger bedenklich sind. Gemäß der EP-A-­167900 werden deshalb insbesondere alkylierte Produkte von Diphenylmethanen, z.B. Ethyldiphenylmethan oder alkylierte Produkte von Diphenylethanen, z.B. Ethyldiphenylethan vorgeschlagen. Als typische Farbbildner sieht diese Schrift Kristallviolettlakton und N-Leukoauramin vor. Die Verfügbarkeit dieser Lösungsmittel ist jedoch nicht in jedem Fall gegeben und es kann auch nicht als gesichert gelten, daß diese Lösungsmittel die in sie gesetzten Erwartungen bezügl. einer weitestgehenden Unbedenklichkeit erfüllen.Color formers based on triphenylmethane leuco dyes have been described in DE-A-2750283. These color formers produce excellent color formation when in contact with acidic reactants. In order to be able to use this class of color formers in pressure-sensitive recording materials, these substances are dissolved in suitable solvents, of which DE-A-2750283 names partially hydrogenated terphenyl, alkylated naphthalenes or dibuthyl phthalate. The dissolved color formers are then enclosed in microcapsules in accordance with known methods. The solvents mentioned have been suspected on various occasions of causing skin irritation when using the carbonless paper produced therewith. On the other hand, there are also concerns about disposal, in particular also regarding the reprocessing of rejects containing microcapsules in the paper mill. This is how it came about Need to replace these solvents with those solvents that are less of concern in this regard. According to EP-A-167900, alkylated products of diphenylmethanes, for example ethyldiphenylmethane or alkylated products of diphenylethanes, for example ethyldiphenylethane, are therefore proposed in particular. This font provides crystal violet lactone and N-leucoauramine as typical color formers. However, the availability of these solvents is not always the case, and it cannot be guaranteed that these solvents will meet the expectations placed on them. meet the greatest possible safety.

In den älteren deutschen Offenlegungsschriften 2242910, 2251350, 2306454 und 2726782 wurden zwar bereits weitestgehend als unbedenklich geltende ölartige Substanzen genannt, wie z.B. Paraffinöl, Sojaöl oder Fischöl, jedoch wurden diese Öle bisher lediglich als Verschnittmittel angesehen und wurden gemäß den drei letztgenannten Schriften in einer Menge von 0 bis 3 Gewichtsteilen Pro Gewichtsteil eines ausgesprochen gut lösenden Mittels für den Farbbildner eingesetzt. Während die DE-A- 22 42 910 lediglich die Möglichkeit der Einkapselung der Öle anspricht, ohne auf die Lösungsmitteleigenschaften für die bekannten Farbbildner einzugehen, gibt die DE-A- 23 06 454 ausdrücklich an, daß diese als Verdünnungsmittel bezeichneten Öle als Lösungsmittel nur einen geringen praktischen Wert aufweisen und die Farbentwicklung inhibieren. Ihre Funktion wird in der Verbilligung und in der Beeinflussung der Physikalischen Eigenschaften wie Viskosität oder Dampfdruck gesehen. Eigene Versuche der Anmelderin haben gezeigt, daß Nachteile für die Farbreaktion entstehen, wenn die Menge des Verschnittmittels höher als 20 bis 30 Gew.%, bezogen auf das Gesamt-Lösungsmittelgemisch, gewählt wurde.In the older German Offenlegungsschriften 2242910, 2251350, 2306454 and 2726782, oily substances, such as paraffin oil, soybean oil or fish oil, were largely considered to be harmless, but so far these oils have only been regarded as blending agents and have been used in a quantity in accordance with the last three documents from 0 to 3 parts by weight per part by weight of an extremely good solvent for the color former. While DE-A-22 42 910 only addresses the possibility of encapsulating the oils without going into the solvent properties for the known color formers, DE-A-23 06 454 expressly states that these oils, called diluents, are only solvents have little practical value and inhibit color development. Their function is seen in the cheapening and in influencing the physical properties such as viscosity or vapor pressure. Own Experiments by the applicant have shown that disadvantages for the color reaction arise if the amount of the extender is chosen to be higher than 20 to 30% by weight, based on the total solvent mixture.

