EP0358839B1 - Electrosensitive recording paper - Google Patents

Electrosensitive recording paper Download PDF

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Publication number
EP0358839B1
EP0358839B1 EP89102994A EP89102994A EP0358839B1 EP 0358839 B1 EP0358839 B1 EP 0358839B1 EP 89102994 A EP89102994 A EP 89102994A EP 89102994 A EP89102994 A EP 89102994A EP 0358839 B1 EP0358839 B1 EP 0358839B1
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EP
European Patent Office
Prior art keywords
layer
zinc
recording paper
recording
paper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP89102994A
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German (de)
French (fr)
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EP0358839A1 (en
Inventor
Wolfgang Wagner
Georg Schneiderat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Papierfabrik Schoeller & Hoesch GmbH
Original Assignee
Papierfabrik Schoeller & Hoesch GmbH
Papierfabrik Schoeller & Hoesch GmbH
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Application filed by Papierfabrik Schoeller & Hoesch GmbH, Papierfabrik Schoeller & Hoesch GmbH filed Critical Papierfabrik Schoeller & Hoesch GmbH
Priority to AT89102994T priority Critical patent/ATE89515T1/en
Publication of EP0358839A1 publication Critical patent/EP0358839A1/en
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Classifications

    • 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
    • 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
    • B41M5/20Duplicating or marking methods; Sheet materials for use therein using electric current

Definitions

  • the invention relates to an electrosensitive registration paper of the type specified in the preamble of claim 1.
  • electrosensitive registration paper is guided with its metallized side over a cylindrical electrode.
  • the counter electrode forms a thin tungsten wire, the tip of which slides on the metallized paper surface.
  • the contact pressure of the counter electrode is between 2,943.10 ⁇ 4 N and 0.0981 N (0.03 and 10 pond) depending on the type of metal layer used. If a direct electrical voltage is applied to the two electrodes, a current flows through the metal layer, which evaporates the metal material in the immediate vicinity of the tungsten tip of the counterelectrode due to the high current density, whereupon the current is interrupted.
  • the base coat of the registration paper appears with good contrast under the metal covering that has evaporated or burned away in this way. If the registration paper is pulled further, the tungsten electrode is energized again and a small amount of metal is burned away again.
  • This registration process requires a very thin layer of metal.
  • zinc is used as the actual registration layer, which, however, naturally adheres poorly to the base lacquer of the paper. Therefore, a pre-seeding layer is first applied to the lacquer layer, which serves as an adhesive base for the zinc layer.
  • the thickness of this metal layer essentially formed by the zinc atoms is of the order of 0.1 ⁇ m.
  • the back of this registration paper is usually covered with a clear protective lacquer.
  • Aluminum has the advantage of adhering directly to the base coat of the registration paper without an additional adhesive layer. In addition to the better contrast compared to the usually black lacquer layer, aluminum has the advantage of a higher corrosion resistance than the known zinc / cadmium layer.
  • the registration paper with a zinc / cadmium layer has a decisive disadvantage in terms of processing and handling.
  • cadmium is a metal of the second subgroup of the periodic table with an atomic weight of 112.41, i.e. a so-called heavy metal, the boiling point of which is 760 ° C. It mainly occurs in the form of its divalent compound as salts, which are extremely toxic when taken orally, leading to vomiting, liver damage and convulsions. When inhaled, the vapors of these salts cause irritation to the mucous membranes and headaches. In addition, these salts are carcinogenic.
  • the object of the invention is to provide an electrosensitive registration paper of the type mentioned in the introduction, which can be written with a lower contact pressure than aluminum-coated registration paper, and which can be produced and handled without the health disadvantages of registration paper which is coated with zinc / cadmium .
  • the invention consists in using silver as the pre-seeding layer for the zinc registration layer, the handling and processing of which is known to be associated with no toxic side effects.
  • the user of the zinc / silver registration paper according to the invention will not see any technical difference from the conventional zinc / cadmium paper, since the sensitivity of the silver substrate, especially the contact force required for perfect registration, is the same as that of the cadmium variant.
  • the registration paper according to the invention is advantageously based on a diagram paper with a thickness of 20 to 80 ⁇ m. A paper thickness of 40 ⁇ m is preferred.
  • a lacquer layer is applied to this paper support, which is advantageously pigmented purely organically. Alternatively, it is provided that the lacquer layer provided with a soot content is additionally pigmented with chromium dioxide (Cr203). This improves the embedding and thus the adhesion of the subsequent zinc vapor deposition.
  • the silver is advantageously vapor-deposited and incompletely evaporated onto this lacquer layer in order to create a pre-germination layer for the external zinc vapor deposition layer.
  • the latter is finally evaporated in such a way that a surface resistance of approximately 5 ohms per unit area arises.
  • the surface resistance is advantageously measured continuously during the vapor deposition with the zinc and the vapor deposition is ended when the surface resistance setpoint is reached.

