EP0262569B2 - Pressure-sensitive recording material - Google Patents
Pressure-sensitive recording material Download PDFInfo
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- EP0262569B2 EP0262569B2 EP87113877A EP87113877A EP0262569B2 EP 0262569 B2 EP0262569 B2 EP 0262569B2 EP 87113877 A EP87113877 A EP 87113877A EP 87113877 A EP87113877 A EP 87113877A EP 0262569 B2 EP0262569 B2 EP 0262569B2
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- Prior art keywords
- oil
- recording material
- sensitive recording
- material according
- colour former
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Classifications
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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
- B41M5/124—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
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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
- B41M5/124—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
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- 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 provide 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. Microcapsules given as examples contain chlorinated biphenyl and dimethylnaphthalene, the wall material consisting of pig skin gelatin .
- EP-A-24898 proposes a solvent mixture of aromatic hydrocarbon and ester components in a certain ratio, the solvent for the dye precursor mixture advantageously consisting of at least 50% by weight of the solvent mixture and only in exceptional cases with higher proportions of inert diluent, e.g. Mineral or vegetable oils can be blended.
- inert diluent e.g. Mineral or vegetable oils
- EP-A-86636 in which aromatic hydrocarbons are preferred over 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 plant-based are less suitable because, despite their known physiological harmlessness, they are known as bad solvents 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.
- EP-A-234 394 which falls under Article 54 (3) EPC and applies to the contracting states CH, DE, FR, GB and LI, discloses, among other things, as a solvent for the triphenylmethane type color formers described therein.
- vegetable oils e.g. Sesame oil or sunflower oil, however, teaches the use of vegetable oils, kerosene and white oil in their examples as solvents only for diluting the main solvents: chlorinated paraffin, dodecylbenzene and diisopropylnaphthalene.
- interfacial reaction processes and polyaddition products of polyisocyanates and polyamines are given as the preferred capsule wall material. Water soluble wall materials are also disclosed, but not for encapsulating color former solutions containing vegetable oils or white oil as the predominant solvent component.
- the present invention is based on the object of providing a pressure-sensitive recording material in which the color formers enclosed in microcapsules are dissolved in a physiologically largely harmless solvent.
- the present invention overcomes this disadvantage of the known vegetable and animal oils as well as paraffin oil by using a color former based on a triphenylmethane leuco dye as defined in the claims, which is dissolved in the above-mentioned solvents.
- 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 for the production of capsule wall materials have proven to be suitable for encapsulating the droplets consisting of solvent and color former dissolved therein.
- 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 methods known per se, such as the coacervation processes described in DE-B-1122495 and DE-A-2225274.
- suitable water-soluble polymeric substances e.g. Pig skin gelatin, gum arabic, cellulose compounds and polyvinyl alcohol are described.
- the production of microcapsules from urea-formaldehyde resins is specified in US Pat. No. 3,516,941.
- the invention is not restricted to the use of the encapsulation processes 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 in water, additional hardening steps possibly being used to form a dense and stable capsule wall, or such substances are added that further harden the Can cause 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, in particular in Examples 1 to 4.
- Examples 5 to 9 also showed good results with regard to color intensity. Satisfactory results were obtained with Examples 10 to 17 .
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
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. Beispielhaft angegebene Mikro kapseln enthalten chloriertes Biphenyl und Dimethylnaphthalin, wobei das Wandmaterial aus Schweinehautgelatine besteht. 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 provide 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. Microcapsules given as examples contain chlorinated biphenyl and dimethylnaphthalene, the wall material consisting of pig skin gelatin . 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. The need arose to replace these solvents with those solvents which are less of a concern in this respect. 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 typeface 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 considered certain 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 laid-open publications 2242910, 2251350, 2306454 and 2726782, oily substances which were considered to be largely harmless were already mentioned, e.g. Paraffin oil, soybean oil or fish oil, however, these oils have hitherto been regarded only as a blending agent and have been used according to the three last-mentioned documents in an amount of 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, referred to as diluents, are only one solvent 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. The applicant's own experiments have shown that there are disadvantages for the color reaction 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 das Lösungsmittel für die Farbstoffvorläufermichung vorteilhafterweise mindestens zu 50 Gew.% aus dem Lösungsmittelgemisch besteht 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 certain ratio, the solvent for the dye precursor mixture advantageously consisting of at least 50% by weight of the solvent mixture and only in exceptional cases with higher proportions of inert diluent, 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 over 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 plant-based are less suitable because, despite their known physiological harmlessness, they are known as bad solvents 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.
