EP0003768A1 - Metallized paper and process for its manufacture - Google Patents

Metallized paper and process for its manufacture Download PDF

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Publication number
EP0003768A1
EP0003768A1 EP79100342A EP79100342A EP0003768A1 EP 0003768 A1 EP0003768 A1 EP 0003768A1 EP 79100342 A EP79100342 A EP 79100342A EP 79100342 A EP79100342 A EP 79100342A EP 0003768 A1 EP0003768 A1 EP 0003768A1
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EP
European Patent Office
Prior art keywords
paper
room temperature
metal
copper
bath
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EP79100342A
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German (de)
French (fr)
Inventor
Harold Dr. Ebneth
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Bayer AG
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Bayer AG
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/02—Metal coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the invention relates to metallized, permanently antistatic, electrical current-conducting paper and a method for its production.
  • absorbent paper e.g. Blotting paper, filter paper, newsprint etc.
  • a hydrochloric acid palladium sol is used as a catalyst at room temperature and the metal deposition is carried out at room temperature with basic metal salt baths.
  • the invention therefore relates to a process for the metallization of paper, which is characterized in that the paper is introduced into an acidic, tin-II-ion in excess colloidal palladium solution and the material thus activated is treated with an acid or alkali and then with a basic metal salt solution electrolessly coated with metal at room temperature.
  • any absorbent i.e. little or not sized paper or cellulose fleece are metallized according to the invention.
  • an activation solution of colloidal palladium is prepared with tin-II salts.
  • the material to be activated is preferably immersed in this activation bath at room temperature with a residence time of a few seconds to a few minutes, for example 10 seconds to 3 minutes, without prior pretreatment.
  • the treatment can also last for several minutes without any impairment of the metallization being found.
  • the product activated in this way is then removed from the activation bath and preferably rinsed with water at room temperature.
  • the rinsing process may be carried out in several stages.
  • the product treated in this way is then treated in an acidic or alkaline medium for about 30 seconds to about 2 minutes.
  • treatment in an acidic medium treatment in 5% sulfuric acid or approx. 20% hydrochloric acid has been shown to be sufficient.
  • the material is preferably treated in an alkaline medium.
  • About 5% sodium hydroxide solution or about 10% by weight sodium carbonate solution showed the best results at room temperature.
  • the product is then rinsed briefly in water at preferably room temperature, for example up to 30 seconds, in order to remove excess treatment medium.
  • the material After this rinsing is added the material at about 16 ° C to about 30 0 C in an alkaline metal salt bath in which the precipitation of the metal takes place on the farm.
  • Such metal salt baths are preferably baths of nickel salts, cobalt salts or mixtures thereof, copper salts, gold salts or other salts from which metals can be precipitated from alkaline baths.
  • Ammoniacal nickel baths or sodium alkaline copper baths are very particularly preferably used according to the invention.
  • mixtures of ammonia and sodium hydroxide solution can also be used to maintain the alkaline environment.
  • Such metallization baths are known in the art of electroless metal deposition.
  • the residence time of the material to be metallized in the metallization bath described depends on the desired metal layer thickness on the surface of the material.
  • the residence time is preferably chosen between 1 and 5 minutes. With a dwell time of approx. 5 minutes layer thickness of the deposited metal of approx. 0.2 ⁇ m can be determined.
  • metallized paper can therefore be produced whose surface resistance, measured according to DIN 54 345, at 50% rh and 23 ° C. max. 1 ⁇ 1 0 3 Chm with a layer thickness of the metal coating of 0.11 ⁇ m and 3. 10 ohms with a layer thickness of 0.2 ⁇ m.
  • a blotting paper with a m 2 weight of 130 g / m2 is immersed in a hydrochloric acid bath (pH ⁇ 1) of a colloidal palladium solution according to DT-AS 1 197 720 at room temperature. After lingering with gentle movement of the goods for between 10 seconds and 2 minutes, the goods are removed and rinsed with water at room temperature. Then put it in an approx. 5% sodium hydroxide solution at room temperature. The goods are treated between about 30 seconds and 2 minutes with gentle movement of the goods, then removed and then rinsed with water for about 30 seconds at room temperature.
  • the product is then carried, for example, into an alkaline nickel bath in a solution of 0.2 mol / l nickel-II chloride, 0.9 mol / l ammonium hydroxide, 0.2 mol / 1 sodium hypophosphite, into which so much ammonia is introduced, that the pH at 20 ° C is 8.9.
  • the surface of the paper begins to discolor darkly with metal deposition.
  • the sample begins to float on the surface of the bath with the evolution of gas (hydrogen).
  • the goods are covered with a fine layer of nickel metal and the well-known yellowish nickel metal shine appears.
  • the nickel layer has reached a thickness of 0.15 ⁇ m. The material is removed from the bath and rinsed thoroughly with room temperature water until neutral.
  • the volume resistance measured according to DIN 54 345 at 50% rh and measured at 23 ° C is 2. 10 ohm cm 2 .
  • L öschpapier with an m 2 weight of 130 g / m2 is immersed a colloidal palladium solution according to DT-AS 1,197,720 at room temperature in a salt-acid bath (pH ⁇ 1). After lingering with gentle movement of the goods between 30 seconds and 2 minutes, the goods are removed and rinsed with water at room temperature. Then put it in an approx. 5% sodium hydroxide solution at room temperature. The goods are treated between 45 seconds and 2 minutes with gentle movement of the goods, then removed and then rinsed with water for about 2 seconds at room temperature. The product is then carried into a solution from an alkaline copper bath, which has a pH value of 12 at 23 ° C.
  • the surface of the paper begins to discolor darkly with the deposition of metallic copper.
  • the material is coated with a copper-colored metal layer and floats on the surface of the bath with the evolution of hydrogen gas. After about 5 minutes, a copper layer with a thickness of 0.2 ⁇ m is deposited.
  • the copper-plated material is removed from the bath and rinsed thoroughly with water at room temperature until neutralized. It is then dried gently at room temperature to avoid superficial oxidation of the copper.
  • the surface resistance according to DIN 54 345 at 50% RH and 23 ° C, measured in ohms, is 1 ⁇ 10.
  • the volume resistance measured according to DIN 54 345 at 50% RH and 23 ° C is 2 ⁇ 10 2 Ohm ⁇ cm2.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Paper (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The paper is metallised by introducing it into a colloidal palladium solution containing acidic tin(II) ions in excess and treating the thus activated material with an acid or alkali and then electrolessly coating it with metal in a basic metal salt solution. The metallised paper has a surface resistance at 50% relative humidity and 23 DEG C, measured in accordance with DIN 54 345, of not more than 1 x 10<3> ohm when the metal coat has a thickness of 0.11 mu m and not more than 3 x 10<1> ohm when the metal coat has a thickness of 0.17 mu m.

