EP0213327A2 - Lacquer transfer film and process for preparing it - Google Patents
Lacquer transfer film and process for preparing it Download PDFInfo
- Publication number
- EP0213327A2 EP0213327A2 EP86109296A EP86109296A EP0213327A2 EP 0213327 A2 EP0213327 A2 EP 0213327A2 EP 86109296 A EP86109296 A EP 86109296A EP 86109296 A EP86109296 A EP 86109296A EP 0213327 A2 EP0213327 A2 EP 0213327A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- film
- paint
- transferable
- lacquer
- 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.)
- Withdrawn
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1733—Decalcomanias applied under pressure only, e.g. provided with a pressure sensitive adhesive
- B44C1/1741—Decalcomanias provided with a layer being specially adapted to facilitate their release from a temporary carrier
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/14—Layer or component removable to expose adhesive
- Y10T428/1452—Polymer derived only from ethylenically unsaturated monomer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2839—Web or sheet containing structurally defined element or component and having an adhesive outermost layer with release or antistick coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
Definitions
- the invention relates to a transferable paint film according to the features of the preamble of claim 1.
- Such a lacquer film is known from EP-PS 50 794.
- this lacquer film there is a neutralizing layer with a wax-like consistency on the silicone layer serving as the solution or release layer, which here is of the dimethylsiloxane type.
- the wax-like neutralization layer enables the formation and adhesion of a uniform, smooth lacquer layer of any kind on the carrier film.
- paint films with paint layers are described, which consist of original automotive paints.
- the original vehicle paint is available here as dry material that a consumer can easily carry with him and, if necessary, use to repair damaged areas on the vehicle body.
- the lacquer film according to the invention has the advantage that a neutralization layer is unnecessary due to the use of another silicone layer.
- the paint film can accordingly be produced with less material and less work.
- adhesive layers can be applied directly, uniformly and well adhering, without wetting difficulties and, if necessary, can be removed again without changing their properties. This is due to the high degree of cross-linking of the silicone layer. This largely prevents free silicones from migrating into the other layers.
- the former could react chemically with one or more constituents of the layers and / or physically attach to constituents of the other layers, which would result in material losses in the lacquer and / or with the adhesive and thus a deterioration in quality.
- Silicone layers of the polyaddition type are known per se. They can be produced, for example, by reacting organosilicon compound bearing hydrogen on the silicon atom with silicon compounds bearing unsaturated groups.
- Silicone layers of the alkenyl group-containing, in particular of the vinyl group-containing, polyaddition type have proven to be particularly suitable for the present application.
- highly cross-linked silicone layers for example of the silicone rubber type, can be produced in a very short period of time, which fulfill all the requirements placed on them.
- the silicone layers can be produced according to the following reaction scheme:
- Plastic films are particularly suitable as the carrier film for the present application.
- the plastic films must be smooth on the surface so that a uniform, smooth lacquer layer can be obtained.
- the plastic films should also be mechanically resistant so that tearing and no wrinkling occur during the further manufacturing process. Furthermore, they should be chemically resistant, in particular to organic solvents which are present in the other components of the paint film or when it is applied.
- the plastic films should also be thermally resistant Temperatures that occur in the paint drying or paint baking process, ie between 100 ° C and 150 ° C. It has been found that polyester films, in particular polyethylene terephthalate films, are particularly suitable for the present application. The use of other plastic films is also possible.
- the adhesive layer must also meet a number of conditions in order to be used for the paint film according to the invention. It should be self-adhesive and have a great adhesive force, especially in relation to metal, plastic and wood surfaces. Their adhesiveness must also be against after the paint layer has dried or hardened. For this reason, it must be chemically resistant to the solid and liquid components such as solvents contained in the paints used. If e.g. If two-component paints based on acrylic resin are used, the components of the adhesive layer should not crosslink with the isocyanates contained in these paints in order to avoid loss of adhesive or loss of effectiveness.
- the adhesives listed in claims 13 and 14 are found to be very suitable for the paint film according to the invention.
- non-crosslinking acrylic adhesives based on solvents or water could also be used, in particular as dispersions, neoprene adhesives, chlorinated rubber adhesives, polyisobutylene adhesives and adhesives made from chlorinated hydrocarbons.
