EP0050716B1 - Process for producing an antifriction layer on the surface of an aluminium layer on a carrier material which is provided on both sides with a lacker layer - Google Patents

Process for producing an antifriction layer on the surface of an aluminium layer on a carrier material which is provided on both sides with a lacker layer Download PDF

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Publication number
EP0050716B1
EP0050716B1 EP81106122A EP81106122A EP0050716B1 EP 0050716 B1 EP0050716 B1 EP 0050716B1 EP 81106122 A EP81106122 A EP 81106122A EP 81106122 A EP81106122 A EP 81106122A EP 0050716 B1 EP0050716 B1 EP 0050716B1
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Prior art keywords
layer
accordance
lacquer
metal
mixture
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EP81106122A
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German (de)
French (fr)
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EP0050716A1 (en
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Dietrich Jürgen Dr. Bahr
Marian Dipl. Ing. Briska
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IBM Deutschland GmbH
International Business Machines Corp
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IBM Deutschland GmbH
International Business Machines Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/24Ablative recording, e.g. by burning marks; Spark recording
    • B41M5/245Electroerosion or spark recording

Definitions

  • the invention relates to a method for producing a sliding layer on the surface of an aluminum layer on a support material provided on both sides with a lacquer layer.
  • EP-A-36 469 which according to Art. 54 (3) and (4) EPC is deemed to be state of the art for DE, FR, GB and IT, a method was proposed for producing a sliding layer A 2 to 1000 nm thick layer of a metal soap from the group of stearates, palmitates, oleates, linoleates, resinates, laurates, naphthenates, tallates or mixtures thereof is applied to the surface of a recording medium coated with a thin aluminum layer. Soaps of the metals tin, zinc, lithium or magnesium are said to be particularly advantageous.
  • the metal soaps according to EP-A-47 360 which also applies to the DE, FR, GB and IT according to Art. 54 (3) and (4) EPC, were dry, mechanical Application method applied and before mechanical application with 10 to 30 percent by weight, based on the sliding layer, of a polyfunctional aliphatic alcohol processed in a mortar or a mill to a homogeneous mass.
  • EP-A-35 105 which according to Art. 54 (3) and (4) EPC applies to DE, FR, GB and IT as the state of the art, a method for at least partially converting an aluminum layer to aluminum salts Fatty acid proposed on a record carrier in which the aluminum is reacted with the vapor of a fatty acid during and / or after the vacuum deposition of the aluminum layer, the degree of conversion being determined by the partial pressure of the fatty acid.
  • the use of oleic acid has been proposed, the reaction leading to the formation of aluminum oleate molecules which form on the surface of the layer and are also embedded within the layer itself.
  • lacquer layers are nitro lacquer layers, the influence of which will be discussed further below.
  • the resulting sliding layers are apparently due to the formation of an aluminum soap.
  • the effectiveness of such a layer has been clearly demonstrated.
  • this layer consists of an aluminum oleate could only be indirectly confirmed by the fact that the layer greatly reduces the abrasion marks that arise when printing with an electroerosion printer and that it is hydrophobic. If, on the other hand, you only apply a thin layer of oleic acid to an aluminum surface, this does not reduce the abrasion marks and the layer is not hydrophobic.
  • oleic acid can only react with aluminum if there are aluminum radicals which can combine with the carboxyl groups of the fatty acid to form an aluminum soap.
  • aluminum layer is evaporated on a base containing nitrocellulose.
  • the nitrocellulose contains a nitrate grouping which apparently can activate the vapor-deposited aluminum.
  • nitrocellulose has a high proportion of free -OH groups, which are activated by the electron-attracting action of the nitrate grouping and which could bring about the reaction with the oleic acid via an exchange reaction.
  • nitrocellulose-containing paints are not particularly suitable for such recording media because of their easy flammability.
  • other cellulose varnishes which, because of their varnishes containing nitrocellulose, are substantially higher in temperature stability this method would fail, such as acetyl cellulose or ethyl cellulose.
  • the content of -OH groups in these celluloses is very much lower (approximately 1%) than that of nitrocellulose. Long-term tests with these materials at room temperature and also implementation tests at temperatures up to 100 ° C have led to very little success.
  • a method for producing a sliding layer on the surface of an aluminum layer on a support material provided on both sides with a lacquer layer is proposed, at least one of the two lacquer layers being admixed with a fatty acid or a mixture of fatty acids and at least one of the two lacquer layers for reaction with fatty acids suitable radical generator is added.
  • the procedure is preferably such that a metal azide Me (N 3 ) n is used as a metal radial former.
  • a metal azide Me (N 3 ) n is used as a metal radial former.
  • azides of aluminum, barium, potassium, calcium, lithium and sodium are to be used.
  • a metal radical-forming metal azide is admixed to the top layer of the back coating and if a fatty acid or a mixture of fatty acids is admixed to the front coating.
  • the proportion of the metal azide should be about 0.1 to 2% by weight of the liquid lacquer, while the proportion of the fatty acid or the mixture of fatty acids can be about 0.1 to 2% by weight of the liquid lacquer.
  • Oleic acid has proven to be particularly suitable; very good results can also be achieved with a mixture of fatty acids, for example with tall oil or a mixture of oleic acid, stearic acid and palmitic acid in a ratio of about 3: 1: 1. _ _
  • the metal azide is used with an excess in relation to the oleic acid.
  • the nitrocellulose obviously favors the desired reaction, but on the other hand the acetylcellulose or the ethylcellulose are obviously not able to activate the aluminum layer for the reaction, the obviously required metal radicals must be formed from an additional compound, the anion of which is chemically unstable and disintegrates and leaves behind a metal radical.
  • a metal azide Me (N 3 ) n ' which is mixed with the fatty acid in the back coat.
  • the metal azide of the back coating i.e. are added to the top layer of the back coating while the fatty acid or mixture of fatty acids is added to the topcoat.
  • Another possibility is to accommodate the metal azide and the fatty acid or the mixture of fatty acids in the back coating.
  • it is also possible to accommodate the metal azide in the topcoat although difficulties still arise at present because the dreaded bakken could still occur with such an admixture.
  • metal azide when used, metal radicals are formed which react accordingly with the fatty acid. This reaction intensifies at elevated temperatures. If both substances, ie the metal azide and the fatty acid are contained in the back coating, then a metal soap forms in the back coating, which diffuses through to the aluminum layer at an elevated temperature of approx. 70 ° C. An effective, highly hydrophobic soap layer can be detected there after only 12 hours. Finely ground NaN 3 was used for the individual experiments. This reaction continues until the supply of metal radicals is used up. By adding other azides, such as LiN 3 or Al (N 3 ) 3 . you get other soaps accordingly.
  • one component for example the metal azide
  • the other component e.g. the fatty acid
  • the two components also diffuse towards one another and react primarily with one another on the aluminum layer.
  • the sodium azide with grain sizes between 0.1 and 3 Ilm is analogous to one inorganic pigment finely dispersed in the paint.
  • the stearic acid acts in such a way that it prevents the granular or crystalline sodium azide from forming lumps.
  • a further essential aspect of the method according to the invention is seen in the fact that this is a reaction between solid substances and not, for example, a reaction between liquid and / or gaseous substances.
  • this process is particularly suitable for paints made on the basis of acetyl cellulose.
  • this in no way excludes their effectiveness in the case of nitrocellulose lacquers; on the contrary, the effect which already occurs there can be further improved by the process according to the invention.
  • nothing is consumed by the already very thin aluminum layer, but the metal required to form a metal soap is obtained from an additional source.
  • lithium azide LiN 3
  • aluminum azide Al (N 3 ) 3 appears to be particularly interesting in this context.
  • These azides can be dissolved in an organic solvent and can be mixed with the paint, which results in a very high degree of dispersion up to the real solution. Accordingly, the metal azide will be in solid solution in the paint.
  • the decomposition temperature of both substances is relatively low, so that the reaction will take place at room temperature at a relatively high rate.