Description

Die Erfindung betrifft metallisiertes, permanent antistatisches, den elektrischen Strom leitendes Papier und ein Verfahren zu seiner Herstellung.The invention relates to metallized, permanently antistatic, electrical current-conducting paper and a method for its production.

Die Abscheidung von Metallen auf Papieroberflächen ist bekannt. Bei den nassen Verfahren stellte es sich aber heraus, daß die bisher hierbei erforderlichen hohen Temperaturen von ca. 55°C und darüber, z.B. bei der Aktivierung mit ionogenen Palladiumsalzlösungen bei pH 2,0 und die hohen Temperaturen bei der Metallisierung in sauren Bädern bei ca. 60°C zu Deformationen der ebenen Papierbahn führen. Nachträgliches Pressen beim Trocknen der gespülten, metallisierten Papierbahnen führte zu weiteren Deformationen, wie Faltenbildung, unterschiedliche Dicke der metallisierten Papiere etc...The deposition of metals on paper surfaces is known. With the wet processes, however, it turned out that the high temperatures of up to 55 ° C and above, e.g. when activated with ionic palladium salt solutions at pH 2.0 and the high temperatures during metallization in acid baths at approx. 60 ° C lead to deformations of the flat paper web. Subsequent pressing when drying the rinsed, metallized paper webs led to further deformations, such as wrinkling, different thicknesses of the metallized papers, etc.