Die unter Artikel 54 (3) EPÜ fallende und für die Vertragsstaaten CH, DE, FR, GB und LI geltende EP-A-234 394 offenbart als Lösungsmittel für die dort beschriebenen Farbbildner vom Triphenylmethantyp u.a. auch pflanzliche Öle, wie z.B. Sesamöl oder Sonnenblumenöl, lehrt in ihren Beispielen als Lösungsmittel jedoch den Einsatz von pflanzlichen Ölen, Kerosin und Weißöl lediglich zur Verdünnung der Hauptlösungsmittel: Chlorparaffin, Dodecylbenzol und Diisopropylnaphthalin. Zur Einkapselung der erhaltenen Farbbildner-Lösungen werden Grenzflächen-Reaktionsverfahren und als bevorzugtes Kapselwandmaterial Polyadditionsprodukte aus Polyisocyanaten und Polyaminen angegeben. Wasserlösliche Wandmaterialien werden ebenfalls offenbart, jedoch nicht zur Einkapselung von Farbbildnerlösungen, die als überwiegende Lösungsmittelkomponente pflanzliche Öle oder Weißöl enthalten.EP-A-234 394, which falls under Article 54 (3) EPC and applies to the contracting states CH, DE, FR, GB and LI, discloses, among other things, as a solvent for the triphenylmethane type color formers described therein. also vegetable oils, e.g. Sesame oil or sunflower oil, however, teaches the use of vegetable oils, kerosene and white oil in their examples as solvents only for diluting the main solvents: chlorinated paraffin, dodecylbenzene and diisopropylnaphthalene. For the encapsulation of the color former solutions obtained, interfacial reaction processes and polyaddition products of polyisocyanates and polyamines are given as the preferred capsule wall material. Water soluble wall materials are also disclosed, but not for encapsulating color former solutions containing vegetable oils or white oil as the predominant solvent component.
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 is based on the object of providing a pressure-sensitive recording material in which the color formers enclosed in microcapsules 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 the known recording materials, such as rapid color development and high color intensity, should not be abandoned when the color former comes into contact with a suitable reactant will.
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, wie in den Ansprüchen definiert, eingesetzt wird, der in den vostehend gennanten Lösungsmitteln aufgelöst ist.The present invention overcomes this disadvantage of the known vegetable and animal oils as well as paraffin oil by using a color former based on a triphenylmethane leuco dye as defined in the claims, which is dissolved in the above-mentioned solvents.
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 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. In the context of the present invention, water-soluble polymers for the production of capsule wall materials have proven to be suitable for encapsulating the droplets consisting of solvent and color former dissolved therein.
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 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 methods known per se, such as the coacervation processes described in DE-B-1122495 and DE-A-2225274. The suitable water-soluble polymeric substances, e.g. Pig skin gelatin, gum arabic, cellulose compounds and polyvinyl alcohol are described. 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 processes 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 in water, additional hardening steps possibly being used to form a dense and stable capsule wall, or such substances are added that further harden the Can cause capsule walls.
Die nachfolgenden Beispiele dienen der näheren Erläuterung der Erfindung.The following examples serve to explain the invention in more detail.
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. Befriedigende Ergebnisse wurden mit den Beispielen 10 bis 17 erzielt.
1 Gew.-Teil eines handelsüblichen Farbbildners für eine grüne Farbe 2' [bis (Phenyl Methyl) Amino]-6'-(Diethyl Amino)-4'-Methyl-Spiro-[Isobenzofuran-1-(3h) ,9'-[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 2 '[bis (phenylmethyl) amino] -6' - (diethylamino) -4'-methyl-spiro- [isobenzofuran-1- (3h), 9'- [9h] Xanthene] -3-one is stirred in at 80 to 90 ° in 100 parts by weight of sunflower oil. The color former did not work even after several hours in solution. 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 (14)
- Pressure-sensitive recording material having microcapsules that contain a colour former that is based on a triphenylmethane leuco dyestuff and is dissolved in a solvent, wherein the colour former is dissolved in a solvent of which at least 80 % by weight consists of vegetable oil, animal oil, white oil or spindle oil, and the microcapsules are formed from a wall material that is water-soluble before the microcapsule formation, and the colour former corresponds to the formula
R₁ represents a C₁-C₄-alkoxy radical or a radical of the formula
R₂ and R₃ each represents, independently of the other, a C₁-C₄-alkyl or aryl radical or R₂, together with the ring A in the o-position to the nitrogen, completes a ring of the formula
R₄ and R₅ are each C₁-C₄-alkyl,R₆ represents hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy,R₇ represents hydroxy or C₁-C₄-alkoxy,R₈ and R₉ each represents, independently of the other, a C₁-C₄-alkyl, aryl or cyano-substituted aryl radical andR₁₀ represents hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy. - Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to claim 1, characterised by a colour former of the formula
- Pressure-sensitive recording material according to any one of claims 1 to 11, characterised in that the vegetable oil is olive oil, cottonseed oil, corn oil, soybean oil, castor oil, thistle oil, peanut oil, sunflower oil, coconut oil, rape oil, sesame oil or a mixture of those oils.