Abstract

An electrosensitive recording paper is described, having a base made of paper which is provided with a basic coating and with a bakeable metal layer comprising a thin pregermination layer and a thicker recording layer made of zinc. As the adhesive pregermination layer for the zinc, known recording papers of this type provide cadmium which is extremely toxic, especially in its salts, and is thus problematic in handling and processing. This disadvantage is avoided according to the invention by the fact that silver is used as the pregermination layer.

Description

Die Erfindung betrifft ein elektrosensitives Registrierpapier der im Oberbegriff des Anspruchs 1 angegebenen Art.The invention relates to an electrosensitive registration paper of the type specified in the preamble of claim 1.

Elektrosensitives Registrierpapier wird für den Registriervorgang mit seiner metallisierten Seite über eine zylindrische Elektrode geführt. Die Gegenelektrode bildet ein dünner Wolframdraht, dessen Spitze auf der metallisierten Papierfläche gleitet. Der Auflagedruck der Gegenelektrode liegt je nach Art der verwendeten Metallschicht etwa zwischen 2.943.10⁻⁴ N und 0.0981 N (0,03 und 10 Pond). Wird an die beiden Elektroden eine elektrische Gleichspannung angelegt, so fließt durch die Metallschicht ein Strom, der das Metallmaterial in unmittelbarer Nähe der Wolframspitze der Gegenelektrode infolge der hohen Stromdichte verdampft, woraufhin der Strom unterbrochen wird. Unter dem derart verdampften bzw. weggebrannten Metallbelag kommt mit gutem Kontrast der Grundlack des Registrierpapiers zum Vorschein. Wird das Registrierpapier weitergezogen, so steht die Wolframelektrode erneut unter Spannung, und es wird erneut eine kleine Menge Metall weggebrannt.For the registration process, electrosensitive registration paper is guided with its metallized side over a cylindrical electrode. The counter electrode forms a thin tungsten wire, the tip of which slides on the metallized paper surface. The contact pressure of the counter electrode is between 2,943.10⁻⁴ N and 0.0981 N (0.03 and 10 pond) depending on the type of metal layer used. If a direct electrical voltage is applied to the two electrodes, a current flows through the metal layer, which evaporates the metal material in the immediate vicinity of the tungsten tip of the counterelectrode due to the high current density, whereupon the current is interrupted. The base coat of the registration paper appears with good contrast under the metal covering that has evaporated or burned away in this way. If the registration paper is pulled further, the tungsten electrode is energized again and a small amount of metal is burned away again.

Dieser Registriervorgang erfordert eine sehr dünne Metallschicht. Bei dem Registrierpapier der eingangs genannten Art wird als eigentliche Registrierschicht Zink eingesetzt, das jedoch naturgemäß schlecht auf dem Grundlack des Papiers haftet. Deshalb wird auf die Lackschicht zunächst eine Vorbekeimungsschicht aufgebracht, die als Haftgrundlage für die Zinkschicht dient. Die Dicke dieser im wesentlichen von den Zinkatomen gebildeten Metallschicht liegt in der Größenordnung von 0,1 µm. Die Rückseite dieses Registrierpapiers ist üblicherweise mit einem klaren Schutzlack versehen.This registration process requires a very thin layer of metal. In the case of the registration paper of the type mentioned at the outset, zinc is used as the actual registration layer, which, however, naturally adheres poorly to the base lacquer of the paper. Therefore, a pre-seeding layer is first applied to the lacquer layer, which serves as an adhesive base for the zinc layer. The thickness of this metal layer essentially formed by the zinc atoms is of the order of 0.1 μm. The back of this registration paper is usually covered with a clear protective lacquer.