Description

Die Erfindung betrifft ein Verfahren zum Erzeugen einer Gleitschicht auf der Oberfläche einer Aluminiumschicht auf einem beidseitig mit einer Lackschicht versehenen Trägermaterial.The invention relates to a method for producing a sliding layer on the surface of an aluminum layer on a support material provided on both sides with a lacquer layer.

Gemäss dem in der DE-C 849 609 offenbarten Stand der Technik hatte man bereits erkannt,dass man zur Erhöhung der Schichtbeständigkeit der Metallschicht, die schon unter atmosphärischen Verhältnissen nach kurzer Zeit eine Veränderung erfährt oder sogar bei längerer Lagerhaltung gänzlich verschwindet, so dass die aufgezeichneten Spuren bald nicht mehr sichtbar sind, dünne Schutzschichten aufbringen sollte. Als solche kommen Schichten aus chemisch beständigen Verbindungen des Belagsmetalls, z.B. Oxide oder Carbonate oder aus Quarz, Paraffin oder Lack mit einer Stärke von höchstens 2 µm in Frage. Als flüchtige Schutzstoffe können auch Öle in molekularer Stärke aufgedampft werden.According to the prior art disclosed in DE-C 849 609, it had already been recognized that in order to increase the layer stability of the metal layer, which undergoes a change after a short time even under atmospheric conditions, or even completely disappears with longer storage, so that the recorded ones Soon traces are no longer visible, thin protective layers should be applied. As such come layers of chemically resistant compounds of the covering metal, e.g. Oxides or carbonates or of quartz, paraffin or lacquer with a thickness of at most 2 µm in question. Oils of molecular strength can also be evaporated as volatile protective substances.