Überraschenderweise wurde gefunden, daß saugfähiges Papier, wie z.B. Löschpapier, Filterpapier, Zeitungspapier usw. einfach und ohne Deformation zu metallisieren ist, wenn man anstelle der Aktivierung mit ionogenen Palladiumsalzbädern und Sensibilisierung mit sauren Zinn-II-Salzen ein salzsaures Palladiumsol bei Raumtemperatur als Katalysator verwendet und die Metallabscheidung bei Raumtemperatur mit basischen Metallsalzbädern durchführt.Surprisingly, it has been found that absorbent paper, e.g. Blotting paper, filter paper, newsprint etc. can be metallized easily and without deformation if, instead of activation with ionogenic palladium salt baths and sensitization with acidic tin-II salts, a hydrochloric acid palladium sol is used as a catalyst at room temperature and the metal deposition is carried out at room temperature with basic metal salt baths.

Die Erfindung betrifft daher ein Verfahren zur Metallisierung von Papier, das dadurch gekennzeichnet ist, daß man das Papier in eine saure, Zinn-II-ionen im Überschuß enthaltene kolloidale Palladiumlösung eingibt und das so aktivierte Material mit einer Säure oder Lauge behandelt und anschließend mit einer basischen Metallsalzlösung bei Raumtemperatur stromlos mit Metall überzieht.The invention therefore relates to a process for the metallization of paper, which is characterized in that the paper is introduced into an acidic, tin-II-ion in excess colloidal palladium solution and the material thus activated is treated with an acid or alkali and then with a basic metal salt solution electrolessly coated with metal at room temperature.

Prinzipiell kann jegliches saugfähige, d.h. wenig oder nicht geleimtes Papier oder Cellulosevlies erfindungsgemäß metallisiert werden.In principle, any absorbent, i.e. little or not sized paper or cellulose fleece are metallized according to the invention.

Die Metallisierung des Papiers gestaltet sich im einzelnen wie folgt:The metallization of the paper is as follows:

Gemäß DT-AS 1 197 720 wird mit Zinn-II-Salzen eine Aktivierungslösung von kolloidalem Palladium hergestellt. Der pH-Wert der Lösung soll immer = 1 sein und es soll ein Überschuß an Zinn-II-ionen vorliegen.According to DT-AS 1 197 720, an activation solution of colloidal palladium is prepared with tin-II salts. The pH of the solution should always be = 1 and there should be an excess of tin (II) ions.

Das zu aktivierende Gut wird vorzugsweise bei Raumtemperatur bei einer Verweilzeit von einigen Sekunden bis wenigen Minuten, beispielsweise 10 Sekunden bis 3 Minuten, in diesem Aktivierungsbad ohne vorherige Vorbehandlung eingetaucht. Die Behandlung kann auch mehrere Minuten betragen, ohne daß sich eine Beeinträchtigung der Metallisierung feststellen läßt.The material to be activated is preferably immersed in this activation bath at room temperature with a residence time of a few seconds to a few minutes, for example 10 seconds to 3 minutes, without prior pretreatment. The treatment can also last for several minutes without any impairment of the metallization being found.

Das so aktivierte Gut wird danach dem Aktivierungsbad entnommen und vorzugsweise bei Raumtemperatur mit Wasser gespült. Gegebenenfalls wird der Spülvorgang in mehreren Stufen durchgeführt.The product activated in this way is then removed from the activation bath and preferably rinsed with water at room temperature. The rinsing process may be carried out in several stages.

Anschließend wird das so behandelte Gut für etwa 30 Sekunden bis etwa 2 Minuten in einem sauren oder alkalischen Medium behandelt. Im Falle der Behandlung in einem sauren Medium hat sich die Behandlung in einer 5 %igen Schwefelsäure oder ca. 20 %igen Salzsäure als ausreichend gezeigt. Vorzugsweise wird das Gut jedoch in einem alkalischen Medium behandelt. Hierbei zeigten etwa 5 %ige Natronlauge oder etwa 10 Gew.-%ige Sodalösung bei vorzugsweise Raumtemperatur die besten Ergebnisse.The product treated in this way is then treated in an acidic or alkaline medium for about 30 seconds to about 2 minutes. In the case of treatment in an acidic medium, treatment in 5% sulfuric acid or approx. 20% hydrochloric acid has been shown to be sufficient. However, the material is preferably treated in an alkaline medium. About 5% sodium hydroxide solution or about 10% by weight sodium carbonate solution showed the best results at room temperature.