- Pressure-sensitive recording material according to any one of claims 1 to 11, characterised in that the animal oil is whale oil, sperm oil, fish oil or a mixture of those oils.
- Pressure-sensitive recording material according to any one of claims 1 to 13, characterised in that the microcapsule walls are formed from urea/formaldehyde, melamine/formaldehyde or gelatin/gum arabic.
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 EP0262569A2 (en) | 1988-04-06 |
| EP0262569A3 EP0262569A3 (en) | 1989-06-07 |
| EP0262569B1 EP0262569B1 (en) | 1991-06-12 |
| EP0262569B2 true 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) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3707548A1 (en) * | 1987-03-10 | 1988-10-06 | Bayer Ag | COLOR IMAGES, THEIR PRODUCTION AND USE |
| DE3727878A1 (en) * | 1987-08-21 | 1989-03-02 | Bayer Ag | TRIARYLMETHANE COLOR IMAGE |
| GB9113086D0 (en) * | 1991-06-18 | 1991-08-07 | Wiggins Teape Group Ltd | Solvent compositions for use in pressure-sensitive copying paper |
| EP0573210B2 (en) * | 1992-06-04 | 2005-11-23 | Arjo Wiggins Limited | Pressure-sensitive record material |
| GB9221621D0 (en) * | 1992-10-15 | 1992-11-25 | Wiggins Teape Group Ltd | Solvents for use in pressure-sensitive record material |
| GB9313790D0 (en) * | 1993-07-03 | 1993-08-18 | Wiggins Teape Group The Ltd | Pressure-sensitive copying material |
| GB9318369D0 (en) * | 1993-09-04 | 1993-10-20 | Carrs Paper Ltd | Pressure-sensitive record materials |
| DE4409265A1 (en) * | 1994-03-18 | 1995-09-21 | Bayer Ag | Pressure sensitive recording material containing natural oils and / or derivatives thereof |
| US5462597A (en) * | 1994-06-30 | 1995-10-31 | Minnesota Mining And Manufacturing | System for inkless fingerprinting |
| GB9414637D0 (en) | 1994-07-20 | 1994-09-07 | Wiggins Teape Group The Limite | Presure-sensitive copying material |
| FR2723032B1 (en) | 1994-07-26 | 1996-11-22 | Copigraph Sa | NOVEL ORGANIC SOLVENT FOR MICROCAPSULES USEFUL IN PARTICULAR FOR PRODUCING PRESSURE SENSITIVE SELF-COPYING PAPER AND LAPRESSION SENSITIVE PAPER COATED WITH SUCH MICROCAPSULES |
| FR2727633A1 (en) | 1994-12-02 | 1996-06-07 | Copigraph | MICROCAPSULES CONTAINING AS A SOLVENT A TERPENIC DERIVATIVE OR ABIETIC ACID AND PRESSURE-SENSITIVE PAPERS COATED WITH SUCH MICROCAPSULES |
| EP1539340B8 (en) * | 2002-09-20 | 2007-11-07 | Papierfabrik August Koehler AG | Method for encapsulating dissolved color reaction partners of color reaction systems, the capsules obtained according thereto, and their use in color reaction papers |
| US20050165131A1 (en) * | 2003-10-06 | 2005-07-28 | Terry Stovold | Invisible ink |
| US20050075420A1 (en) * | 2003-10-06 | 2005-04-07 | Terry Stovold | Invisible ink |
| US8053494B2 (en) * | 2003-10-06 | 2011-11-08 | Nocopi Technologies, Inc. | Invisible ink and scratch pad |
| US7815723B2 (en) * | 2006-04-19 | 2010-10-19 | Crayola Llc | Water-based ink system |
| US7727319B2 (en) * | 2006-04-19 | 2010-06-01 | Crayola Llc | Water-based ink system |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR408465A (en) * | 1900-01-01 | |||
| US3516941A (en) * | 1966-07-25 | 1970-06-23 | Minnesota Mining & Mfg | Microcapsules and process of making |
| JPS5312473B1 (en) * | 1971-05-24 | 1978-05-01 | ||
| US3886085A (en) * | 1971-08-31 | 1975-05-27 | Fuji Photo Film Co Ltd | Process for producing fine oil-containing microcapsules having strong protective shells and microcapsules produced thereby |
| BE790321A (en) * | 1971-10-20 | 1973-04-19 | Monsanto Co | SOLVENTS FOR COLORANTS OF PRESSURE SENSITIVE RECORDING MATERIALS |
| BE795255A (en) * | 1972-02-11 | 1973-08-09 | Monsanto Co | PRESSURE SENSITIVE RECORDING MATERIAL, AND DYE SOLVENTS THEREFOR |
