EP0090907B1 - Overlapping overprint inking ribbon - Google Patents

Overlapping overprint inking ribbon Download PDF

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Publication number
EP0090907B1
EP0090907B1 EP83100124A EP83100124A EP0090907B1 EP 0090907 B1 EP0090907 B1 EP 0090907B1 EP 83100124 A EP83100124 A EP 83100124A EP 83100124 A EP83100124 A EP 83100124A EP 0090907 B1 EP0090907 B1 EP 0090907B1
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EP
European Patent Office
Prior art keywords
fatty acid
acid ester
typewriter
color
printer ribbon
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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
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EP83100124A
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German (de)
French (fr)
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EP0090907A1 (en
Inventor
Ulrich Kohle
Hans Paffhausen
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Pelikan Produktions AG
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Pelikan GmbH
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Priority to AT83100124T priority Critical patent/ATE16368T1/en
Publication of EP0090907A1 publication Critical patent/EP0090907A1/en
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Publication of EP0090907B1 publication Critical patent/EP0090907B1/en
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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
    • B41M5/10—Duplicating or marking methods; Sheet materials for use therein by using carbon paper or the like
    • 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 relates to an overlapping rewritable ink ribbon consisting of a carrier film and an ink-releasing coating applied thereon in the form of a plastic matrix with a carbon black and / or color pigment dispersed therein, a fat dye and fine-particle fillers with a large inner surface containing paste based on a fatty acid ester a polyhydric alcohol.
  • Such an ink ribbon is known from US-A-3682683.
  • overlap overwrite means that the tape transport, which is usually slightly more than one type width, per stop on e.g. 1/3 or 1/5 of the type width is shortened, so that each type stop only hits a fresh area of the ribbon with a small proportion of the area, while the larger area proportion of the type stop lies on an area of the ribbon that has already been struck once or several times.
  • Such an ink ribbon which is also referred to in technical terms as an “overstrike ribbon" only needs to be transported in one direction like a single-use ribbon and is nevertheless used several times (e.g. 3.3 times or 5 times). Compared to those rewritable ink ribbons that are fed forward and backward (with a full transport step of approximately one type width per stroke), this saves the time-consuming and fault-prone switching mechanism for the tape running direction.
  • the overstrike tapes normally consist of a thin carrier film to which an ink-releasing coating in the form of a matrix of a plastic binder and a color paste dispersed therein is applied.
  • the color paste consists of e.g. in the form of a fatty acid ester of a polyhydric alcohol with the plastic of the matrix largely incompatible oil and color pigments.
  • a solution of the binder is applied to the carrier film using a solvent which also serves as a solubilizer for the oil.
  • the oil then separates into numerous, ideally communicating, microdroplets in the solidifying matrix.
  • the color-releasing coating of these ribbons can be viewed as a «sponge layer» applied to the carrier film and filled with the color paste, from which part of the color paste is pressed out at each type stop and forms the typeface on the paper behind it.
  • overstrike tapes An important requirement for overstrike tapes is that the same amount of color paste emerges from the ink-releasing coating at every point on the tape at each type stop. There must be no drop in color intensity between the first and the last overwriting, otherwise a spotted typeface would result. On the other hand, after the last overwriting, the yield of the ribbon can and should drop steeply, because the relevant ribbon point is not used again and does not need to give up any more color.
  • overstrike tapes in which oils such as castor oil, claw oil, peanut oil, glycerol triolein or corresponding natural or synthetic oils or generally fatty acid esters of polyhydric alcohols are used for the color paste, meet these requirements up to a 5-fold overstrike from good to satisfactory.
  • an even higher overstrike i.e. a reduction in tape transport to less than 1/5 of the type width
  • the known tapes no longer write out properly when the overstrike is higher, but instead result in a spotty font that is particularly noticeable in the underline.
  • fat dye an oil-soluble dye
  • the invention is therefore based on the object of developing the ink ribbon described at the outset in such a way that it permits a more than 10-fold overstrike with a uniform deep black and sharp-edged font intensity even in typewriter printers with a high stroke speed.
  • the fatty acid ester is a polyethoxylated fatty acid ester of a polyhydric alcohol and the finely divided fillers have a particle size distribution of 0.2 to 20 micrometers.
  • the invention is based on the completely surprising finding that the above special fatty acid ester has an unexpectedly high dissolving power for fatty dyes, which increases with an increasing number of ethoxy groups.
  • a solvent can absorb 50% fat dyes.
  • the polyethoxylated fatty acid esters according to the invention are also sufficiently incompatible with the binder of the color-releasing coating in order to form the required sponge layer in the production of the tapes. This property was also unpredictable. Normally, the introduction of ethoxy groups into the molecule increases the compatibility of the oils with plastic binders so much that the formation of a sponge layer becomes impossible, i.e. no color-releasing coating can be produced at all with these compounds.
  • those fatty acid esters which are derived from fatty acids with 12 to 25 C atoms and from alcohols with 3 to 6 OH groups and which contain 20 to 60 ethoxy groups per molecule have proven to be particularly suitable.
  • a typical and preferred example is polyoxyethylene (40) sorbitol pentaoleate, polyoxyethylene glycerol triricinolate and corresponding compounds of other fatty acids with an average of about 40 ethoxy groups.
  • oils-soluble dyes such as Sudan deep black or fat black HB, are suitable as fat dyes.
  • other colors or fluorescent characters can also be created by using appropriate oil-soluble dyes.
  • the color-releasing coating also contains an addition of finely divided fillers, for example diatomaceous earth, activated carbon or burst hollow spheres with a larger inner surface accessible to the color paste.
  • these fillers hold the (most) part of the color paste that has penetrated their pores very firmly, so that when you first overwrite it, only as much color paste is freely available as is required to form a clear type impression.
  • the fillers are also partially shattered by the stroke of the writing type, so that part of the supply of color paste originally held in the pores of the fillers is released and pressed out during the subsequent overwriting can. This process is repeated for each subsequent overwrite.
  • the fillers have the further advantage that, because most of the fatty acid ester is embedded in their pores in the color-releasing coating, there is so little free fatty acid ester that the high affinity of the binder for the carrier film is sufficient to anchor the color-releasing layer on the carrier film. This means that the previously required insertion of an adhesion-promoting intermediate layer is no longer absolutely necessary.
  • cationic wetting agents are fatty amine salts, ie the salts of long-chain, natural or Synthetic fatty acids obtained alkylamines or diamines, in particular with long-chain or short-chain fatty acids.
  • the invention thus creates a color-releasing coating in which the color paste, in addition to its content of color pigments, is also colored in an extremely high concentration with a fatty dye, that is to say it has an extremely high color strength and can therefore be kept sufficiently thin-layered.
  • the color paste is dispensed with the desired constant intensity each time it is overwritten, and it is so strong in color that striking fluctuations in the type stop are not noticeable in the intensity of the print.
  • the polyethoxylated fatty acid esters mentioned in the first place can also be replaced in whole or in part by conventional oils, such as castor oil, glycerol triolein or possibly also mineral oil.
  • the binders in the system according to the invention can be the plastic binders customary for color ribbons, such as polyacrylates, polyvinyl chloride / acetate copolymers, linear polyesters, polyvinyl acetate and polystyrene, polyamide.
  • the solvents or solvent mixtures customary in ribbon production such as e.g. Methyl ethyl ketone, toluene and isopropyl alcohol.
  • the solvent is partly introduced into the system in the form of, for example, a 25% solution of the binder. After the coating has dried, the solvent is no longer contained in the finished product.
  • the proportions of the individual components vary depending on the specific substances used, their optimal values can be easily determined by simple manual tests.
  • the coating mixture is applied and dried in accordance with the framework recipe described on a carrier film made of conventional polymers such as polyester, polyethylene, polypropylene or polyamide. Since the total thickness of the finished tape (in the interest of the longest possible tape length per cassette) should not exceed 26 11m, the carrier film is kept as thin as possible and has a layer thickness of 8 ⁇ m, for example. If necessary, the use of an antistatic intermediate layer with a thickness of approximately 2 11 m is possible.
  • PSSO fatty acid ester to be used according to the invention with an average of 40 ethoxy groups per molecule
  • an ink-releasing coating of approximately 16 / lm thickness was produced on an 8 / lm thick polyester film.
  • the ribbons obtained in this way gave a uniform, sharp-edged typeface, even in a high-speed typewriter printer, in a 12-fold overstrike, especially when the type stroke was extremely strong.