Anschließend wird das Gut in Wasser bei vorzugsweise Raumtemperatur kurzzeitig gespült, beispielsweise bis zu 30 Sekunden, um überschüssiges Behandlungsmedium zu entfernen.The product is then rinsed briefly in water at preferably room temperature, for example up to 30 seconds, in order to remove excess treatment medium.

Nach diesem Spülen gibt man das Gut bei etwa 16°C bis etwa 300C in ein alkalisches Metallsalzbad, in dem der Niederschlag des Metalles auf dem Gut stattfindet.After this rinsing is added the material at about 16 ° C to about 30 0 C in an alkaline metal salt bath in which the precipitation of the metal takes place on the farm.

Solche Metallsalzbäder sind vorzugsweise Bäder von Nickelsalzen, Cobaltsalzen oder deren Gemischen, Kupfersalze, Goldsalzen oder anderen Salzen, aus denen sich Metalle aus alkalischen Bädern niederschlagen lassen.Such metal salt baths are preferably baths of nickel salts, cobalt salts or mixtures thereof, copper salts, gold salts or other salts from which metals can be precipitated from alkaline baths.

Ganz besonders bevorzugt werden erfindungsgemäß ammoniakalische Nickelbäder oder natronalkalische Kupferbäder verwendet. Selbstverständlich können auch Mischungen aus Ammoniak und Natronlauge zur Aufrechterhaltung des alkalischen Milieus verwendet werden.Ammoniacal nickel baths or sodium alkaline copper baths are very particularly preferably used according to the invention. Of course, mixtures of ammonia and sodium hydroxide solution can also be used to maintain the alkaline environment.

Solche Metallisierungsbäder sind in der Technik der stromlosen Metallabscheidung bekannt.Such metallization baths are known in the art of electroless metal deposition.

Als besonders vorteilhaft haben sich Bäder folgender Zusammensetzung erwiesen:Baths of the following composition have proven to be particularly advantageous:

Ein Nickelbad aus 0,2 Mol/1 Nickel-II-Chlorid, 0,9 Mol/l Ammoniumhydroxid (25 Gew.-%ige Lösung), 0,2 Mol/l Natriumhypophosphit und soviel freiem Ammoniak, daß der pH-Wert bei 20°C 8,9 - 9,4 beträgt oder ein Kupferbad aus 30 g/1 Kupfer-II-Sulfat, 100 g/1 Seignette-Salz und 50 ml/1 37 Gew.-%ige Formaldehydlösung. Dieses Kupferbad wird mit Natriumhydroxid auf einen pH-Wert von 11 bis 12 eingestellt.A nickel bath of 0.2 mol / 1 nickel (II) chloride, 0.9 mol / l ammonium hydroxide (25% by weight solution), 0.2 mol / l sodium hypophosphite and so much free ammonia that the pH value at 20 ° C is 8.9 - 9.4 or a copper bath of 30 g / 1 copper (II) sulfate, 100 g / 1 Seignette salt and 50 ml / 1 37% by weight formaldehyde solution. This copper bath is adjusted to a pH of 11 to 12 with sodium hydroxide.

Die Verweilzeit des zu metallisierenden Gutes im beschriebenen Metallisierungsbad hängt von der gewünschten Metallschichtdicke auf der Oberfläche des Gutes ab. Vorzugsweise wird die Verweilzeit zwischen 1 und 5 Minuten gewählt. Bei einer Verweilzeit von ca. 5 Minuten ließen sich Schichtdicken des niedergeschlagenen Metalles von ca. 0,2 µm feststellen.The residence time of the material to be metallized in the metallization bath described depends on the desired metal layer thickness on the surface of the material. The residence time is preferably chosen between 1 and 5 minutes. With a dwell time of approx. 5 minutes layer thickness of the deposited metal of approx. 0.2 µm can be determined.