Die EP-A- 24898 schlägt ein Lösungsmittelgemisch aus aromatischem Kohlenwasserstoff- und Esterkomponenten in bestimmtem Verhältnis vor, wobei dieses Lösungsmittelgemisch vorteilhafterweise mindestens zu 50 Gew.% und nur in Ausnahmefällen mit höheren Anteilen von inertem Verdünnungsmittel, wie z.B. Mineral- oder pflanzlichen Ölen verschnitten werden kann.EP-A-24898 proposes a solvent mixture of aromatic hydrocarbon and ester components in a specific ratio, this solvent mixture advantageously at least 50% by weight and only in exceptional cases with higher proportions of inert diluent, such as e.g. Mineral or vegetable oils can be blended.

Auch die EP-A- 86636, in der unter einer Vielzahl von hochsiedenden Lösungsmitteln den aromatischen Kohlenwasserstoffen der Vorzug gegenüber Ölen tierischer oder pflanzlicher Herkunft sowie Mineralölen gegeben wird, bringt die allgemein vorherrschende Auffassung zum Ausdruck, daß die natürlich vorkommenden Öle auf mineralischer, tierischer oder pflanzlicher Basis weniger gut geeignet sind, weil sie trotz ihrer an sich bekannten physiologischen Unbedenklichkeit als Schlechtlöser für die üblichen Farbbildner bekannt sind und ihre Verwendung in signifikanten Mengen ein geringeres Farbbildungsvermögen, insbesondere eine geringere Farbintensität zur Folge haben würde.EP-A-86636, in which aromatic hydrocarbons are preferred to oils of animal or vegetable origin and mineral oils among a large number of high-boiling solvents, expresses the generally prevailing view that the naturally occurring oils are based on mineral, animal or Vegetable-based are less suitable because, despite their known physiological harmlessness, they are known as a bad solvent for the usual color formers and their use in significant amounts would result in a lower color-forming capacity, in particular a lower color intensity.

Ausgehend von diesem Stand der Technik liegt der vorliegenden Erfindung die Aufgabe zugrunde, ein druckempfindliches Aufzeichnungsmaterial zur Verfügung zu stellen, bei dem die in Mikrokapseln eingeschlossenen Farbbildner in einem physiologisch weitestgehend unbedenklichen Lösungsmittel gelöst sind.Starting from this prior art, the present invention has for its object to provide a pressure-sensitive recording material in which the in microcapsules included color formers are dissolved in a physiologically largely harmless solvent.

Dabei sollen die Vorteile der bekannten Aufzeichnungsmaterialien, wie z.B. schnelle Farbentwicklung und hohe Farbintensität, bei Kontakt des Farbbildners mit einem geeigneten Reaktanten nicht aufgegeben werden.The advantages of known recording materials, e.g. rapid color development and high color intensity, should not be abandoned when the color former comes into contact with a suitable reactant.

Diese Aufgabe wird bei einem Gegenstand nach dem Oberbegriff des Anspruchs 1 gelöst, durch dessen Merkmale im kennzeichnenden Teil.This object is achieved with an object according to the preamble of claim 1, by the features in the characterizing part.

Bisher hat man versucht, die anstehenden Probleme der Unbedenklichkeit des Lösungsmittels für den Farbbildner bzw. die Erzielung einer schnellen Farbreaktion und hohen Farbintensität dadurch zu erreichen, daß immer neue Lösungsmittel für den Farbbildner oder Abmischungen bekannter Lösungsmittel vorgeschlagen wurden. Die vorliegende Erfindung verläßt diese Entwicklungsrichtung und löst die anstehende Aufgabe unter Rückgriff auf die aus dem Stand der Technik bekannten Öle, deren Unbedenklichkeit sich in langen Jahren erwiesen hat, denen aber bisher der Ruf anhaftete, eine schlechte Lösekraft für den Farbbildner zu besitzen und damit zu einem schlechten Farbbildevermögen, genauer: zu einer langsamen Farbreaktion und zu einer geringen Farbintensität zu führen.So far, attempts have been made to achieve the problems of harmlessness of the solvent for the color former or the achievement of a rapid color reaction and high color intensity by the fact that ever new solvents for the color former or mixtures of known solvents have been proposed. The present invention leaves this direction of development and solves the task at hand by using the oils known from the prior art, the safety of which has been proven over many years, but which has hitherto had the reputation of having a poor dissolving power for the color former and thus a poor color image ability, more precisely: to lead to a slow color reaction and to a low color intensity.