Landscapes

  • Impression-Transfer Materials And Handling Thereof (AREA)
  • Duplication Or Marking (AREA)
  • Photographic Developing Apparatuses (AREA)
  • Audible-Bandwidth Dynamoelectric Transducers Other Than Pickups (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Hydrogenated Pyridines (AREA)
  • Accessory Devices And Overall Control Thereof (AREA)
  • Decoration By Transfer Pictures (AREA)

Abstract

An overstrike ribbon has its color transfer layer formed with an oleaginic face which includes a polyoxyethylene fatty acid ester of polyhydric alcohol which as increased ability to backup the fatty dyestuff, and also contains a filler from the pores of which the color paste can be released with successive impacts.

Description

Die Erfindung betrifft ein überlappend überschreibbares Farbband aus einer Trägerfolie und einer darauf aufgebrachten farbabgebenden Beschichtung in Form einer Kunststoff-Matrix mit einer darin dispergierten, Russ- und/oder Farbpigmente, einen Fettfarbstoff sowie feinteilige Füllstoffe mit grosser innerer Oberfläche enthaltenden Paste auf der Basis eines Fettsäureesters eines mehrwertigen Alkohols.The invention relates to an overlapping rewritable ink ribbon consisting of a carrier film and an ink-releasing coating applied thereon in the form of a plastic matrix with a carbon black and / or color pigment dispersed therein, a fat dye and fine-particle fillers with a large inner surface containing paste based on a fatty acid ester a polyhydric alcohol.

Ein derartiges Farbband ist aus der US-A-3682683 bekannt.Such an ink ribbon is known from US-A-3682683.