- the carrier film provided with a silicone layer according to the invention can be used without any difficulty to produce a uniform, well adhering lacquer layer if it is provided with the adhesive layer before the lacquer layer is applied. A product is thus obtained in which the lacquer is present as the top layer.
- the layer of varnish together with the adhesive can be simple removed by hand from the carrier film and glued directly to the object to be treated with paint.
- a solvent-containing system which contains at least one organosilicon compound carrying hydrogen on the silicon atom and at least one organosilicon compound bearing alkenyl groups, and a platinum or iridium catalyst, onto one side of a web-like carrier film using a suitable device, or, if that solvent-based system should be more viscous to apply.
- organosilicon compounds bearing vinyl groups are particularly suitable for this. This enables a highly cross-linked silicone to be obtained at room temperature within a few seconds. After subsequent drying, there is an even silicone layer on the carrier film. The drying temperature depends on the solvent used and the type of carrier film. For polyethylene terephthalate films it can be 150 ° C. A certain amount of crosslinking of the silicone layer also takes place during the drying. Silicone layers with a thickness of one or a few micrometers have proven to be particularly suitable for producing a paint film according to the invention.
- a uniformly thick adhesive layer can be produced particularly easily on the carrier film provided with a silicone layer according to the invention if the procedure is as claimed in claim 18. With the help of the proposed solvent, a perfect wetting of the silicone layer and a relatively quick drying of the adhesive layer is possible.
- the film thus produced is not to be further processed immediately, ie to be provided with one or more layers of lacquer, it is proposed that it be provided with a web-like cover film, which must have the property that it has the adhesive layer not damaged, cover.
- the film can be stored in one or more layers in sheets or rolled up without any problems until it is processed further.
- Another possibility is to provide the back of the carrier film with a release layer. The film can be stored in multiple layers in sheets or rolled up until it is processed further.
- Polyester films coated with a silicone layer according to the invention are particularly suitable as cover films. It is sufficient if a film of a smaller thickness than that of the carrier film is used as the cover film, since the former is subjected to less mechanical stress than the latter.
- Papers coated with a silicone layer according to the invention are also particularly suitable as cover films.
- the lacquer is applied in liquid form to the adhesive layer and then dried. The process is repeated for multi-layer paints.
- the product can then either be rolled up or stored in pieces. If necessary, a large piece of the area to be covered with lacquer can be cut off from the product, the lacquer layer together with the adhesive layer can be pulled off from the silicon-coated carrier film by hand and stuck onto the surface to be covered in the manner of a plaster.
- the paint film according to the invention can also be prepared according to claim 25.
- the individual areas can be cut free by a stamping process. That way you can sharp, self-adhesive symbols, numbers and letters made of lacquer can also be produced in a rational manner.
- composition and shape of the individual components of the new paint film are described below.
- the new paint film is preferably produced with a continuously operating device, as described and shown schematically in EP-PS 50 794.
- a polyethylene terephthalate film of about 50 to 80 micrometers thick and about one meter wide is used as the carrier film for the lacquer film, which is wound into a roll.
- This carrier film has optimal conditions for producing the lacquer film according to the invention because it is smooth on the surface and has excellent mechanical, chemical and thermal resistance.
- the carrier film can be fed to the device endlessly from the roll or in sheets. In a previous process, this carrier film was provided on one side with an approximately one micrometer thick silicone layer which is highly crosslinked and of the alkenyl group-containing, especially of the vinyl group-containing, polyaddition type.
- the carrier film has been dried at about 150 ° C.
- the surface tension of the silicone layer is 22 dynes / cm.
- the average separation value of the silicone layer was determined to be 11.25 + 3.75 cN / cm, using the test method listed below:
- the test adhesive tape is a polyvinyl chloride film on which an adhesive layer based on rubber is anchored.
- Such a test adhesive tape is available, for example, under the name Tesa 154 from Beiersdorf AG, Hamburg.
- the test tape is placed on the silicone layer with the adhesive layer and the sample is stored for about 20 hours at room temperature under a pressure of 8 to 10 kPa.
- the mean separation value is then determined by measuring the peel force of several samples using suitable equipment.