Die Überwindung dieses Nachteils der bekannten pflanzlichen und tierischen Öle sowie von Paraffinöl gelingt der vorliegenden Erfindung dadurch, daß ein Farbbildner auf Basis eines Triphenylmethanleukofarbstoffes eingesetzt wird, der in den vorstehend genannten Lösungsmitteln löslich ist.Overcoming this disadvantage of the well-known vegetable and animal oils as well as paraffin oil The present invention succeeds in that a color former based on a triphenylmethane leuco dye is used which is soluble in the solvents mentioned above.

Gemäß einer bevorzugten Ausführungsform besteht das Lösungsmittel für den Farbbildner vollständig aus z.B. pflanzlichen Ölen. Zur Erreichung einer weitestgehenden Unbedenklichkeit hat es sich aber als ausreichend erwiesen, wenn mindestens 80 Gew.% des verwendeten Lösungsmittels aus den erfindungsgemäß vorgeschlagenen Ölen bestehen. Als restliche Lösungsmittel können an sich die für Farbbildner bekannten Lösungsmittel, wie alkylierte Naphtaline, hydrierte Terphenyle, alkylierte Biphenyle, Diphenyläthane, Alkylbenzole, Chlorparaffine, oder Mischungen dieser Verbindungen eingesetzt werden. Bei einem Zusatz von mehr als 20 Gew.% solcher Lösungsmittel bestehen erhöhte Bedenken bezüglich der Unbedenklichkeit.According to a preferred embodiment, the solvent for the color former consists entirely of e.g. vegetable oils. To achieve the greatest possible harmlessness, however, it has proven sufficient if at least 80% by weight of the solvent used consists of the oils proposed according to the invention. The solvents known per se for color formers, such as alkylated naphthalenes, hydrogenated terphenyls, alkylated biphenyls, diphenylethanes, alkylbenzenes, chlorinated paraffins, or mixtures of these compounds can be used as residual solvents. If more than 20% by weight of such solvents is added, there are increased concerns about the safety.

Eine erhebliche Bedeutung im Rahmen der vorliegenden Erfindung kommt auch der Auswahl des Kapselwandmaterials zu, das zur Herstellung der Mikrokapseln in gelöstem Zustand vorliegen muß. Zur Einkapselung der aus Lösungsmittel und darin gelöstem Farbbildner bestehenden Tröpfchen haben sich im Rahmen der vorliegenden Erfindung wasserlösliche Polymere oder wasserdispergierbare Hydrokolloide aber auch dispergierbare Kunststoffe zur Herstellung von Kapselwandmaterialien als geeignet erwiesen.The selection of the capsule wall material, which must be present in the dissolved state for the production of the microcapsules, is also of considerable importance in the context of the present invention. For the encapsulation of the droplets consisting of solvent and color former dissolved therein, water-soluble polymers or water-dispersible hydrocolloids, but also dispersible plastics for the production of capsule wall materials have proven to be suitable in the context of the present invention.

Vorteilhafte Weiterbildungen der Erfindung sind durch die Unteransprüche gekennzeichnet. Insbesondere sieht die Erfindung auch Abmischungen der genannten Farbbildner vor, die zur Erreichung eines bestimmten Farbtones besonders vorteilhaft sind.Advantageous developments of the invention are characterized by the subclaims. In particular, the invention also provides mixtures of the color formers mentioned, which are particularly advantageous for achieving a specific color tone.

Von den Mineralölen haben sich insbesondere Weißöl und Spindelöl und ferner das aus dem medizinischen Bereich bekannte paraffinum liquidum nach DAB 8 (Deutsches Arzneimittelbuch, 8. Auflage) als besonders geeignet erwiesen.Of the mineral oils, white oil and spindle oil in particular, and also paraffinum liquidum known from the medical field according to DAB 8 (German Pharmaceutical Book, 8th edition) have proven to be particularly suitable.