Der Begriff «überlappend überschreibbar» bedeutet, dass der normalerweise etwas mehr als eine Typenbreite betragende Bandtransport pro Anschlag auf z.B. 1/3 oder 1/5 der Typenbreite verkürzt ist, so dass jeder Typenanschlag nur noch mit einem geringen Flächenanteil auf einen frischen Bereich des Farbbandes trifft, während der grössere Flächenanteil des Typenanschlages auf einem bereits unmittelbar vorher einmal oder mehrmals angeschlagenen Bereich des Farbbandes liegt. Ein solches Farbband, das in der Fachsprache auch als «Overstrike-Band» bezeichnet wird, braucht wie ein Einmal-Band nur noch in einer Richtung transportiert zu werden und wird dennoch mehrfach (z.B. 3,3-fach oder 5-fach) ausgenutzt. Gegenüber denjenigen mehrfach überschreibbaren Farbbändern, die (mit einem vollen Transportschritt von etwa einer Typenbreite pro Anschlag) entsprechend oft vorwärts und rückwärts geführt werden, erspart dies den aufwendigen und störanfälligen Umschaltmechanismus für die Bandlaufrichtung.The term "overlap overwrite" means that the tape transport, which is usually slightly more than one type width, per stop on e.g. 1/3 or 1/5 of the type width is shortened, so that each type stop only hits a fresh area of the ribbon with a small proportion of the area, while the larger area proportion of the type stop lies on an area of the ribbon that has already been struck once or several times. Such an ink ribbon, which is also referred to in technical terms as an "overstrike ribbon", only needs to be transported in one direction like a single-use ribbon and is nevertheless used several times (e.g. 3.3 times or 5 times). Compared to those rewritable ink ribbons that are fed forward and backward (with a full transport step of approximately one type width per stroke), this saves the time-consuming and fault-prone switching mechanism for the tape running direction.

Normalerweise bestehen die Overstrike-Bänder aus einer dünnen Trägerfolie, auf die eine farbabgebende Beschichtung in Form einer Matrix aus einem Kunststoff-Bindemittel und einer darin dispergierten Farbpaste aufgebracht ist. Die Farbpaste setzt sich dabei aus einem z.B. in Form eines Fettsäureesters eines mehrwertigen Alkohols mit dem Kunststoff der Matrix weitgehend unverträglichen Öl und Farbpigmenten zusammen. Zur Herstellung der Beschichtung wird eine Lösung des Bindemittels irr.einem Lösungsmittel, das zugleich für das Öl als Lösungsvermittler dient, auf die Trägerfolie aufgetragen. Während der Trocknung, also der Verdampfung des Lösungsmittels scheidet sich dann das Öl in zahlreichen, im Idealfall miteinander kommunizierenden Mikrotröpfchen in der sich verfestigenden Matrix ab. Infolge dessen kann die farbabgebende Beschichtung dieser Farbbänder als eine auf die Trägerfolie aufgebrachte und mit der Farbpaste gefüllte «Schwammschicht» angesehen werden, aus der bei jedem Typenanschlag ein Teil der Farbpaste ausgepresst wird und das Schriftbild auf dem dahinter liegenden Papier bildet.The overstrike tapes normally consist of a thin carrier film to which an ink-releasing coating in the form of a matrix of a plastic binder and a color paste dispersed therein is applied. The color paste consists of e.g. in the form of a fatty acid ester of a polyhydric alcohol with the plastic of the matrix largely incompatible oil and color pigments. To produce the coating, a solution of the binder is applied to the carrier film using a solvent which also serves as a solubilizer for the oil. During the drying process, i.e. the evaporation of the solvent, the oil then separates into numerous, ideally communicating, microdroplets in the solidifying matrix. As a result, the color-releasing coating of these ribbons can be viewed as a «sponge layer» applied to the carrier film and filled with the color paste, from which part of the color paste is pressed out at each type stop and forms the typeface on the paper behind it.

Eine wichtige Forderung an Overstrike-Bänder besteht darin, dass bei jedem Typenanschlag an jeder Stelle des Bandes die gleiche Menge an Farbpaste aus der farbabgebenden Beschichtung austritt. Es darf kein Abfall der Farbintensität zwischen der ersten und der letzten Überschreibung auftreten, weil sich sonst ein geflecktes Schriftbild ergeben würde. Nach der letzten Überschreibung dagegen kann und sollte sogar die Ergiebigkeit des Bandes steil abfallen, weil die betreffende Bandstelle nicht noch einmal benutzt wird und keine weitere Farbe mehr abzugeben braucht.An important requirement for overstrike tapes is that the same amount of color paste emerges from the ink-releasing coating at every point on the tape at each type stop. There must be no drop in color intensity between the first and the last overwriting, otherwise a spotted typeface would result. On the other hand, after the last overwriting, the yield of the ribbon can and should drop steeply, because the relevant ribbon point is not used again and does not need to give up any more color.