Überraschenderweise können mit der erfindungsgemäßen Metallisierung, d.h. bei Verwendung dieser Palladium-sol-Aktivierungslösungen bei Raumtemperatur ohne jegliche Vorbehandlungen unter Verwendung alkalischer Metallisierungsbäder bei Raumtemperatur am metallisierten Gut Oberflächenwiderstände erhalten werden, die um Zehnerpotenzen niedriger liegen als die bei der Verwendung von ionogenen Aktivierungsbädern und sauren Metallisierungsbädern erzielbaren.Surprisingly, with the metallization according to the invention, i.e. When using these palladium sol activation solutions at room temperature without any pretreatments using alkaline metallization baths at room temperature, surface resistances are obtained which are ten orders of magnitude lower than those which can be achieved using ionogenic activation baths and acidic metallization baths.

Erfindungsgemäß kann daher metallisiertes Papier hergestellt werden, dessen Oberflächenwiderstand, gemessen nach DIN 54 345, bei 50 % r.F. und 230C max. 1 · 10 3 Chm bei einer Schichtdicke des Metallüberzuges von 0,11µm und 3 . 10 Ohm bei einer Schichtdicke von 0,2µm beträgt.According to the invention, metallized paper can therefore be produced whose surface resistance, measured according to DIN 54 345, at 50% rh and 23 ° C. max. 1 · 1 0 3 Chm with a layer thickness of the metal coating of 0.11 µm and 3. 10 ohms with a layer thickness of 0.2 µm.

Beispiel 1example 1

Ein Löschpapier mit einem m2-Gewicht von 130 g/m2 wird bei Raumtemperatur in ein salzsaures Bad (pH≤1)einer kolloidalen Palladiumlösung gemäß DT-AS 1 197 720 eingetaucht. Nach Verweilen unter leichter Warenbewegung zwischen 10 Sekunden und 2 Minuten wird das Gut entnommen und mit Wasser bei Raumtemperatur gespült. Danach gibt man es in eine ca. 5 %ige Natronlauge bei Raumtemperatur. Unter leichter Warenbewegung wird das Gut zwischen ca. 30 Sekunden und 2 Minuten behandelt, anschließend entnommen und dann mit Wasser ca. 30 Sekunden bei Raumtemperatur gespült. Anschließend trägt man das Gut z.B. in ein alkalisches Nickelbad in eine Lösung aus 0,2 Mol/l Nickel-II-Chlorid, 0,9 Mol/l Ammoniumhydroxid, 0,2 Mol/1 Natriumhypophosphit, in das man so viel Ammoniak einleitet, daß der pH-Wert bei 20°C 8,9 beträgt.A blotting paper with a m 2 weight of 130 g / m2 is immersed in a hydrochloric acid bath (pH≤1) of a colloidal palladium solution according to DT-AS 1 197 720 at room temperature. After lingering with gentle movement of the goods for between 10 seconds and 2 minutes, the goods are removed and rinsed with water at room temperature. Then put it in an approx. 5% sodium hydroxide solution at room temperature. The goods are treated between about 30 seconds and 2 minutes with gentle movement of the goods, then removed and then rinsed with water for about 30 seconds at room temperature. The product is then carried, for example, into an alkaline nickel bath in a solution of 0.2 mol / l nickel-II chloride, 0.9 mol / l ammonium hydroxide, 0.2 mol / 1 sodium hypophosphite, into which so much ammonia is introduced, that the pH at 20 ° C is 8.9.