Anstelle einer Zink/Cadmium-Schicht ist es auch bekannt, Aluminium als Metallbeschichtung für ein elektrosensitives Registrierpapiers zu verwenden. Aluminium hat den Vorteil, ohne zusätzliche Haftschicht unmittelbar auf dem Grundlack des Registrierpapiers gut zu haften. Neben dem besseren Kontrast gegenüber der übelicherweise schwarzen Lackschicht hat Aluminium noch den Vorteil einer höheren Korrosionsbeständigkeit als die bekannte Zink/Cadmium-Schicht.Instead of a zinc / cadmium layer, it is also known to use aluminum as a metal coating for an electrosensitive registration paper. Aluminum has the advantage of adhering directly to the base coat of the registration paper without an additional adhesive layer. In addition to the better contrast compared to the usually black lacquer layer, aluminum has the advantage of a higher corrosion resistance than the known zinc / cadmium layer.

Durch die Bildung von Aluminiumoxid wird jedoch der Stromübergang beim Registriervorgang erheblich erschwert. Für einen ausreichenden Kontakt der Registrierelektrode mit der Aluminiumschicht ist deshalb im Vergleich zu der Zink/Cadmium-Metallschicht eine wesentlich höhere Auflagekraft erforderlich. Infolge der höheren Auflagekraft erfolgt die Registrierung auf aluminiumbeschichtetem Papier zudem wesentlich träger als auf einer Zink/Cadmiumschicht. Die benötigte Auflagekraft bei der Registrierung auf der Aluminiumschicht läßt sich durch eine Beigabe von Fremdmetallen etwas reduzieren. In diesem Fall reicht eine Auflagekraft von etwa 9.81.10⁻⁴, (0,1 Pond) aus. Im Vergleich dazu erlaubt eine Zink/Cadmium-Schicht eine Registrierung bei einer Auflagekraft von etwa 4.905.10⁻⁴ N (0,05 Pond).However, the formation of aluminum oxide makes the transfer of electricity during the registration process considerably more difficult. For a sufficient contact of the registration electrode with the aluminum layer, a significantly higher contact force is required compared to the zinc / cadmium metal layer. Due to the higher tracking force, registration on aluminum-coated paper is also much slower than on a zinc / cadmium layer. The required contact force when registering on the aluminum layer can be reduced somewhat by adding foreign metals. In this case, a contact force of approximately 9.81.10⁻⁴, (0.1 pond) is sufficient. In comparison, a zinc / cadmium layer allows registration with a contact force of approximately 4,905.10⁻⁴ N (0.05 pond).

Das mit einer Zink/Cadmiumschicht versehene Registrierpapier weist jedoch einen entscheidenden Nachteil bei der Verarbeitung und Handhabung auf.However, the registration paper with a zinc / cadmium layer has a decisive disadvantage in terms of processing and handling.

Cadmium ist bekanntlich ein Metall der zweiten Nebengruppe des Periodensystems mit einem Atomgewicht von 112,41, also ein sogenanntes Schwermetall, dessen Siedepunkt bei 760° C liegt. Es tritt hauptsächlich in Form seiner zweiwertigen Verbindung als Salze auf, die bei oraler Einnahme extrem toxisch sind, zu Erbrechen, Leberschädigungen und Krämpfen führen. Beim Einatmen rufen die Dämpfe dieser Salze Reizungen der Schleimhäute und Kopfschmerzen hervor. Außerdem wirken diese Salze karzinogen.As is known, cadmium is a metal of the second subgroup of the periodic table with an atomic weight of 112.41, i.e. a so-called heavy metal, the boiling point of which is 760 ° C. It mainly occurs in the form of its divalent compound as salts, which are extremely toxic when taken orally, leading to vomiting, liver damage and convulsions. When inhaled, the vapors of these salts cause irritation to the mucous membranes and headaches. In addition, these salts are carcinogenic.

Nach Untersuchungen der Weltgesundheitsorganisation darf zur Vermeidung von Langzeitschädigungen der Gesundheit ein Grenzwert von 0.07 mg pro Tag nicht überschritten werden. In der Bundesrepublik Deutschland wurde eine MAK-Wert von 0,05 mg pro Tag festgesetzt.According to studies by the World Health Organization, Avoidance of long-term damage to health does not exceed a limit of 0.07 mg per day. A MAK value of 0.05 mg per day was set in the Federal Republic of Germany.