Die bekannten Overstrike-Bänder, bei denen Öle, wie Ricinusöl, Klauenöl, Erdnussöl, Glycerintriolein oder entsprechende natürliche oder synthetische Öle oder allgemein Fettsäureester mehrwertiger Alkohole für die Farbpaste verwendet werden, erfüllen diese Forderungen bis etwa zu einem 5-fachen Overstrike gut bis befriedigend. Im Interesse eines geringeren Bandverbrauches und damit geringerer Kosten wird jedoch zunehmend ein noch höherer Overstrike (d.h. eine Verkürzung des Bandtransportes auf weniger als 1/5 der Typenbreite) verlangt. Es hat sich jedoch gezeigt, dass die bekannten Bänder bei einem höheren Overstrike nicht mehr einwandfrei ausschreiben, sondern eine fleckige Schrift ergeben, die sich besonders stark im Unterstreichungsstrich bemerkbar macht.The known overstrike tapes, in which oils such as castor oil, claw oil, peanut oil, glycerol triolein or corresponding natural or synthetic oils or generally fatty acid esters of polyhydric alcohols are used for the color paste, meet these requirements up to a 5-fold overstrike from good to satisfactory. In the interest of lower tape consumption and thus lower costs, however, an even higher overstrike (i.e. a reduction in tape transport to less than 1/5 of the type width) is increasingly required. However, it has been shown that the known tapes no longer write out properly when the overstrike is higher, but instead result in a spotty font that is particularly noticeable in the underline.

Dies beruht offenbar darauf, dass sich bei den bekannten Bändern nach einer gewissen Anzahl von Überschreibungen (deren Grenze bei 6 Überschreibungen der gleichen Bandstelle zu liegen scheint) der Farbvorrat im Band zu erschöpfen beginnt. Es hat bislang keine Möglichkeit gegeben, diesen Farbvorrat nachhaltig zu erhöhen. Eine Erhöhung der Dicke der farbabgebenden Beschichtung verbietet sich allein deshalb, weil das Band im Interesse einer grossen Bandlänge pro Kassette möglichst dünn gehalten sein muss, ganz abgesehen davon, dass zu dicke Beschichtungen keine konstante Farbabgabe mehr gewährleisten. Eine Erhöhung des Mengenanteils der Farbpaste in der farbabgebenden Beschichtung ist ebenfalls nicht möglich, weil zur Herstellung einer ordnungsgemässen Schwammschicht ein bestimmtes Mindestverhältnis von Farbpaste zu Bindemittel eingehalten werden muss. Schliesslich hat sich auch die weitere Möglichkeit einer Erhöhung der Farbkraft der Farbpaste bisher nicht als ausführbar erwiesen. Bei einer Erhöhung der Pigment-Konzentration verliert die Paste die erforderliche Fliessfähigkeit. Versuche, durch zusätzliches Einfärben des Öles mit einem öllöslichen Farbstoff (nachfolgend «Fettfarbstoff» genannt) eine höhere FarbIntensität zu schaffen, sind ergebnislos geblieben, weil sich die Fettfarbstoffe in den bisher verwendeten Ölen nur in geringer Konzentration lösen lassen und damit keine ausreichende Farbtiefe ergeben.This is obviously due to the fact that the known tapes begin to run out of color after a certain number of overwrites (whose limit seems to be 6 overwrites of the same tape position). So far there has been no way to increase this color supply sustainably. An increase in the thickness of the ink-releasing coating is forbidden simply because the tape must be kept as thin as possible in the interest of a long tape length, not to mention that coatings that are too thick no longer guarantee constant ink delivery. It is also not possible to increase the proportion of color paste in the color-releasing coating because a certain minimum ratio of color paste to binder must be observed in order to produce a proper sponge layer. Finally, the further possibility of increasing the color strength of the color paste has so far not proven to be feasible. If the pigment concentration increases, the paste loses the required fluidity. Attempts to achieve a higher color intensity by additionally coloring the oil with an oil-soluble dye (hereinafter referred to as “fat dye”) have been unsuccessful because the fat dyes can only be dissolved in a low concentration in the oils used previously and therefore do not result in a sufficient depth of color.

Im Ergebnis ist bisher kein Farbband bekannt, das auch in Typenrad-Druckern mit hoher Anschlaggeschwindigkeit einen befriedigend hohen Overstrike guter Schriftqualität gewährleistet. Das gilt auch für das in der CH-A-475088 beschriebene Farbband, das durch eine besondere Schichtstruktur gekennzeichnet ist. Auf einer schwammartigen Harzmatrix dieses Bandes befindet sich eine praktisch reine Schicht aus gefülltem Farbmittel. Dieses Farbband erfordert den bereits angesprochenen nachteiligen Umschaltmechanismus für die Bandlaufrichtung und ist daher für hohe Overstrike-Werte nicht geeignet. Die US-A-3682683 erörtert allgemein die Herstellung eines Farbbandes, wobei die Tinte in einer auf dem Substrat vorliegenden porösen Harzmatrix enthalten ist. Es soll ein mindestens 5-facher Overstrike erzielbar sein. Overstrike-Werte dieser Grössenordnung befriedigen nicht. Das gleiche gilt auch für das Farbband, das in der US-A-3336150 beschrieben wird. Auch dieses Farbband ist von schwammartig poröser Struktur. In dieser Struktur ist ein nicht flüchtiger, flüssiger, partiell veresterter mehrwertiger Alkohol enthalten. Ein solcher Alkohol löst den jeweils eingesetzten Fettfarbstoff nur ungenügend. Der DE-A-2418066 lassen sich keinerlei Anregungen entnehmen, wie die mit den bekannten Farbbändern verbundenen Probleme behoben werden können. Diese Druckschrift erläutert nämlich die Einfärbung von Kunststoff-Granulaten mit Farbpasten, wobei die eingefärbten Granulate gute Fliesseigenschäften zeigen sollen. Hierzu werden Farben in Pastenform herangezogen, da mit Farbpasten eine bessere Verteilung der Farbsubstanz in den Spritz- und Presskörpern als mit reinen Pigmenten, sogenannten Trockenfarben, erzielt werden soll. Diese Technologie zeigt keinerlei wesentliche Parallelen zu derjenigen von überlappend überschreibbaren Farbbändern.As a result, no ink ribbon is known so far that guarantees a satisfactorily high overstrike of good font quality even in typewriter printers with a high stroke speed. This also applies to the ribbon described in CH-A-475088, which is characterized by a special layer structure. There is a practically pure layer of filled colorant on a sponge-like resin matrix of this tape. This ribbon requires the disadvantageous switching mechanism already mentioned for the tape running direction and is therefore not suitable for high overstrike values. US-A-3682683 generally discusses the manufacture of an ink ribbon wherein the ink is contained in a porous resin matrix present on the substrate. An at least 5-fold overstrike should be achievable. Overstrike values of this magnitude are unsatisfactory. The same also applies to the ribbon described in US-A-3336150. This ribbon is also of a spongy, porous structure. This structure contains a non-volatile, liquid, partially esterified polyhydric alcohol. Such an alcohol only dissolves the fat dye used inadequately. DE-A-2418066 does not provide any suggestions as to how the problems associated with the known ribbons can be eliminated. This publication explains the coloring of plastic granules with color pastes, the colored granules being said to show good flow properties. For this purpose, colors in paste form are used, because with color pastes a better distribution of the color substance in the injection and molding bodies is to be achieved than with pure pigments, so-called dry colors. This technology shows no significant parallels to that of overlapping overwritable ribbons.