Nach ca. 20 Sekunden beginnt sich die Oberfläche des Papiers dunkel unter Metallabscheidung zu verfärben. Nach ca. 40 Sekunden beginnt die Probe an der Oberfläche des Bades zu schwimmen unter Gasentwicklung (Wasserstoff). Nach ca. 100 Sekunden ist das Gut mit einer feinen Nickelmetallschicht bedeckt und der bekannte gelbliche Nickelmetallglanz tritt auf. Nach ca. 3 Minuten hat die Nickelschicht eine Dicke von 0,15µm erreicht. Das Gut wird dem Bad entnommen und bis zur Neutralreaktion gründlich mit Wasser von Raumtemperatur gespült.After approx. 20 seconds, the surface of the paper begins to discolor darkly with metal deposition. After approx. 40 seconds the sample begins to float on the surface of the bath with the evolution of gas (hydrogen). After about 100 seconds, the goods are covered with a fine layer of nickel metal and the well-known yellowish nickel metal shine appears. After approx. 3 minutes the nickel layer has reached a thickness of 0.15 µm. The material is removed from the bath and rinsed thoroughly with room temperature water until neutral.

Der Oberflächenwiderstand gemäß DIN 54 345 bei 50 % r.F. und 23°C, gemessen in Ohm, beträgt 3 · 10 bei einer Nickelschichtdicke von 0,17µm. Der Durchgangswiderstand gemessen nach DIN 54 345 bei 50 % r.F. und 23°C gemessen beträgt 2 . 10 Ohm cm 2 . The surface resistance according to DIN 54 345 at 50% RH and 23 ° C, measured in ohms, is 3 · 10 at Nickel layer thickness of 0.17 µm. The volume resistance measured according to DIN 54 345 at 50% rh and measured at 23 ° C is 2. 10 ohm cm 2 .

Beispiel 2Example 2

Löschpapier mit einem m2-Gewicht von 130 g/m2 wird bei Raumtemperatur in ein salzsaures Bad (pH ≤1) einer kolloidalen Palladiumlösung gemäß DT-AS 1 197 720 eingetaucht. Nach Verweilen unter leichter Warenbewegung zwischen 30 Sekunden und 2 Minuten wird das Gut entnommen und mit Wasser bei Raumtemperatur gespült. Danach gibt man es in eine ca. 5 %ige Natronlauge bei Raumtemperatur. Unter leichter Warenbewegung wird das Gut zwischen ca. 45 Sekunden bis 2 Minuten behandelt, anschließend entnommen und dann mit Wasser ca. 2 Sekunden bei Raumtemperatur gespült. Anschließend trägt man das Gut in eine Lösung aus einem alkalischen Kupferbad, das einen pH-Wert bei 23°C von 12 hat. Nach ca. 20 Sekunden beginnt sich die Oberfläche des Papiers dunkel unter Abscheidung von metallischem Kupfer zu verfärben. Nach etwa 50 Sekunden ist das Gut mit einer kupferfarbenen Metallschicht überzogen und schwimmt unter Wasserstoffgasentwicklung an der Badoberfläche. Nach ca. 5 Minuten ist eine Kupferschicht in einer Dicke von 0,2µm abgeschieden. Das verkupferte Gut wird dem Bad entnommen und bis zur Neutralisierung gründlich mit Wasser bei Raumtemperatur gespült. Anschließend wird schonend bei Raumtemperatur getrocknet, um eine oberflächliche Oxidation des Kupfers zu vermeiden. Der Oberflächenwiderstand gemäß DIN 54 345 bei 50 % r.F. und 23°C, gemessen in Ohm, beträgt 1 · 10 . Der Durchgangswiderstand gemessen nach DIN 54 345 bei 50 % r.F. und 23°C gemessen beträgt 2 · 102 Ohm · cm2. L öschpapier with an m 2 weight of 130 g / m2 is immersed a colloidal palladium solution according to DT-AS 1,197,720 at room temperature in a salt-acid bath (pH ≤1). After lingering with gentle movement of the goods between 30 seconds and 2 minutes, the goods are removed and rinsed with water at room temperature. Then put it in an approx. 5% sodium hydroxide solution at room temperature. The goods are treated between 45 seconds and 2 minutes with gentle movement of the goods, then removed and then rinsed with water for about 2 seconds at room temperature. The product is then carried into a solution from an alkaline copper bath, which has a pH value of 12 at 23 ° C. After about 20 seconds, the surface of the paper begins to discolor darkly with the deposition of metallic copper. After about 50 seconds, the material is coated with a copper-colored metal layer and floats on the surface of the bath with the evolution of hydrogen gas. After about 5 minutes, a copper layer with a thickness of 0.2 µm is deposited. The copper-plated material is removed from the bath and rinsed thoroughly with water at room temperature until neutralized. It is then dried gently at room temperature to avoid superficial oxidation of the copper. The surface resistance according to DIN 54 345 at 50% RH and 23 ° C, measured in ohms, is 1 · 10. The volume resistance measured according to DIN 54 345 at 50% RH and 23 ° C is 2 · 10 2 Ohm · cm2.