Zum Erzeugen einer Gleitschicht wurde in der EP-A- 36 469, welche gemäss Art. 54(3) und (4) EPÜ für DE, FR, GB, und IT als Stand der Technik gilt, ein Verfahren vorgeschlagen, gemäss dem auf die Oberfläche eines mit einer dünnen Aluminiumschicht überzogenen Aufzeichnungsträgers eine 2 bis 1000 nm dicke Schicht einer Metallseife aus der Gruppe der Stearate, Palmitate, Oleate, Linoleate, Resinate, Laurate, Naphthenate, Tallate oder Mischungen derselben aufgetragen wird. Als besonders vorteilhaft werden Seifen der Metalle Zinn, Zink, Lithium oder Magnesium bezeichnet.In EP-A-36 469, which according to Art. 54 (3) and (4) EPC is deemed to be state of the art for DE, FR, GB and IT, a method was proposed for producing a sliding layer A 2 to 1000 nm thick layer of a metal soap from the group of stearates, palmitates, oleates, linoleates, resinates, laurates, naphthenates, tallates or mixtures thereof is applied to the surface of a recording medium coated with a thin aluminum layer. Soaps of the metals tin, zinc, lithium or magnesium are said to be particularly advantageous.

In einer Weiterbildung dieses Verfahrens wurden die Metallseifen gemäss der EP-A-47 360, welche ebenfalls gemäss Art. 54(3) und (4) EPÜ für DE, FR, GB und IT als Stand der Technik gilt, in einem trockenen, mechanischen Auftragverfahren aufgebracht und vor dem mechanischen Auftragen mit 10 bis 30 Gewichtsprozent, bezogen auf die Gleitschicht, eines mehrfunktionellen aliphatischen Alkohols in einem Mörser oder einer Mühle zu einer homogenen Masse verarbeitet.In a further development of this method, the metal soaps according to EP-A-47 360, which also applies to the DE, FR, GB and IT according to Art. 54 (3) and (4) EPC, were dry, mechanical Application method applied and before mechanical application with 10 to 30 percent by weight, based on the sliding layer, of a polyfunctional aliphatic alcohol processed in a mortar or a mill to a homogeneous mass.

Des weiteren wurde in der EP-A-35 105, welche gemäss Art. 54(3) und (4) EPÜ für DE, FR, GB und IT als Stand der Technik gilt, ein Verfahren zum mindestens partiellen Umsetzen einer Aluminiumschicht zu Aluminiumsalzen einer Fettsäure auf einem Aufzeichnungsträger vorgeschlagen, bei dem während und/oder nach dem Vakuumniederschlagen der Aluminiumschicht das Aluminium mit dem Dampf einer Fettsäure umgesetzt wird, wobei der Grad der Umsetzung durch den Partialdruck der Fettsäure bestimmt wird. Insbesondere wurde die Verwendung von Ölsäure vorgeschlagen, wobei die Umsetzung zur Bildung von Aluminiumoleatmolekülen führt, die sich auf der Oberfläche der Schicht bilden und auch innerhalb der Schicht selbst eingelagert werden.Furthermore, in EP-A-35 105, which according to Art. 54 (3) and (4) EPC applies to DE, FR, GB and IT as the state of the art, a method for at least partially converting an aluminum layer to aluminum salts Fatty acid proposed on a record carrier in which the aluminum is reacted with the vapor of a fatty acid during and / or after the vacuum deposition of the aluminum layer, the degree of conversion being determined by the partial pressure of the fatty acid. In particular, the use of oleic acid has been proposed, the reaction leading to the formation of aluminum oleate molecules which form on the surface of the layer and are also embedded within the layer itself.

Des weiteren würde gemäss der EP-A-50 704, die prioritätsgleich mit der vorliegenden Patentanmeldung ist und für die benannten Vertragsstaaten DE, FR, GB und IT gilt, ein Verfahren zum Erzeugen einer Gleitschicht auf der Oberfläche der Aluminiumschicht eines Aufzeichnungsträgermaterials durch Einwirkung einer oder mehrerer Fettsäuren vorgeschlagen, bei dem das Aufzeichnungsträgermaterial auf der Vorderseite mit einer und auf der Rückseite mit einer oder mehreren Nitrolackschichten beschichtet wird und der jeweils letzten Lackschicht auf der Rückseite 0,1 bis 2 Gew.-%, bezogen auf den nassen Lack, einer oder mehrerer Fettsäuren beigemischt werden, die Vorderseite des Aufzeichnungsträgermaterials im Vakuum mit Aluminium beschichtet wird und das beschichtete Aufzeichnungsträgermaterial noch in der Vakuumkammer zur Rolle aufgewikkelt und in dieser Form einer längeren Alterungsperiode ausgesetzt wird.Furthermore would g emäss EP-A-50 704, which is equal priority with the present patent application and is applicable to the designated contracting states DE, FR, GB and IT, a method for generating a sliding layer on the surface of the aluminum layer of a record carrier material by the action of a or several fatty acids, in which the recording medium is coated on the front with one and on the back with one or more nitro lacquer layers and the last lacquer layer on the back 0.1 to 2 wt .-%, based on the wet lacquer, one or more fatty acids are admixed, the front side of the recording medium is coated with aluminum in a vacuum and the coated recording medium is wound up into a roll in the vacuum chamber and is exposed in this form to a longer aging period.