Der Erfindung liegt daher die Aufgabe zugrunde, das eingangs beschriebene Farbband so weiterzuentwickeln, dass es auch in Typenrad-Druckern mit hoher Anschlaggeschwindigkeit einen mehr als 10-fachen Overstrike mit gleichmässiger tiefschwarzer und randscharfer Schriftintensität zulässt.The invention is therefore based on the object of developing the ink ribbon described at the outset in such a way that it permits a more than 10-fold overstrike with a uniform deep black and sharp-edged font intensity even in typewriter printers with a high stroke speed.

Erfindungsgemäss wird diese Aufgabe dadurch gelöst, dass der Fettsäureester ein polyäthoxylierter Fettsäureester eines mehrwertigen Alkohols ist und die feinteiligen Füllstoffe eine Teilchengrössenverteilung von 0,2 bis 20 Mikrometer aufweisen.According to the invention, this object is achieved in that the fatty acid ester is a polyethoxylated fatty acid ester of a polyhydric alcohol and the finely divided fillers have a particle size distribution of 0.2 to 20 micrometers.

Die Erfindung beruhtauf der völlig überraschenden Erkenntnis, dass obiger spezieller Fettsäureester ein unerwartet hohes Lösungsvermögen für Fettfarbstoffe besitzt, das mit steigender Anzahl an Äthoxygruppen ansteigt. So kann ein derartiges Lösungsmittel 50% Fettfarbstoffe aufnehmen. Die bisher bekannten üblichen Öle bzw. Fettsäureester lösen maximal 1 % oder meistens noch sehr viel weniger Fettfarbstoff. Durch die Erfindung lässt sich nunmehr erstmals ein Öl in einer ausreichenden Farbintensität einfärben.The invention is based on the completely surprising finding that the above special fatty acid ester has an unexpectedly high dissolving power for fatty dyes, which increases with an increasing number of ethoxy groups. Such a solvent can absorb 50% fat dyes. The conventional oils or fatty acid esters known up to now dissolve a maximum of 1% or mostly much less fat dye. With the invention, an oil can now be colored for the first time in a sufficient color intensity.

Die polyäthoxylierten Fettsäureester gemäss der Erfindung sind ausserdem mit dem Bindemittel der farbabgebenden Beschichtung hinreichend unverträglich, um bei der Herstellung der Bänder die erforderliche Schwammschicht auszubilden. Auch diese Eigenschaft war nicht vorhersehbar. Normalerweise erhöht sich nämlich durch die Einführung von Äthoxygruppen in das Molekül die Verträglichkeit der Öle mit Kunststoff-Bindemitteln so stark, dass die Bildung einer Schwammschicht unmöglich wird, d.h. mit diesen Verbindungen überhaupt keine farbabgebende Beschichtung herstellbar ist.The polyethoxylated fatty acid esters according to the invention are also sufficiently incompatible with the binder of the color-releasing coating in order to form the required sponge layer in the production of the tapes. This property was also unpredictable. Normally, the introduction of ethoxy groups into the molecule increases the compatibility of the oils with plastic binders so much that the formation of a sponge layer becomes impossible, i.e. no color-releasing coating can be produced at all with these compounds.