| US3968301A (en) * | 1972-02-11 | 1976-07-06 | Monsanto Company | Pressure-sensitive record material and dye solvents therefor |
| JPS5318921B2 (en) * | 1972-07-28 | 1978-06-17 | ||
| JPS5321328B2 (en) * | 1973-10-31 | 1978-07-01 | ||
| FR2294055A1 (en) * | 1974-12-10 | 1976-07-09 | Ciba Geigy Ag | Diamino-triphenyl-carbinol ethers for use as colour formers - in (thermo)graphic material, giving blue to green colours with acid developer (BE090676) |
| GB1517647A (en) * | 1976-06-16 | 1978-07-12 | Monsanto Europe Sa | Solvents |
| DE2750283C2 (en) * | 1977-11-10 | 1985-08-22 | Bayer Ag, 5090 Leverkusen | Pressure and heat sensitive recording material |
| US4335013A (en) * | 1979-08-24 | 1982-06-15 | Monsanto Company | Solvents useful in pressure-sensitive mark-recording systems |
| US4343652A (en) * | 1979-08-24 | 1982-08-10 | Monsanto Europe S.A. | Chromogen solutions for pressure-sensitive mark-recording systems |
| US4398753A (en) * | 1980-12-26 | 1983-08-16 | Mitsui Toatsu Chemicals, Incorporated | Pressure sensitive recording unit |
| JPS57197192A (en) * | 1981-05-29 | 1982-12-03 | Fuji Photo Film Co Ltd | Microcapsule-containing sheet for pressure sensitive copying paper |
| JPS58138689A (en) * | 1982-02-13 | 1983-08-17 | Mitsubishi Paper Mills Ltd | Pressure-sensitive recording medium |
| JPS6027589A (en) * | 1983-07-26 | 1985-02-12 | Kanzaki Paper Mfg Co Ltd | Recording material |
| JPS615982A (en) * | 1984-06-21 | 1986-01-11 | Nippon Petrochem Co Ltd | Pressure-sensitive copying material |
| DE3447298C1 (en) * | 1984-12-24 | 1986-04-24 | Papierfabrik August Koehler AG, 7602 Oberkirch | Process for microencapsulation of oils with colour coreactants dissolved therein, and microcapsules produced according to the process |
| US4730057A (en) * | 1985-01-17 | 1988-03-08 | Kanzaki Paper Manufacturing Co., Ltd. | Phthalide derivatives useful as colorless chromogenic material |
| US4737587A (en) * | 1985-11-25 | 1988-04-12 | Mitsubishi Paper Mills, Ltd. | Colorless carbazole dyes for recording materials |
-
1986
- 1986-09-30 DE DE19863633116 patent/DE3633116A1/en not_active Withdrawn
-
1987
- 1987-09-11 IL IL83870A patent/IL83870A/en not_active IP Right Cessation
- 1987-09-23 ES ES87113877T patent/ES2022247T5/en not_active Expired - Lifetime
- 1987-09-23 AT AT87113877T patent/ATE64340T1/en not_active IP Right Cessation
- 1987-09-23 DE DE8787113877T patent/DE3770735D1/en not_active Expired - Fee Related
- 1987-09-23 EP EP87113877A patent/EP0262569B2/en not_active Expired - Lifetime
- 1987-09-25 FI FI874231A patent/FI88900C/en not_active IP Right Cessation
- 1987-09-30 JP JP62244449A patent/JPS6395980A/en active Pending
- 1987-09-30 US US07/103,115 patent/US4859650A/en not_active Expired - Fee Related
- 1987-09-30 DK DK514287A patent/DK167384B1/en active
-
1991
- 1991-06-27 GR GR91400896T patent/GR3002214T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES2022247T5 (en) | 1995-08-16 |
| IL83870A0 (en) | 1988-02-29 |
| DE3770735D1 (en) | 1991-07-18 |
| GR3002214T3 (en) | 1992-12-30 |
| EP0262569B1 (en) | 1991-06-12 |
| FI874231A0 (en) | 1987-09-25 |
| ES2022247B3 (en) | 1991-12-01 |
| EP0262569A3 (en) | 1989-06-07 |
| DK167384B1 (en) | 1993-10-25 |
| FI88900B (en) | 1993-04-15 |
| EP0262569A2 (en) | 1988-04-06 |
| JPS6395980A (en) | 1988-04-26 |
| FI88900C (en) | 1993-07-26 |
| DE3633116A1 (en) | 1988-04-07 |
| US4859650A (en) | 1989-08-22 |
| DK514287A (en) | 1988-03-31 |
| DK514287D0 (en) | 1987-09-30 |
| FI874231A (en) | 1988-03-31 |
| ATE64340T1 (en) | 1991-06-15 |
| IL83870A (en) | 1991-12-15 |
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