Bei diesem Verfahren ist ganz wesentlich, dass es sich bei den Lackschichten um Nitrolackschichten handelt, deren Einfluss weiter unten noch erörtert wird. Die entstehenden Gleitschichten sind offenbar auf die Bildung einer Aluminiumseife zurückzuführen. Die Wirksamkeit einer solchen Schicht wurde eindeutig nachgewiesen. Dass jedoch diese Schicht aus einem Aluminiumoleat besteht, konnte nur indirekt dadurch bestätigt werden, dass die Schicht Schleifspuren, die beim Drucken mit einem Elektroerosionsdrukker entstehen, stark reduziert und dass sie hydrophob ist. Bringt man dagegen lediglich eine dünne Ölsäureschicht auf eine Aluminiumoberfläche auf, so werden dadurch die Schleifspuren nicht verringert, und die Schicht ist nicht hydrophob.It is very important in this process that the lacquer layers are nitro lacquer layers, the influence of which will be discussed further below. The resulting sliding layers are apparently due to the formation of an aluminum soap. The effectiveness of such a layer has been clearly demonstrated. However, the fact that this layer consists of an aluminum oleate could only be indirectly confirmed by the fact that the layer greatly reduces the abrasion marks that arise when printing with an electroerosion printer and that it is hydrophobic. If, on the other hand, you only apply a thin layer of oleic acid to an aluminum surface, this does not reduce the abrasion marks and the layer is not hydrophobic.

Der Mechanismus dieser Wirkung ist nicht vollständig klar. Es ist jedoch darauf hinzuweisen, dass Ölsäure mit Aluminium nur dann reagieren kann, wenn Aluminiumradikale vorhanden sind, die sich mit den Carboxylgruppen der Fettsäure zu einer Aluminiumseife verbinden können. Hierzu ist es jedoch notwendig, dass die Aluminiumschicht auf einer Nitrocellulose haltigen Unterlage aufgedampft wird. Die Nitrocellulose enthält eine Nitratgruppierung,

Figure imgb0001
die offenbar eine Aktivierung des aufgedampften Aluminiums bewirken kann. Ferner hat bekanntlich die Nitrocellulose einen hohen Anteil an freien -OH-Gruppen, welche durch die elektronenanziehende Wirkung der Nitratgruppierung aktiviert sind und die Umsetzung mit der Ölsäure über eine Austauschreaktion bewirken könnten.The mechanism of this effect is not entirely clear. However, it should be pointed out that oleic acid can only react with aluminum if there are aluminum radicals which can combine with the carboxyl groups of the fatty acid to form an aluminum soap. For this, however, it is necessary that the aluminum layer is evaporated on a base containing nitrocellulose. The nitrocellulose contains a nitrate grouping
Figure imgb0001
which apparently can activate the vapor-deposited aluminum. Furthermore, it is known that nitrocellulose has a high proportion of free -OH groups, which are activated by the electron-attracting action of the nitrate grouping and which could bring about the reaction with the oleic acid via an exchange reaction.

Es ist jedoch wichtig, darauf hinzuweisen, dass Nitrocellulosehaltige Lacke wegen ihrer leichten Brennbarkeit für derartige Aufzeichnungsträger nicht sonderlich gut geeignet sind. Bei Verwendung anderer Celluloselacke, die wegen ihrer gegenüber den Nitrocellulose haltigen Lacken wesentlich höheren Temperaturstabilität wesentlich geeigneter wären, wie z.B. Acetylcellulose oder Athylcellulose, versagt dieses Verfahren. Dies ist wohl darauf zurückzuführen, dass die Estergruppen des Acetobutyrats eine wesentlich geringere Polarität aufweisen, als die oben erwähnte Nitrat-Gruppe