Claims (5)

1) Verfahren zur Metallisierung von Papier, dadurch gekennzeichnet, daß man das Papier in eine saure, Zinn-II-ionen im Überschuß enthaltene kolloidale.Palladium- lösung eingibt und das so aktivierte Material mit einer Säure oder Lauge behandelt und anschließend mit einer basischen Metallsalzlösung bei Raumtemperatur stromlos mit Metall überzieht.1) Process for the metallization of paper, characterized in that the paper is introduced into an acidic, tin (II) ion in excess colloidal palladium solution and the material thus activated is treated with an acid or alkali and then with a basic metal salt solution Electrolessly coated with metal at room temperature. 2) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß in dem Metallisierungsbad bei Raumtemperatur gearbeitet wird.2) Method according to claim 1, characterized in that one works in the metallization bath at room temperature. 3) Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß ammoniakalisch-alkalisch vernickelt oder verkupfert wird.3) Process according to claims 1 and 2, characterized in that ammoniacal-alkaline is nickel-plated or copper-plated. 4) Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß natronalkalisch verkupfert wird.4) Process according to claims 1 and 2, characterized in that copper-hydroxide is copper-alkaline. 5) Metallisiertes Papier, gekennzeichnet durch einen Oberflächenwiderstand, gemessen nach DIN 54 345, bei 50 % r.F. und 23°C von max. 1 · 103 Ohm bei einer Schichtdicke des Metallüberzuges von 0,11 µm und von max. 3 . 101 Ohm bei einer Schichtdicke von 0,17µm des Metallüberzuges.5) Metallized paper, characterized by a surface resistance, measured according to DIN 54 345, at 50% RH and 23 ° C of max. 1 · 10 3 Ohm with a layer thickness of the metal coating of 0.11 µm and of max. 3rd 10 1 ohm with a layer thickness of 0.17 µm of the metal coating.
EP79100342A 1978-02-17 1979-02-06 Metallized paper and process for its manufacture Ceased EP0003768A1 (en)

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DE19782806835 DE2806835A1 (en) 1978-02-17 1978-02-17 METALIZED PAPER
DE2806835 1978-02-17

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US4792645A (en) * 1984-09-03 1988-12-20 The Agency Of Industrial Science & Technology Process for producing electroconductive fibrous shaped-articles
US6290914B1 (en) * 2000-10-11 2001-09-18 Lamplight Farms, Inc. Fragrance ring for oil lamps

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JPS5994676A (en) * 1982-11-20 1984-05-31 中越パルプ工業株式会社 Conductive cellulose material and production thereof

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DE1197720B (en) * 1959-06-08 1965-07-29 Shipley Co Process for the pretreatment of, in particular, dielectric carriers prior to electroless metal deposition
US3438798A (en) * 1965-08-23 1969-04-15 Arp Inc Electroless plating process
DE1621326A1 (en) * 1965-09-13 1971-05-13 Omara M Process for non-electrical plating of non-conductive objects
DE2111137A1 (en) * 1971-03-09 1972-11-09 Kalle Ag Metallized, porous molded body and process for its production
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Publication number Priority date Publication date Assignee Title
US4792645A (en) * 1984-09-03 1988-12-20 The Agency Of Industrial Science & Technology Process for producing electroconductive fibrous shaped-articles
US6290914B1 (en) * 2000-10-11 2001-09-18 Lamplight Farms, Inc. Fragrance ring for oil lamps

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JPS54117330A (en) 1979-09-12
FI790498A (en) 1979-08-18

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