Die Herstellung der Mikrokapseln erfolgt nach an sich bekannten Verfahren, wie z.B. den in der DE-B- 1122495 und der DE-A- 2225274 beschriebenen Koazervationverfahren. Dort werden auch die geeigneten wasserlöslichen polymeren Stoffe, wie z.B. Schweinehautgelatine, Gummiarabikum, Celluloseverbindungen und Polyvinylalkohol beschrieben. Die Herstellung von Mikrokapseln aus Harnstoff-Formaldehydharzen ist in der US-PS 3516941 angegeben. Es ist aber hervorzuheben, daß die Erfindung nicht auf die Anwendung der in den vorstehenden Schriften beschriebenen Verkapselungsverfahren und Kapselwandmaterialien beschränkt ist. Vielmehr kann das erfindungsgemäße Aufzeichnungsmaterial mit allen Mikrokapseln hergestellt werden, deren Wände sich aus einem zunächst in Wasser gelösten oder dispergierten Material bilden, wobei zur Ausbildung einer dichten und beständigen Kapselwand ggf. noch zusätzliche Aushärtungsschritte angewendet, bzw. solche Stoffe zugegeben werden, die eine weitere Aushärtung der Kapselwände bewirken können.The microcapsules are produced by processes known per se, such as, for example, the coacervation processes described in DE-B-1122495 and DE-A-2225274. The suitable water-soluble polymeric substances such as pig skin gelatin, gum arabic, cellulose compounds and polyvinyl alcohol are also described there. The production of microcapsules from urea-formaldehyde resins is specified in US Pat. No. 3,516,941. However, it should be emphasized that the invention is not restricted to the use of the encapsulation methods and capsule wall materials described in the above documents. Rather, the recording material according to the invention can be produced with all microcapsules, the walls of which are formed from a material initially dissolved or dispersed in water, additional hardening steps possibly being used to form a dense and stable capsule wall, or such substances being added that add another Can cause hardening of the capsule walls.

Die nachfolgenden Beispiele dienen der näheren Erläuterung der Erfindung.The following examples serve to explain the invention in more detail.

Beispiele 1 bis 18:Examples 1 to 18:

Entsprechend der nachfolgenden Tabelle wurden bei Temperaturen von 25 bis 40 °C Lösungen von Farbbildnern hergestellt und die hergestellten Lösungen in einem Melaminformaldehyd-Vorkondensat verkapselt. Die fertigen Mikrokapseln wurden auf die Rückseite eines holzfreien Papiers aufgetragen. Bei Druckkontakt mit einem mit sauren Farbreaktanten beschichteten Nehmerpapier wurde eine gute Farbreaktion und eine hervorragende Farbintensität beobachtet, insbesondere bei den Beispielen 1 bis 4. Gute Ergebnisse bezüglich der Farbintensität zeigten auch die Beispiele 5 bis 9, wohingegen Beispiel 10 eine geringfügig geringere Farbintensität aufwies. Befriedigende Ergebnisse wurden mit den Beispielen 11 bis 18 erzielt.

Figure imgb0001
According to the table below, solutions of color formers were prepared at temperatures of 25 to 40 ° C. and the solutions prepared were encapsulated in a melamine-formaldehyde precondensate. The finished microcapsules were applied to the back of a wood-free paper. A good color reaction and an excellent color intensity were observed on pressure contact with a receiver paper coated with acidic color reactants, in particular in Examples 1 to 4. Examples 5 to 9 also showed good results with regard to color intensity, whereas Example 10 had a slightly lower color intensity. Satisfactory results were obtained with Examples 11 to 18.
Figure imgb0001

Vergleichsbeispiele:Comparative examples:

1 Gew.-Teil eines handelsüblichen Farbbildners für eine grüne Farbe 2ʹ[bis (Phenyl Methyl) Amino]-6ʹ-(Diethyl Amino)-4ʹ-Methyl-Spiro-[Isobenzofuran-1-(3h),9ʹ-­[9h] Xanthen]-3-on wird bei 80 bis 90° in 100 Gew.-Teile Sonnenblumenöl eingerührt. Selbst nach mehreren Stunden ging der Farbbildner nicht vollständig in Lösung. Trägt man das Gemisch mittels eines RK-Coaters (Tiefdruckplatte) auf ein Nehmerpapier auf, so beobachtet man eine äußerst langsame Farbreaktion, die zu einer unbefriedigenden Farbintensität führt. Wiederholt man diesen Versuch mit einem Gemisch aus 75 Gew.-Teilen Sonnenblumenöl und 25 Gew.-Teilen Diisopropylnaphthalin, so geht zwar augenscheinlich mehr in Lösung, aber die Effekte, langsame Farbbildung und geringe Farbintensität, bleiben.1 part by weight of a commercial color former for a green color 2ʹ [bis (phenyl methyl) amino] -6ʹ- (diethyl amino) -4ʹ-methyl-spiro- [isobenzofuran-1- (3h), 9ʹ- [9h] xanthene ] -3-one is stirred in at 80 to 90 ° in 100 parts by weight of sunflower oil. Even after several hours, the color former did not completely dissolve. If the mixture is applied to an acceptor paper using an RK coater (gravure printing plate), an extremely slow color reaction is observed, which leads to an unsatisfactory color intensity. If you repeat this experiment with a mixture of 75 parts by weight of sunflower oil and 25 parts by weight of diisopropylnaphthalene, more is evidently dissolved, but the effects, slow color formation and low color intensity remain.

Erst die Lösung in reinem Diisopropylnaphthalin zeigt ein ausreichendes Tempo bei der Farbbildung und hohe Farbintensität.Only the solution in pure diisopropylnaphthalene shows a sufficient pace in color formation and high color intensity.

Claims (15)

1. Druckempfindliches Aufzeichnungsmaterial mit Mikrokapseln, die einen auf Basis eines Triphenylmethanleukofarbstoffes hergestellten und in einem Lösungsmittel gelösten Farbbildner enthalten, dadurch gekennzeichnet, daß der Farbbildner in einem zumindest zu 80 Gew.% aus pflanzlichem, tierischem oder Paraffinöl bestehenden Lösungsmittel gelöst ist und die Mikrokapseln aus einem Wandmaterial gebildet sind, das vor der Mikrokapselbildung wasserlöslich oder wasserdispergierbar ist.1. Pressure-sensitive recording material with microcapsules containing a color former based on a triphenylmethane leuco dye and dissolved in a solvent, characterized in that the color former is dissolved in at least 80% by weight of vegetable, animal or paraffin oil and the microcapsules are made from a wall material is formed which is water-soluble or water-dispersible before the microcapsule formation. 2. Druckempfindliches Aufzeichnungsmaterial nach Anspruch 1, gekennzeichnet durch einen Farbbildner der Formel:
Figure imgb0002
 worin,
R₁ ein C₁-C₄-Alkoxy oder ein Rest der Formel
Figure imgb0003
 R₂ und R₃ unabhängig voneinander ein C₁-C₄-Alkyl oder Aryl bedeuten oder R₂ mit dem Ring A in o-Stellung zum Stickstoff einen Ring schließt mit der Formel
Figure imgb0004
 R₄ und R₅ ein C₁-C₄-Alkyl

R₆ Wasserstoff, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy

R₇ Hydroxy oder C₁-C₄-Alkoxy

R₈ und R₉ unabhängig voneinander ein C₁-C₄-Alkyl, Aryl oder Cyan-substituiertes Aryl und

R₁₀ Wasserstoff, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy bedeuten.2. Pressure-sensitive recording material according to claim 1, characterized by a color former of the formula:
Figure imgb0002
 wherein,
R₁ is a C₁-C₄ alkoxy or a radical of the formula
Figure imgb0003
 R₂ and R₃ independently of one another represent a C₁-C₄-alkyl or aryl or R₂ with the ring A in the o-position to nitrogen closes a ring with the formula
Figure imgb0004
 R₄ and R₅ are C₁-C₄ alkyl

R₆ is hydrogen, C₁-C₄ alkyl or C₁-C₄ alkoxy

R₇ hydroxy or C₁-C₄ alkoxy

R₈ and R₉ independently of one another a C₁-C₄ alkyl, aryl or cyano-substituted aryl and