Figure imgb0002
wobei RButyrat = CH3CH2CH2, d.h. der Propylrest der Buttersäure ist. Ferner muss darauf hingewiesen werden, dass der Gehalt dieser Cellulosen an -OH-Gruppen sehr viel geringer ist (ungefähr 1%) als der der Nitrocellulose. Langzeitversuche mit diesen Materialien bei Raumtemperatur und auch Umsetzungsversuche bei Temperaturen bis zu 100 °C haben nur zu sehr geringen Erfolgen geführt.However, it is important to point out that nitrocellulose-containing paints are not particularly suitable for such recording media because of their easy flammability. When using other cellulose varnishes, which, because of their varnishes containing nitrocellulose, are substantially higher in temperature stability this method would fail, such as acetyl cellulose or ethyl cellulose. This is probably due to the fact that the ester groups of acetobutyrate have a much lower polarity than the nitrate group mentioned above
Figure imgb0002
where R is butyrate = CH 3 CH 2 CH 2 , ie the propyl radical of butyric acid. It must also be pointed out that the content of -OH groups in these celluloses is very much lower (approximately 1%) than that of nitrocellulose. Long-term tests with these materials at room temperature and also implementation tests at temperatures up to 100 ° C have led to very little success.

Da jedoch die Acetylcelluloselacke eine wesentlich grössere Bedeutung für mit Aluminium beschichtete Aufzeichnungsträger als Nitrocellulose haltige Lacke haben, galt es, eine Lösung zu finden, die nach derzeitiger Erkenntnis praktisch für alle Lacke brauchbar ist.However, since acetyl cellulose lacquers are of much greater importance for aluminum-coated recording media than lacquers containing nitrocellulose, it was necessary to find a solution which, according to current knowledge, can be used practically for all lacquers.

Erfindungsgemäss wird daher ein Verfahren zum Erzeugen einer Gleitschicht auf der Oberfläche einer Aluminiumschicht auf einem beidseitig mit einer Lackschicht versehenen Trägermaterial vorgeschlagen, wobei mindestens einer der beiden Lackschichten eine Fettsäure oder ein Gemisch von Fettsäuren beigemischt wird und mindestens einer der beiden Lackschichten ein zur Umsetzung mit Fettsäuren geeigneter Radikalbildner beigemischt wird.According to the invention, therefore, a method for producing a sliding layer on the surface of an aluminum layer on a support material provided on both sides with a lacquer layer is proposed, at least one of the two lacquer layers being admixed with a fatty acid or a mixture of fatty acids and at least one of the two lacquer layers for reaction with fatty acids suitable radical generator is added.

Vorzugsweise geht man dabei so vor, dass als ein Metallradialbildner ein Metallazid Me(N3)n verwendet wird. Insbesondere sollen dabei Azide von Aluminium, Barium, Kalium, Calcium, Lithium und Natrium verwendet werden. Von ganz besonderem Vorteil ist es, wenn der obersten Schicht der Rückseitenlackierung ein metallradikalbildendes Metallazid beigemischt wird, und wenn der Vorderseitenlackierung eine Fettsäure oder ein Gemisch von Fettsäuren beigemischt wird. Der Anteil des Metallazids soll dabei etwa 0,1 bis 2 Gew.-% des flüssigen Lacks betragen, während der Anteil der Fettsäure oder des Gemisches von Fettsäuren etwa 0,1 bis 2 Gew.-% des flüssigen Lackes betragen kann. Als besonders geeignet hat sich die Ölsäure erwiesen, ebenfalls sehr gute Ergebnisse lassen sich mit einem Gemisch von Fettsäuren, beispielsweise mit Tallöl oder einem Gemisch aus Ölsäure, Stearinsäure und Palmitinsäure im Verhältnis von etwa 3:1:1 erzielen. _ _The procedure is preferably such that a metal azide Me (N 3 ) n is used as a metal radial former. In particular, azides of aluminum, barium, potassium, calcium, lithium and sodium are to be used. It is particularly advantageous if a metal radical-forming metal azide is admixed to the top layer of the back coating and if a fatty acid or a mixture of fatty acids is admixed to the front coating. The proportion of the metal azide should be about 0.1 to 2% by weight of the liquid lacquer, while the proportion of the fatty acid or the mixture of fatty acids can be about 0.1 to 2% by weight of the liquid lacquer. Oleic acid has proven to be particularly suitable; very good results can also be achieved with a mixture of fatty acids, for example with tall oil or a mixture of oleic acid, stearic acid and palmitic acid in a ratio of about 3: 1: 1. _ _

Von ganz besonderem Vorteil ist es aber, wenn das Metallazid im Verhältnis zur Ölsäure mit einem Übergewicht verwendet wird.However, it is particularly advantageous if the metal azide is used with an excess in relation to the oleic acid.