Die Aufgabe der Erfindung besteht darin, ein elektrosensitives Registrierpapier der eingangs genannten Art zu schaffen, das mit einem niedrigeren Auflagedruck als aluminiumbeschichtetes Registrierpapier beschrieben werden kann, und das ohne die gesundheitlichen Nachteile von Registrierpapier hergestellt und gehandhabt werden kann, das mit Zink/Cadmium beschichtet ist.The object of the invention is to provide an electrosensitive registration paper of the type mentioned in the introduction, which can be written with a lower contact pressure than aluminum-coated registration paper, and which can be produced and handled without the health disadvantages of registration paper which is coated with zinc / cadmium .

Gelöst wird diese Aufgabe durch das kennzeichnende Merkmal des Anspruchs 1. Vorteilhafte Ausgestaltungen des erfindunsgemäßen Registrierpapiers sind in den Unteransprüchen angegeben. Der Anspruch 6 betrifft ein besonders vorteilhaftes Herstellungverfahren für das erfindungsgemäße Registrierpapier.This object is achieved by the characterizing feature of claim 1. Advantageous refinements of the registration paper according to the invention are specified in the subclaims. Claim 6 relates to a particularly advantageous production method for the registration paper according to the invention.

Demnach besteht die Erfindung darin, als Vorbekeimungsschicht für die Zink-Registrierschicht Silber zu verwenden, dessen Handhabung und Verarbeitung bekanntlicherweise mit keinen toxischen Nebenwirkungen verbunden ist.Accordingly, the invention consists in using silver as the pre-seeding layer for the zinc registration layer, the handling and processing of which is known to be associated with no toxic side effects.

Eine Bedampfung des lackierten Papierträgers mit Silber verlangt zwar aufgrund des höheren Siedepunktes von Silber gegenüber Cadmium einen etwas höheren technischen Aufwand. Dieser höhere technische Aufwand wird jedoch ausgeglichen durch einen wesentlich geringeren Aufwand bezüglich der Umweltschutzauflagen im Vergleich zur Cadmiumverarbeitung.Evaporation of the coated paper carrier with silver does require a slightly higher technical effort due to the higher boiling point of silver compared to cadmium. However, this higher technical effort is offset by a much lower effort in terms of environmental protection requirements compared to cadmium processing.

Schließlich wird der Anwender des erfindungsgemäßen Zink/Silber-Registrierpapiers keinen technischen Unterschied zum herkömmlichen Zink/Cadmium-Papier erkennen, da die Empfindlichkeit des Silbersubstrats, vor allem die für eine einwandfreie Registrierung erforderliche Auflagekraft dieselbe ist wie bei der Cadmiumvariante.Finally, the user of the zinc / silver registration paper according to the invention will not see any technical difference from the conventional zinc / cadmium paper, since the sensitivity of the silver substrate, especially the contact force required for perfect registration, is the same as that of the cadmium variant.

Vorteilhafterweise basiert das erfindungsgemäße Registrierpapier auf einem Diagrammpapier einer Dicke von 20 bis 80 µm. Bevorzugt ist eine Papierdicke von 40 µm. Auf diesen Papierträger wird eine Lackschicht aufgebracht, die vorteilhafterweise rein organisch pigmentiert ist. Alternativ hierzu ist es vorgesehen, die mit einem Rußanteil versehene Lackschicht zusätzlich mit Chromdioxid (Cr₂0₃) zu pigmentieren. Hierdurch wird die Einbettung und damit die Haftung der späteren Zinkbedampfung verbessert.The registration paper according to the invention is advantageously based on a diagram paper with a thickness of 20 to 80 μm. A paper thickness of 40 μm is preferred. A lacquer layer is applied to this paper support, which is advantageously pigmented purely organically. Alternatively, it is provided that the lacquer layer provided with a soot content is additionally pigmented with chromium dioxide (Cr₂0₃). This improves the embedding and thus the adhesion of the subsequent zinc vapor deposition.