Für die Zwecke der Erfindung haben sich solche Fettsäureester, die sich von Fettsäuren mit 12 bis 25 C-Atomen und von Alkoholen mit 3 bis 6 OH-Gruppen ableiten und die 20 bis 60 Äthoxygruppen pro Molekül enthalten, als besonders geeignet erwiesen. Typisches und bevorzugtes Beispiel ist Polyoxyäthylen (40)-Sorbitpentaoleat, Polyoxyäthylen-Glycerintriricinolat sowie entsprechende Verbindungen anderer Fettsäuren mit im Durchschnitt etwa 40 Äthoxygruppen.For the purposes of the invention, those fatty acid esters which are derived from fatty acids with 12 to 25 C atoms and from alcohols with 3 to 6 OH groups and which contain 20 to 60 ethoxy groups per molecule have proven to be particularly suitable. A typical and preferred example is polyoxyethylene (40) sorbitol pentaoleate, polyoxyethylene glycerol triricinolate and corresponding compounds of other fatty acids with an average of about 40 ethoxy groups.

Aufgrund des höheren Lösungsvermögens der polyäthoxylierten Fettsäureester für Fettfarbstoffe ist es nicht erforderlich, dass die gesamte Ölbasis der farbabgebenden Beschichtung aus diesen Fettsäureestern besteht. Vielmehr können diese Fettsäureester ohne weiteres mit bis zu 50% mit den bisher für Overstrike-Bänder üblichen Ölen einschliesslich auch Mineralölen verschnitten werden, ohne dass dadurch die Farbstoff-Konzentration der Farbpaste zu gering wird.Due to the higher solvency of the polyethoxylated fatty acid esters for fatty dyes, it is not necessary that the entire oil base of the color-releasing coating consists of these fatty acid esters. Rather, these fatty acid esters can easily be blended with up to 50% with the oils previously used for overstrike tapes, including mineral oils, without the dye concentration of the color paste becoming too low.

Als Fettfarbstoffe sind alle öllöslichen Farbstoffe, wie beispielsweise Sudantiefschwarz oder Fettschwarz HB, geeignet. Selbstverständlich lassen sich auch andere Farben oder fluoreszierende Schriftzeichen durch Einsatz entsprechender öllöslicher Farbstoffe erzeugen.All oil-soluble dyes, such as Sudan deep black or fat black HB, are suitable as fat dyes. Of course, other colors or fluorescent characters can also be created by using appropriate oil-soluble dyes.

Neben den beiden Bestandteilen Fettfarbstoff und Fettsäureester enthält die farbabgebende Beschichtung auch noch einen Zusatz von feinteiligen Füllstoffen, beispielsweise Kieselgur, Aktivkohle oder aufgeplatzte Hohlkugeln mitgrosserfür die Farbpaste zugänglicher innerer Oberfläche. Diese Füllstoffe halten den in ihre Poren eingedrungenen (grössten) Teil der Farbpaste sehr fest, so dass bei der ersten Überschreibung nur gerade so viel Farbpaste frei zur Verfügung steht, wie zur Bildung eines klaren Typenabdruckes benötigt wird. Gleichzeitig mit dem Auspressen der freien Farbpaste aus der schwammartigen Kunststoff-Matrix werden die Füllstoffe durch den Anschlag der Schreibtype aber auch teilweise zerschlagen, so dass ein Teil des ursprünglich in den Poren der Füllstoffe festgehaltenen Vorrats an Farbpaste freigesetzt wird und bei der nachfolgenden Überschreibung herausgepresst werden kann. Dieser Vorgang wiederholt sich bei jeder nachfolgenden Überschreibung.In addition to the two constituents fat dye and fatty acid ester, the color-releasing coating also contains an addition of finely divided fillers, for example diatomaceous earth, activated carbon or burst hollow spheres with a larger inner surface accessible to the color paste. These fillers hold the (most) part of the color paste that has penetrated their pores very firmly, so that when you first overwrite it, only as much color paste is freely available as is required to form a clear type impression. Simultaneously with the squeezing out of the free color paste from the sponge-like plastic matrix, the fillers are also partially shattered by the stroke of the writing type, so that part of the supply of color paste originally held in the pores of the fillers is released and pressed out during the subsequent overwriting can. This process is repeated for each subsequent overwrite.

Die Füllstoffe haben den weiteren Vorteil, dass wegen der Einlagerung des grössten Teils des Fettsäureesters in deren Poren in derfarbabgebenden Beschichtung so wenig freier Fettsäureester vorhanden ist, dass die hohe Affinität des Bindemittels gegenüber der Trägerfolie zur Verankerung der farbabgebenden Schicht an der Trägerfolie ausreicht. Somit ist die bislang notwendige Einfügung einer haftvermittelnden Zwischenschicht nicht mehr unbedingt erforderlich.The fillers have the further advantage that, because most of the fatty acid ester is embedded in their pores in the color-releasing coating, there is so little free fatty acid ester that the high affinity of the binder for the carrier film is sufficient to anchor the color-releasing layer on the carrier film. This means that the previously required insertion of an adhesion-promoting intermediate layer is no longer absolutely necessary.

Zweckmässig ist im übrigen der Zusatz von kationischen Netzmitteln zur farbabgebenden Beschichtung, weil sie eine zu intensive Benetzung der Schwamm-Innenflächen mit den (normalerweise sauer eingestellten) Pigmentteilchen verhindern und damit deren Mobilität begünstigen. Bevorzugt sind als Netzmittel Fettamin-Salze, d.h. die Salze von langkettigen, aus natürlichen oder synthetischen Fettsäuren gewonnenen Alkylaminen oder -diaminen insbesondere mit langkettigen oder kurzkettigen Fettsäuren.In addition, it is advisable to add cationic wetting agents to the color-releasing coating, because they prevent the inside of the sponge from being over-wetted with the (normally acidic) pigment particles and thus promote their mobility. Preferred wetting agents are fatty amine salts, ie the salts of long-chain, natural or Synthetic fatty acids obtained alkylamines or diamines, in particular with long-chain or short-chain fatty acids.