Der Hintergrund der Erfindung soll nun noch etwas näher betrachtet werden. Da die Nitrocellulose einerseits offensichtlich die erwünschte Reaktion begünstigt, andererseits aber die Acetylcellulose bzw. die Äthylcellulose offensichtlich nicht in der Lage sind, die Aluminiumschicht zur Reaktion zu aktivieren, müssen die offensichtlich erforderlichen Metallradikale aus einer zusätzlichen Verbindung gebildet werden, deren Anion chemisch instabil ist und zerfällt und ein Metallradikal zurücklässt. Das kann beispielsweise mit einem Metallazid Me(N3)n' erfolgen das neben der Fettsäure dem Rückseitenlack beigemischt wird. Beim Zerfall des Metallazids, z.B.

Figure imgb0003
bilden sich Metallradikale, die mit der Fettsäure entsprechend reagieren.The background of the invention will now be considered in more detail. Since on the one hand the nitrocellulose obviously favors the desired reaction, but on the other hand the acetylcellulose or the ethylcellulose are obviously not able to activate the aluminum layer for the reaction, the obviously required metal radicals must be formed from an additional compound, the anion of which is chemically unstable and disintegrates and leaves behind a metal radical. This can be done, for example, with a metal azide Me (N 3 ) n 'which is mixed with the fatty acid in the back coat. When the metal azide decays, e.g.
Figure imgb0003
metal radicals are formed which react accordingly with the fatty acid.

Prinzipiell gibt es dabei mehrere Möglichkeiten. Einmal kann das Metallazid der Rückseitenlackierung, d.h. der obersten Schicht der Rückseitenlackierung beigemischt werden, während die Fettsäure oder das Gemisch von Fettsäuren dem Decklack beigemischt wird. Eine weitere Möglichkeit besteht darin, das Metallazid und die Fettsäure bzw. das Gemisch von Fettsäuren im Rückseitenlack unterzubringen. Im Prinzip ist es ausserdem möglich, das Metallazid auch im Decklack unterzubringen, wobei sich derzeit aber noch Schwierigkeiten ergeben, weil bei einer derartigen Beimischung teilweise noch das gefürchtete Bakken auftreten könnte.In principle, there are several options. On the one hand, the metal azide of the back coating, i.e. are added to the top layer of the back coating while the fatty acid or mixture of fatty acids is added to the topcoat. Another possibility is to accommodate the metal azide and the fatty acid or the mixture of fatty acids in the back coating. In principle, it is also possible to accommodate the metal azide in the topcoat, although difficulties still arise at present because the dreaded bakken could still occur with such an admixture.

Wie oben ausgeführt, bilden sich bei Verwendung des Metallazids Metallradikale, die mit der Fettsäure entsprechend reagieren. Bei erhöhten Temperaturen verstärkt sich diese Reaktion. Wenn beide Stoffe, d.h. das Metallazid und die Fettsäure in der Rückseitenlackierung enthalten sind, dann bildet sich in der Rückseitenlackschicht eine Metallseife, die bei erhöhter Temperatur von ca. 70 °C auf die Aluminiumschicht durchdiffundiert. Schon nach 12 Stunden lässt sich dort eine wirksame, stark hydrophobe Seifenschicht nachweisen. Für die einzelnen Versuche wurde mit feingemahlenem NaN3 gearbeitet. Diese Reaktion verläuft so lange, bis der Vorrat an Metallradikalen aufgebraucht ist. Durch Zusatz von anderen Aziden, wie z.B. von LiN3 oder AI(N3)3. erhält man entsprechend andere Seifen.As stated above, when the metal azide is used, metal radicals are formed which react accordingly with the fatty acid. This reaction intensifies at elevated temperatures. If both substances, ie the metal azide and the fatty acid are contained in the back coating, then a metal soap forms in the back coating, which diffuses through to the aluminum layer at an elevated temperature of approx. 70 ° C. An effective, highly hydrophobic soap layer can be detected there after only 12 hours. Finely ground NaN 3 was used for the individual experiments. This reaction continues until the supply of metal radicals is used up. By adding other azides, such as LiN 3 or Al (N 3 ) 3 . you get other soaps accordingly.

Wesentlich effizienter ist es jedoch, wenn die eine Komponente, beispielsweise das Metallazid, in der Rückseitenlackierung enthalten ist, während die andere Komponente, z.B. die Fettsäure in der unter der Aluminiumschicht liegenden Lackschicht enthalten ist. In diesem Fall besteht ein Konzentrationsgefälle, und die beiden Komponenten diffundieren auch aufeinander zu und reagieren miteinander vornehmlich auf der Aluminiumschicht.However, it is much more efficient if one component, for example the metal azide, is contained in the rear coating, while the other component, e.g. the fatty acid is contained in the paint layer under the aluminum layer. In this case there is a concentration gradient, and the two components also diffuse towards one another and react primarily with one another on the aluminum layer.