- a highly viscous, trichlorethylene-containing styrene-isoprene-styrene block polymer system is knife-coated onto the silicon-coated side of the carrier film to produce an adhesive layer.
- the adhesive is applied in such an amount that an adhesive layer of 10 to 14 g / m2 is obtained after it has dried.
- the carrier film is then dried at a temperature which is above 85 ° C.
- the adhesive layer thus produced is self-adhesive and has great adhesiveness, e.g. compared to metal, plastic and glass surfaces, which can also be painted, as well as a high degree of cohesion.
- Automotive paint is applied to the adhesive side of the cooled carrier film prepared in this way. If a solid color is desired, a solvent-containing two-component acrylic isocyanate system is sprayed on evenly and dried. The system networks well with the adhesive layer. The process is continued until ei ne layer thickness of about 20 to 40 microns is reached.
- the paint film produced in this way is strong, very flexible, colourfast and weatherproof.
- a physically drying acrylic lacquer is sprayed evenly onto the adhesive layer and dried as the first layer.
- the paint adheres perfectly to the adhesive layer.
- a two-component acrylic isocyanate clear lacquer is sprayed on and dried.
- the clear coat adheres perfectly to the first coat of paint.
- the total lacquer layer thickness is also about 25 to 45 micrometers here. This paint film corresponds to the paint layer structure and thus the optical effect of original metallic automotive stove enamels, is strong, very flexible, colourfast and weatherproof.
- the lacquer film initially has a continuous lacquer layer. Punching out individual, handy, large areas of the lacquer layer is now cut free from lacquer layer regions adjoining them laterally, the adhesive layer regions underneath also being detected and also cut free. The lacquer film is then cut into pieces and packaged. If necessary, dry pieces of lacquer layer can be peeled off from the sections by the consumer and glued onto their surfaces to be repaired with their adhesive layer side. It does not matter if the silicone layer has also been cut free in some areas in the previously described stamping process. The silicone layer adheres so little to the adhesive layer that it is never peeled off.
Landscapes
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Adhesive Tapes (AREA)
- Decoration By Transfer Pictures (AREA)
- Vehicle Waterproofing, Decoration, And Sanitation Devices (AREA)
Abstract
Die Erfindung betrifft einen übertragbaren Lackfilm, der eine als Ablösungsschicht dienende Silikonschicht, welche hochvernetzt und vom alkenylgruppenhaltigen Polyadditionstyp ist und eine Klebstoffschicht sowie eine Lackschicht aufweist. Die Lackschicht kann mitsamt der Klebstoffschicht von Hand abgezogen und auf eine mit Lack zu behandelnde Oberfläche aufgeklebt werden.The invention relates to a transferable lacquer film which has a silicone layer serving as a release layer, which is highly crosslinked and of the alkenyl group-containing polyaddition type and has an adhesive layer and a lacquer layer. The lacquer layer together with the adhesive layer can be peeled off by hand and glued to a surface to be treated with lacquer.
Description
Die Erfindung betrifft einen übertragbaren Lackfilm gemäß den Merkmalen des Oberbegriffes des Anspruches 1.The invention relates to a transferable paint film according to the features of the preamble of claim 1.
Eine derartiger Lackfilm ist aus der EP-PS 50 794 bekannt. Bei diesem Lackfilm befindet sich auf der als Lösungs- bzw. Ablösungsschicht dienenden Silikonschicht,welche hier vom Dimethylsiloxan-Typ ist, eine Neutralisierungsschicht mit wachsartiger Konsistenz. Die wachsartige Neutralisierungsschicht ermöglicht die Ausbildung und Haftung einer gleichmäßigen, glatten Lackschicht, gleich welcher Art, auf dem Trägerfilm. Beispielsweise sind Lackfolien mit Lackschichten beschrieben, die aus Originalkraftfahrzeuglacken bestehen. Der Originalkraftfahrzeuglack liegt hier als Trockenmaterial vor, das ein Verbraucher problemlos mit sich führen und bei Bedarf zur Ausbesserung schadhafter Stellen an der Fahrzeugkarosserie verwenden kann.Such a lacquer film is known from EP-PS 50 794. In this lacquer film, there is a neutralizing layer with a wax-like consistency on the silicone layer serving as the solution or release layer, which here is of the dimethylsiloxane type. The wax-like neutralization layer enables the formation and adhesion of a uniform, smooth lacquer layer of any kind on the carrier film. For example, paint films with paint layers are described, which consist of original automotive paints. The original vehicle paint is available here as dry material that a consumer can easily carry with him and, if necessary, use to repair damaged areas on the vehicle body.