Im Ergebnis schafft die Erfindung somit eine farbabgebende Beschichtung, bei der die Farbpaste zusätzlich zu ihrem Gehalt an Farbpigmenten noch in extrem hoher Konzentration mit einem Fettfarbstoff eingefärbt ist, also eine extrem hohe Farbkraft besitzt und sich deshalb ausreichend dünnschichtig halten lässt. Die Farbpaste wird bei jeder Überschreibung in der gewünschten konstanten Intensität abgegeben, und sie ist so farbstark, dass sich auffällige Schwankungen des Typenanschlags nicht in der Intensität des Abdrukkes bemerkbar machen.As a result, the invention thus creates a color-releasing coating in which the color paste, in addition to its content of color pigments, is also colored in an extremely high concentration with a fatty dye, that is to say it has an extremely high color strength and can therefore be kept sufficiently thin-layered. The color paste is dispensed with the desired constant intensity each time it is overwritten, and it is so strong in color that striking fluctuations in the type stop are not noticeable in the intensity of the print.

Es lassen sich ohne weiteres Overstrike-Zahlen von 12 und mehr erreichen, bevor ein relativ steiler Abfall der Farbintensität eintritt. Damit wird die Bandlebensdauer gegenüber den besten bisher bekannten Bändern mehr als verdoppelt.Overstrike numbers of 12 and more can easily be reached before a relatively steep drop in color intensity occurs. This more than doubles the tape life compared to the best tapes known to date.

Für die Mengenanteile, mit denen die Bestandteile der farbabgebenden Beschichtung bei dem erfindungsgemässen Farbband eingesetzt werden können, hat sich die folgende Rahmenrezeptur (in Gewichtsteilen) als zweckmässig erwiesen:

Figure imgb0001
The following general formula (in parts by weight) has proven to be useful for the proportions with which the components of the color-releasing coating can be used in the ink ribbon according to the invention:
Figure imgb0001

In dieser Rahmenrezeptur können die an erster Stelle genannten polyäthoxylierten Fettsäureester auch ganz oder teilweise durch herkömmliche Öle, wie Ricinusöl, Glycerintriolein oder ggf. auch Mineralöl, ersetzt sein.In this general formulation, the polyethoxylated fatty acid esters mentioned in the first place can also be replaced in whole or in part by conventional oils, such as castor oil, glycerol triolein or possibly also mineral oil.

Als Bindemittel im erfindungsgemässen System können die für Farbbänder üblichen Kunststoff-Bindemittel, wie Polyacrylate, Polyvinylchlorid/acetat-Copolymerisate, lineare Polyester, Polyvinylacetat und Polystyrol, Polyamid verwendet werden. Als Lösungsmittel dienen die bei der Farbband-Herstellung üblichen Lösungsmittel bzw. Lösungsmittel-Gemische, wie z.B. Methyläthylketon, Toluol und Isopropylalkohol. Das Lösungsmitte) wird dabei zum Teil in Form einer beispielsweise 25%-igen Lösung des Bindemittels in das System eingebracht. Nach dem Trocknen der Beschichtung ist das Lösungsmittel nicht mehr im Fertigprodukt enthalten. Im übrigen variieren die Mengenanteile der einzelnen Bestandteile in Abhängigkeit von den jeweils konkret eingesetzten Stoffen, ihre optimalen Werte lassen sich leicht durch einfache Handversuche ermitteln.The binders in the system according to the invention can be the plastic binders customary for color ribbons, such as polyacrylates, polyvinyl chloride / acetate copolymers, linear polyesters, polyvinyl acetate and polystyrene, polyamide. The solvents or solvent mixtures customary in ribbon production, such as e.g. Methyl ethyl ketone, toluene and isopropyl alcohol. The solvent) is partly introduced into the system in the form of, for example, a 25% solution of the binder. After the coating has dried, the solvent is no longer contained in the finished product. In addition, the proportions of the individual components vary depending on the specific substances used, their optimal values can be easily determined by simple manual tests.

Zur Herstellung des erfindungsgemässen Farbbandes wird die Beschichtungsmischung gemäss der beschriebenen Rahmenrezeptur auf eine Trägerfolie aus dafür üblichen Polymeren, wie Polyester, Polyäthylen, Polypropylen oder Polyamid, aufgetragen und getrocknet. Da die Gesamtdicke des fertigen Bandes (im Interesse einer möglichst grossen Bandlänge pro Kassette) den Wert von 26 11m nicht überschreiten sollte, ist die Trägerfolie so dünn wie möglich gehalten und hat z.B. eine Schichtdicke von 8 µm. Bei Bedarf ist die Verwendung einer antistatischen Zwischenschicht in einer Stärke von etwa 2 11m möglich.To produce the ink ribbon according to the invention, the coating mixture is applied and dried in accordance with the framework recipe described on a carrier film made of conventional polymers such as polyester, polyethylene, polypropylene or polyamide. Since the total thickness of the finished tape (in the interest of the longest possible tape length per cassette) should not exceed 26 11m, the carrier film is kept as thin as possible and has a layer thickness of 8 µm, for example. If necessary, the use of an antistatic intermediate layer with a thickness of approximately 2 11 m is possible.