Ausgedehnte Versuche haben ergeben, dass besonders günstige Ergebnisse mit Natriumazid erzielt werden können. In diesem Fall wird Natriumazid NaN3 mit etwa 1 Gew.-% Ölsäure (CH3(CH2)-CH=CH(CH2)7 -COOH) den jeweiligen Lacken beigemischt. Mit besonderem Vorteil verwendet man auch 0,1 Gew.-% Stearinsäure, die zusammen mit dem Natriumazid zugegeben wird. Das Natriumazid mit Korngrössen zwischen 0,1 und 3 Ilm wird in Analogie zu einem anorganischen Pigment in dem Lack fein dispergiert. Die Stearinsäure wirkt in der Weise, dass sie eine Klumpenbildung des körnigen oder kristallinen Natriumazids verhindert.Extensive tests have shown that particularly favorable results can be achieved with sodium azide. In this case, sodium azide NaN 3 is mixed with about 1% by weight of oleic acid (CH 3 (CH 2 ) -CH = CH (CH 2 ) 7 -COOH) in the respective paints. It is also particularly advantageous to use 0.1% by weight of stearic acid, which is added together with the sodium azide. The sodium azide with grain sizes between 0.1 and 3 Ilm is analogous to one inorganic pigment finely dispersed in the paint. The stearic acid acts in such a way that it prevents the granular or crystalline sodium azide from forming lumps.

Ein weiterer wesentlicher Gesichtspunkt des erfindungsgemässen Verfahrens wird darin gesehen, dass es sich hierbei um eine Reaktion zwischen festen Stoffen handelt und nicht etwa um eine Reaktion zwischen flüssigen und/oder gasförmigen Stoffen.A further essential aspect of the method according to the invention is seen in the fact that this is a reaction between solid substances and not, for example, a reaction between liquid and / or gaseous substances.

Unter diesen Voraussetzungen durchgeführte Versuche ergaben, dass sich mit den oben angegebenen Prozentsätzen allerbeste Ergebnisse dann erzielen liessen, wenn nach Fertigstellung des beschichteten Aufzeichnungsträgers dieser für etwa 12 Stunden bei etwa 70 °C einer Wärmenachbehandlung unterzogen wurde.Tests carried out under these conditions showed that the best results could be achieved with the percentages given above if, after the coated recording medium had been finished, it was subjected to a post-heat treatment at about 70 ° C. for about 12 hours.

Wie eingangs bereits angedeutet, eignet sich dieses Verfahren vor allen Dingen für die auf Basis von Acetylcellulose hergestellten Lacke. Dies schliesst jedoch ihre Wirksamkeit bei Nitrocelluloselacken keinesfalls aus, im Gegenteil, die dort an sich schon auftretende Wirkung lässt sich durch das erfindungsgemässe Verfahren noch weiter verbessern. Darüber hinaus wird von der an sich schon sehr dünnen Aluminiumschicht nichts verbraucht, sondern man erhält das zur Bildung einer Metallseife benötigte Metall aus einer zusätzlichen Quelle.As already indicated at the beginning, this process is particularly suitable for paints made on the basis of acetyl cellulose. However, this in no way excludes their effectiveness in the case of nitrocellulose lacquers; on the contrary, the effect which already occurs there can be further improved by the process according to the invention. In addition, nothing is consumed by the already very thin aluminum layer, but the metal required to form a metal soap is obtained from an additional source.

Besonders interessant erscheint in diesem Zusammenhang die Verwendung von Lithiumazid, LiN3, und von Aluminiumazid AI(N3)3. Diese Azide können in einem organischen Lösungsmittel gelöst werden, und können damit dem Lack beigemischt werden, wodurch sich ein sehr hoher Dispergierungsgrad bis hin zur echten Lösung ergibt. Dementsprechend wird das Metallazid in dem Lack in fester Lösung vorliegen. Bei beiden Stoffen liegt die Zersetzungstemperatur relativ niedrig, so dass die Umsetzung bereits bei Zimmertemperatur mit relativ hoher Geschwindigkeit ablaufen wird.The use of lithium azide, LiN 3 , and aluminum azide Al (N 3 ) 3 appears to be particularly interesting in this context. These azides can be dissolved in an organic solvent and can be mixed with the paint, which results in a very high degree of dispersion up to the real solution. Accordingly, the metal azide will be in solid solution in the paint. The decomposition temperature of both substances is relatively low, so that the reaction will take place at room temperature at a relatively high rate.

Zusammenfassend kann also gesagt werden, dass mit dem neuen Verfahren gemäss der Erfindung Gleitschichten auf der Oberfläche von. mit Aluminium beschichteten Aufzeichnungsträgern für praktisch alle bisher bei derartigen beschichteten Papieren verwendete Lacke erzeugt werden können, die nach derzeitigen Erkenntnissen ein Optimum für mit Elektroerosionsdruckern zu bedruckende Aufzeichnungsträgermaterialien darstellen.In summary it can be said that with the new method according to the invention, sliding layers on the surface of. aluminum-coated recording media can be produced for practically all lacquers previously used in such coated papers, which according to current knowledge represent an optimum for recording medium materials to be printed with electroerosion printers.