Auf diese Lackschicht wird vorteilhafterweise das Silber, dessen Siedpunkt 2170° beträgt, hauchdünn und unvollständig aufgedampft, um eine Vorbekeimungsschicht für die außenliegende Zinkbedampfungsschicht zu schaffen. Leztere wird schließlich in der Weise aufgedampft, daß ein Oberflächenwiderstand von etwa 5 Ohm pro Flächeneinheit entsteht. Der Oberflächenwiderstand wird dabei vorteilhafterweise während der Bedampfung mit dem Zink kontinuierlich gemessen und die Bedampfung wird bei Erreichen des Oberflächenwiderstand-Sollwertes beendet.The silver, the boiling point of which is 2170 °, is advantageously vapor-deposited and incompletely evaporated onto this lacquer layer in order to create a pre-germination layer for the external zinc vapor deposition layer. The latter is finally evaporated in such a way that a surface resistance of approximately 5 ohms per unit area arises. The surface resistance is advantageously measured continuously during the vapor deposition with the zinc and the vapor deposition is ended when the surface resistance setpoint is reached.

Claims (6)

  1. Electrosensitive recording paper, in particular in strip form, with a paper carrier on which a coating layer and a metal layer, which can be burnt out and consists of a thin preliminary nucleation layer and a thicker zinc recording layer, are applied, characterised in that the preliminary nucleation layer consists of silver.
  2. Recording paper according to Claim 1, characterised in that the paper carrier is between 20 µm and 80 µm, especially 40 µm, thick.
  3. Recording paper according to Claim 1 or 2, characterised in that the coating layer is organically pigmented.
  4. Recording paper according to Claim 1 or 2, characterised in that the coating layer provided with a proportion of carbon black is additionally pigmented with chromium dioxide.
  5. Recording paper according to one of Claims 1 to 4, characterised in that the zinc recording layer has a surface resistivity of approximately 5 ohm per unit area.
  6. Process for producing the electrosensitive recording paper according to one of Claims 1 to 5, characterised in that an extremely thin and incomplete silver layer is vapeur-deposited on the paper carrier, provided with the coating layer, as preliminary nucleation layer for the zinc recording layer to be subsequently vapour-deposited, and in that the vapour-deposition of zinc is controlled as a function of the resulting surface resistivity and in particular is terminated when a predetermined value for the surface resistivity per unit area is reached.
EP89102994A 1988-06-20 1989-02-21 Electrosensitive recording paper Revoked EP0358839B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89102994T ATE89515T1 (en) 1988-06-20 1989-02-21 ELECTROSENSITIVE REGISTRATION PAPER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3820803A DE3820803C1 (en) 1988-06-20 1988-06-20
DE3820803 1988-06-20

Publications (2)

Publication Number Publication Date
EP0358839A1 EP0358839A1 (en) 1990-03-21
EP0358839B1 true EP0358839B1 (en) 1993-05-19

Family

ID=6356853

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89102994A Revoked EP0358839B1 (en) 1988-06-20 1989-02-21 Electrosensitive recording paper

Country Status (4)

Country Link
EP (1) EP0358839B1 (en)
AT (1) ATE89515T1 (en)
DE (2) DE3820803C1 (en)
ES (1) ES2040912T3 (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE880218C (en) * 1951-05-31 1958-08-21 Bosch Gmbh Robert Recording measuring device with metallized recording medium
CH323961A (en) * 1953-04-23 1957-08-31 Bosch Gmbh Robert Process for the production of a recording medium for recording measuring devices
US3786518A (en) * 1972-09-22 1974-01-15 Nig Mason Ltd Electrosensitive recording materials
DE2641232C2 (en) * 1976-09-14 1982-10-21 Robert Bosch Gmbh, 7000 Stuttgart Layer structure and process for its manufacture
DE2645485C3 (en) * 1976-10-08 1979-10-31 Robert Bosch Gmbh, 7000 Stuttgart Recording media for registration purposes in electrosensitive registration devices
DE3329981A1 (en) * 1983-08-19 1985-03-07 Robert Bosch Gmbh, 7000 Stuttgart RECORD CARRIER FOR REGISTRATION DEVICES

Also Published As

Publication number Publication date
DE3820803C1 (en) 1990-02-15
DE58904409D1 (en) 1993-06-24
ATE89515T1 (en) 1993-06-15
EP0358839A1 (en) 1990-03-21
ES2040912T3 (en) 1993-11-01

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