Die nachfolgenden Beispiele erläutern die Erfindung (wobei die Abkürzung «PSSO» jeweils einen erfindungsgemäss einzusetzenden Fettsäureester mit durchschnittlich 40 Äthoxygruppen pro Molekül bedeutet):The following examples illustrate the invention (the abbreviation “PSSO” in each case meaning a fatty acid ester to be used according to the invention with an average of 40 ethoxy groups per molecule):

Beispiel 1example 1

Figure imgb0002
Figure imgb0002

Beispiel 2Example 2

Figure imgb0003
Figure imgb0003

Beispiel 3Example 3

Figure imgb0004
Figure imgb0004

Beispiel 4'Example 4 '

Figure imgb0005
Figure imgb0005

Nach diesen Beispielen wurde auf eine 8 /lm starke Polyesterfolie eine farbabgebende Beschichtung von etwa 16 /lm Stärke hergestellt. Die so erhaltenen Farbbänder gaben bei 12-fachem Overstrike auch in einem schnellaufenden Typenrad-Drucker sämtlich ein gleichmässiges und randscharfes Schriftbild, insbesondere auch bei extrem starkem Typenanschlag noch einwandfreie Unterstreichungsstriche.According to these examples, an ink-releasing coating of approximately 16 / lm thickness was produced on an 8 / lm thick polyester film. The ribbons obtained in this way gave a uniform, sharp-edged typeface, even in a high-speed typewriter printer, in a 12-fold overstrike, especially when the type stroke was extremely strong.

Claims (6)

1. An overlappingly overstrikable typewriter or printer ribbon comprising a carrier film and an ink-releasing coating applied thereon in the form of a plastics material matrix with a paste dispersed therein containing carbon black and/or coloured pigments and having a colouring agent as well as fine-particle fillers of large internal surface area in a base of a fatty acid ester of a polyhydric alcohol, characterized in that the fatty acid ester is a polyethoxylated fatty acid ester of a polyhydric alcohol and the fine-particle fillers have a particle size distribution of 0.2 to 20 micron.
2. A typewriter or printer ribbon according to claim 1, characterized in that the polyethoxylated fatty acid ester is an ester of fatty acids with 12 to 25 C atoms and alcohols with 3 to 6 OH groups and contain 20 to 60 ethoxy groups in the molecule.
3. A typewriter or printer ribbon according to claim 2, characterized in that the fatty acid ester is a polyoxyethylene (40)-sorbitol pentaoleate.
4. A typewriter or printer ribbon according to one of the claims 1 to 3, characterized in that the filler is in the form of kieselguhr, precipitated sali- ca, activated carbon and/or burst-open hollow spheres.
5. A typewriter or printer ribbon according to one of the claims 1 to 4, characterized in that the polyoxyethylated fatty acid ester is supplemented with up to 50% of a natural or synthetic oil.
6. A typewriter or printer ribbon according to one of the claims 1 to 5, characterized in that the ink-releasing coating additionally contains a cationic wetting agent.
EP83100124A 1982-04-07 1983-01-08 Overlapping overprint inking ribbon Expired EP0090907B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100124T ATE16368T1 (en) 1982-04-07 1983-01-08 OVERLAPPING OVERWRITE RIBBON.

Applications Claiming Priority (2)

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CH216582 1982-04-07
CH2165/82 1982-04-07

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EP0090907A1 EP0090907A1 (en) 1983-10-12
EP0090907B1 true EP0090907B1 (en) 1985-11-06

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JP (1) JPS5935969A (en)
AT (1) ATE16368T1 (en)
AU (1) AU549464B2 (en)
CA (1) CA1193782A (en)
DE (2) DE3361130D1 (en)
FR (1) FR2524845A1 (en)
GB (1) GB2118584B (en)
IT (1) IT1161810B (en)
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JPH0729483B2 (en) * 1985-06-27 1995-04-05 沖電気工業株式会社 Ink ribbon for impact printer
US4794039A (en) * 1985-12-17 1988-12-27 Fuji Kagakushi Kogyo Co., Ltd. Multi-usable pressure-sensitive transfer recording medium
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NL8300794A (en) 1983-11-01
DE3361130D1 (en) 1985-12-12
AU1181883A (en) 1983-10-13
CA1193782A (en) 1985-09-17
JPS5935969A (en) 1984-02-27
GB2118584B (en) 1985-08-29
FR2524845A1 (en) 1983-10-14
JPH0415108B2 (en) 1992-03-16
ATE16368T1 (en) 1985-11-15
DE3307432A1 (en) 1983-10-20
DE3307432C2 (en) 1986-01-02
IT1161810B (en) 1987-03-18
IT8320384A0 (en) 1983-03-30
AU549464B2 (en) 1986-01-30
US4544292A (en) 1985-10-01
EP0090907A1 (en) 1983-10-12
GB8304360D0 (en) 1983-03-23
GB2118584A (en) 1983-11-02

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