Claims (12)

1. Process for generating a sliding layer on the surface of an aluminium layer on a carrier material coated on both sides with a lacquer layer, at least one of the two lacquer layers having a fatty acid or a mixture of fatty acids admixed thereto, and where to at least one of the two lacquer layers a material is admixed which forms a radical and is suitable for reaction with fatty acids.
2. Process in accordance with claim 1, characterized in that a metal azide Me(N3)n is used as a material suitable for forming a metal radical.
3. Process in accordance with claim 2, characterized in that an azide of the group of aluminum, barium, potassium, calcium, lithium, and sodium is used.
4. Process in accordance with any one of claims 1 to 3, characterized in that a metal azide forming a metal radical is admixed to the top-most layer of the lacquer on the back of the record c ier, and that a fatty acid or a mixture of fatty acids is admixed to the lacquer on the front.
5. Process in accordance with claim 2, characterized in that the percentage of the metal azide is 0,1 to 2 percent by weight relative to the liquid lacquer.
6. Process in accordance with any one of claims 1 and 2, characterized in that the percentage of the fatty acid or the mixture of fatty acids is 0,1 to 2 percent by weight relative to the liquid lacquer.
7. Process in accordance with claim 6, characterized in that oleic acid is used as a fatty acid.
8. Process in accordance with claim 6, characterized in that tall oil is used as a fatty acid mixture.
9. Process in accordance with claim 6, characterized in that a mixture of oleic acid, stearic acid and palmitic acid at a ratio of 3:1:1 is used as fatty acid mixture.
10. Process in accordance with any one of claims 1, 2 and 6, characterized in that the metal azide is used with an excess relative to the oleic acid.
11. Process in accordance with claim 10, characterized in that sodium azide is used.
12. Process in accordance with claim 11, characterized in that the finished record carrier material is subjected for 12 hours to a heat treatment at 70 °C.
EP81106122A 1980-10-28 1981-08-05 Process for producing an antifriction layer on the surface of an aluminium layer on a carrier material which is provided on both sides with a lacker layer Expired EP0050716B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3040513 1980-10-28
DE19803040513 DE3040513A1 (en) 1980-10-28 1980-10-28 METHOD FOR PRODUCING A SLIDING LAYER ON THE SURFACE ENES WITH ALUMINUM-COATED RECORDING CARRIER

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EP0050716A1 EP0050716A1 (en) 1982-05-05
EP0050716B1 true EP0050716B1 (en) 1985-02-06

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US (1) US4387119A (en)
EP (1) EP0050716B1 (en)
JP (1) JPS5783498A (en)
AU (1) AU543869B2 (en)
CA (1) CA1180236A (en)
DE (2) DE3040513A1 (en)
DK (1) DK150710C (en)
ES (1) ES8207046A1 (en)
ZA (1) ZA816774B (en)

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Publication number Priority date Publication date Assignee Title
DE3372272D1 (en) * 1983-01-21 1987-08-06 Ibm Deutschland Process for the production of a metal soap layer as an antifriction layer on a metallized registration support
DE3329981A1 (en) * 1983-08-19 1985-03-07 Robert Bosch Gmbh, 7000 Stuttgart RECORD CARRIER FOR REGISTRATION DEVICES
DE202005007923U1 (en) * 2005-05-20 2005-08-11 Trw Automotive Gmbh Steering gear e.g. for toothed rack steering in vehicles, has housing with rack along axle can be adjusted and auxiliary support is at axial end of housing with auxiliary support limits bend of rack

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Publication number Priority date Publication date Assignee Title
DE849609C (en) * 1950-11-06 1952-09-15 Bosch Gmbh Robert Tape-shaped recording medium for recording measuring instruments
DE2925766A1 (en) * 1978-06-26 1980-01-03 Fuji Photo Film Co Ltd THERMAL RECORDING MATERIAL

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ES506377A0 (en) 1982-09-01
AU543869B2 (en) 1985-05-09
ZA816774B (en) 1982-09-29
EP0050716A1 (en) 1982-05-05
DK474381A (en) 1982-04-29
ES8207046A1 (en) 1982-09-01
CA1180236A (en) 1985-01-02
DE3040513A1 (en) 1982-06-03
JPS5783498A (en) 1982-05-25
AU7556681A (en) 1982-09-09
DK150710B (en) 1987-06-01
DK150710C (en) 1988-02-08
US4387119A (en) 1983-06-07
DE3168776D1 (en) 1985-03-21

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