R₁₀ is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy. 3. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0005
 3. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0005
 4. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0006
 4. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0006
 5. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0007
 5. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0007
 6. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0008
 6. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0008
 7. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0009
 7. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0009
 8. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0010
 8. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0010
 9. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0011
 9. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0011
 10. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0012
 10. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0012
 11. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0013
 11. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0013
 12. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 und 2, gekennzeichnet durch einen Farbbildner der Formel
Figure imgb0014
 12. Pressure-sensitive recording material according to one of claims 1 and 2, characterized by a color former of the formula
Figure imgb0014
 13. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß das pflanzliche Öl: Olivenöl, Baumwollsaatöl, Maisöl, Sojaöl, Rizinusöl, Distelöl, Erdnußöl, Sonnenblumenöl, Kokusnußöl, Rapsöl, Sesamöl oder eine Mischung dieser Öle ist.13. Pressure-sensitive recording material according to one of claims 1 to 12, characterized in that the vegetable oil: olive oil, cottonseed oil, corn oil, soybean oil, castor oil, safflower oil, peanut oil, sunflower oil, coconut oil, rapeseed oil, sesame oil or a mixture of these oils. 14. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß das tierische Öl: Walöl, Spermöl, Fischöl oder eine Mischung dieser Öle ist.14. Pressure-sensitive recording material according to one of claims 1 to 12, characterized in that the animal oil: whale oil, sperm oil, fish oil or a mixture of these oils. 15. Druckempfindliches Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß die Mikrokapselwände aus Harnstoff-Formaldehyd, Melamin-Formaldehyd oder Gelatine-Gummiarabikum gebildet sind.15. Pressure-sensitive recording material according to one of claims 1 to 14, characterized in that the microcapsule walls are formed from urea-formaldehyde, melamine-formaldehyde or gelatin-gum arabic.
EP87113877A 1986-09-30 1987-09-23 Pressure-sensitive recording material Expired - Lifetime EP0262569B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87113877T ATE64340T1 (en) 1986-09-30 1987-09-23 PRESSURE SENSITIVE RECORDING MATERIAL.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3633116 1986-09-30
DE19863633116 DE3633116A1 (en) 1986-09-30 1986-09-30 PRESSURE SENSITIVE RECORDING MATERIAL

Publications (4)

Publication Number Publication Date
EP0262569A2 true EP0262569A2 (en) 1988-04-06
EP0262569A3 EP0262569A3 (en) 1989-06-07
EP0262569B1 EP0262569B1 (en) 1991-06-12
EP0262569B2 EP0262569B2 (en) 1994-03-02

Family

ID=6310630

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87113877A Expired - Lifetime EP0262569B2 (en) 1986-09-30 1987-09-23 Pressure-sensitive recording material

Country Status (10)

Country Link
US (1) US4859650A (en)
EP (1) EP0262569B2 (en)
JP (1) JPS6395980A (en)
AT (1) ATE64340T1 (en)
DE (2) DE3633116A1 (en)
DK (1) DK167384B1 (en)
ES (1) ES2022247T5 (en)
FI (1) FI88900C (en)
GR (1) GR3002214T3 (en)
IL (1) IL83870A (en)

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EP0281891A2 (en) * 1987-03-10 1988-09-14 Bayer Ag Dye builders, their preparation and use
EP0573210A2 (en) * 1992-06-04 1993-12-08 The Wiggins Teape Group Limited Pressure-sensitive record material
US5281266A (en) * 1991-06-18 1994-01-25 The Wiggins Teape Group Limited Solvent compositions for use in pressure-sensitive copying paper
EP0633144A1 (en) * 1993-07-03 1995-01-11 The Wiggins Teape Group Limited Pressure-sensitive copying material
US5478380A (en) * 1992-10-15 1995-12-26 The Wiggins Teape Group Limited Chromogenic composition for use in pressure-sensitive record material
EP0697293A1 (en) 1994-07-26 1996-02-21 Copigraph New organic solvent for microcapsules useful notably for pressure-sensitive copy paper and pressure-sensitive copy coated with such microcapsules
EP0697292A1 (en) 1994-07-20 1996-02-21 The Wiggings Teape Group Limited Pressure-sensitive copying material
EP0714786A1 (en) 1994-12-02 1996-06-05 Copigraph New microcapsules comprising as solvent a terpene derivative or an abietic acid derivative, notably for chemical copy papers and messure sensitive papers coated with such microcapsules
US5552365A (en) * 1994-03-18 1996-09-03 Bayer Aktiengesellschaft Pressure-sensitive recording material which comprises natural oils and/or derivatives thereof