Der erfindungsgemäße Lackfilm hat demgegenüber den Vorteil, daß aufgrund der Verwendung einer anderen Silikonschicht eine Neutralisierungsschicht entbehrlich ist. Der Lackfilm kann demgemäß mit einem geringeren Material- und Arbeitsaufwand gefertigt werden. Auf einen mit einer erfindungsgemäßen Silikonschicht beschichteten Trägerfilm lassen sich Klebstoffschichten ohne Benetzungsschwierigkeiten direkt gleichmäßig sowie gut haftend auftragen und bei Bedarf wieder problemlos entfernen, ohne daß sie ihre Eigenschaften verändert hätten. Das beruht auf dem hohen Vernetzungsgrad der Silikonschicht. Dadurch wird eine Überwanderung von freien Silikonen in die übrigen Schichten weitgehen vermieden. Bei einer Überwanderung freier Silikone in die übrigen Schichten könnten erstere mit einem oder mehreren Bestandteilen der Schichten chemisch reagieren und/oder sich physikalisch an Bestandteile der übrigen Schichten anlagern, was Materialverluste beim Lack und/ oder beim Klebstoff und damit eine Qualitätsbeeinträchtigung bedeuten würde.In contrast, the lacquer film according to the invention has the advantage that a neutralization layer is unnecessary due to the use of another silicone layer. The paint film can accordingly be produced with less material and less work. On a carrier film coated with a silicone layer according to the invention, adhesive layers can be applied directly, uniformly and well adhering, without wetting difficulties and, if necessary, can be removed again without changing their properties. This is due to the high degree of cross-linking of the silicone layer. This largely prevents free silicones from migrating into the other layers. If free silicones migrate into the other layers, the former could react chemically with one or more constituents of the layers and / or physically attach to constituents of the other layers, which would result in material losses in the lacquer and / or with the adhesive and thus a deterioration in quality.
Silikonschichten vom Polyadditionstyp sind an sich bekannt. Sie können beispielsweise durch Umsetzung von Wasserstoff am Siliciumatom tragenden Organosiliciumverbindung mit ungesättigte Gruppen tragenden Siliciumverbindungen hergestellt werden.Silicone layers of the polyaddition type are known per se. They can be produced, for example, by reacting organosilicon compound bearing hydrogen on the silicon atom with silicon compounds bearing unsaturated groups.
Für den vorliegenden Anwendungsfalls als besonders geeignet haben sich Silikonschichten vom alkenylgruppenhaltigen, insbesondere vom vinylgruppenhaltigen Polyadditionstyp, erwiesen. Damit lassen sich in einem sehr kurzen Zeitraum hochvernetzte Silikonschichten etwa vom Silikonkautschuktyp herstellen, die alle hier an sie gestellten Anforderungen erfüllen. Die Silikonschichten können nach folgendem Reaktionsschema hergestellt werden:
Weitere Vorteile bezüglich des Ablaufes der Silikonschichtbildung und der gewünschten Wirkung der Silikonschicht als Ablösungsschicht werden erzielt, wenn dieselbe ein Gerüst von Dimentylpolysiloxangruppen enthält.Further advantages with regard to the course of the silicone layer formation and the desired effect of the silicone layer as a release layer are achieved if the latter contains a skeleton of dimentylpolysiloxane groups.