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GB9318369D0 (en) * 1993-09-04 1993-10-20 Carrs Paper Ltd Pressure-sensitive record materials
US5462597A (en) * 1994-06-30 1995-10-31 Minnesota Mining And Manufacturing System for inkless fingerprinting
ES2277101T3 (en) * 2002-09-20 2007-07-01 Papierfabrik August Koehler Ag PROCEDURE FOR ENCAPSULATING DISSOLVED COLORED CORREACTANTS OF CHROMATIC REACTION SYSTEMS, THE CAPSULES OBTAINED AFTER, AS WELL AS THEIR USE IN CHROMATIC REACTION PAPERS.
US8053494B2 (en) * 2003-10-06 2011-11-08 Nocopi Technologies, Inc. Invisible ink and scratch pad
US20050165131A1 (en) * 2003-10-06 2005-07-28 Terry Stovold Invisible ink
US20050075420A1 (en) * 2003-10-06 2005-04-07 Terry Stovold Invisible ink
US7727319B2 (en) * 2006-04-19 2010-06-01 Crayola Llc Water-based ink system
US7815723B2 (en) * 2006-04-19 2010-10-19 Crayola Llc Water-based ink system

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Publication number Priority date Publication date Assignee Title
EP0281891A2 (en) * 1987-03-10 1988-09-14 Bayer Ag Dye builders, their preparation and use
EP0281891A3 (en) * 1987-03-10 1991-11-13 Bayer Ag Dye builders, their preparation and use
US5472489A (en) * 1991-06-18 1995-12-05 The Wiggins Teape Group Limited Solvent compositions for use in pressure-sensitive copying paper
US5281266A (en) * 1991-06-18 1994-01-25 The Wiggins Teape Group Limited Solvent compositions for use in pressure-sensitive copying paper
US5464803A (en) * 1992-06-04 1995-11-07 The Wiggins Teape Group Limited Pressure-sensitive record material
EP0573210A3 (en) * 1992-06-04 1995-01-25 Wiggins Teape Group Ltd Pressure-sensitive record material.
EP0573210A2 (en) * 1992-06-04 1993-12-08 The Wiggins Teape Group Limited Pressure-sensitive record material
US5478380A (en) * 1992-10-15 1995-12-26 The Wiggins Teape Group Limited Chromogenic composition for use in pressure-sensitive record material
EP0633144A1 (en) * 1993-07-03 1995-01-11 The Wiggins Teape Group Limited Pressure-sensitive copying material
US5552365A (en) * 1994-03-18 1996-09-03 Bayer Aktiengesellschaft Pressure-sensitive recording material which comprises natural oils and/or derivatives thereof
EP0697292A1 (en) 1994-07-20 1996-02-21 The Wiggings Teape Group Limited Pressure-sensitive copying material
EP0697293A1 (en) 1994-07-26 1996-02-21 Copigraph New organic solvent for microcapsules useful notably for pressure-sensitive copy paper and pressure-sensitive copy coated with such microcapsules
EP0714786A1 (en) 1994-12-02 1996-06-05 Copigraph New microcapsules comprising as solvent a terpene derivative or an abietic acid derivative, notably for chemical copy papers and messure sensitive papers coated with such microcapsules

Also Published As

Publication number Publication date
US4859650A (en) 1989-08-22
DK167384B1 (en) 1993-10-25
DK514287A (en) 1988-03-31
EP0262569B2 (en) 1994-03-02
IL83870A0 (en) 1988-02-29
DE3633116A1 (en) 1988-04-07
IL83870A (en) 1991-12-15
ATE64340T1 (en) 1991-06-15
GR3002214T3 (en) 1992-12-30
EP0262569B1 (en) 1991-06-12
DK514287D0 (en) 1987-09-30
ES2022247T5 (en) 1995-08-16
ES2022247B3 (en) 1991-12-01
FI874231A (en) 1988-03-31
FI874231A0 (en) 1987-09-25
EP0262569A3 (en) 1989-06-07
FI88900B (en) 1993-04-15
JPS6395980A (en) 1988-04-26
DE3770735D1 (en) 1991-07-18
FI88900C (en) 1993-07-26

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