Als Trägerfilm für den vorliegenden Anwendungsfall kommen insbesondere Kunststoffolien in Betracht. Die Kunststoffolien müssen oberflächenglatt sein, damit eine gleichmäßige, glatte Lackschicht erhalten werden kann. Auch sollen die Kunststofffolien mechanisch beständig sein, damit ein Einreißen und keine Faltenbildung beim weiteren Herstellungsvorgang auftreten. Weiterhin sollen sie chemisch beständig sein, insbesondere gegen organische Lösungsmittel, die in den übrigen Komponenten des Lackfilmes bzw. bei dessen Aufbringen vorhanden sind. Auch sollen die Kunststoffolien thermisch beständig sein bei Temperaturen, die im Lacktrocknungs- bzw. Lackeinbrennungsverfahren auftreten, d.h. zwischen 100°C und 150°C. Es hat sich herausgestellt, daß Polyesterfolien, insbesondere Polyäthylenterephtalatfolien für den vorliegenden Anwendungsfall besonders geeignet sind. Die Verwendung anderer Kunststoffolien ist ebenfalls möglich.Plastic films are particularly suitable as the carrier film for the present application. The plastic films must be smooth on the surface so that a uniform, smooth lacquer layer can be obtained. The plastic films should also be mechanically resistant so that tearing and no wrinkling occur during the further manufacturing process. Furthermore, they should be chemically resistant, in particular to organic solvents which are present in the other components of the paint film or when it is applied. The plastic films should also be thermally resistant Temperatures that occur in the paint drying or paint baking process, ie between 100 ° C and 150 ° C. It has been found that polyester films, in particular polyethylene terephthalate films, are particularly suitable for the present application. The use of other plastic films is also possible.
Die Klebstoffschicht muß ebenfalls eine Reihe von Bedingungen erfüllen, um für den erfindungsgemäßen Lackfilm Anwendung finden zu können. Sie soll selbstklebend sein und eine große Haftkraft, insbesondere gegenüber Metall-, Kunststoff- und Holzoberflächen besitzen. Ihre Klebfähigkeit muß auch nach dem Trocknen oder Aushärten der Lackschicht gegen sein. Deswegen muß sie gegen die in den zur Anwendung kommenden Lacken enthaltenen festen und flüssigen Komponenten, wie Lösungsmittel, chemisch beständig sein. Wenn z.B. Zweikomponentenlacke auf Acrylatharzbasis zur Anwendung kommen, sollten die Bestandteile der Klebstoffschicht nicht mit den in diesen Lacken enthaltenen Isocyanaten vernetzen, um Klebstoffverluste bzw. Klebstoffwirkungsverluste zu vermeiden. Die in den Ansprüchen 13 und 14 aufgeführten Klebstoffe sind, wie sich herausgestellt hat, für den erfindungsgemäßen Lackfilm sehr gut geeignet. Alternativ könnten auch nicht vernetzende Acrylklebstoff auf Lösungsmittel- oder wässriger Basis, insbesondere als Dispersionen, Neopren-Klebstoffe, Chlorkautschukklebstoffe, Poly-Isobutylen-Klebstoffe und Klebstoffe aus chlorierten Kohlenwasserstoffen Anwendung finden.The adhesive layer must also meet a number of conditions in order to be used for the paint film according to the invention. It should be self-adhesive and have a great adhesive force, especially in relation to metal, plastic and wood surfaces. Their adhesiveness must also be against after the paint layer has dried or hardened. For this reason, it must be chemically resistant to the solid and liquid components such as solvents contained in the paints used. If e.g. If two-component paints based on acrylic resin are used, the components of the adhesive layer should not crosslink with the isocyanates contained in these paints in order to avoid loss of adhesive or loss of effectiveness. The adhesives listed in claims 13 and 14 are found to be very suitable for the paint film according to the invention. Alternatively, non-crosslinking acrylic adhesives based on solvents or water could also be used, in particular as dispersions, neoprene adhesives, chlorinated rubber adhesives, polyisobutylene adhesives and adhesives made from chlorinated hydrocarbons.
In der Praxis hat sich herausgestellt, daß sich der mit einer erfindungsgemäßen Silikonschicht versehene Trägerfilm ohne jede Schwierigkeit zur Erzeugung einer gleichmäßigen, gut haftenden Lackschicht verwenden läßt, wenn sie vor dem Auftragen der Lackschicht mit der Klebstoffschicht versehen wird. Damit wird ein Produkt erhalten, bei welcher der Lack als oberste Schicht vorliegt. Die Lackschicht kann mitsamt dem Klebstoff einfach von Hand vom Trägerfilm abgezogen und unmittelbar auf den mit Lack zu behandelnden Gegenstand aufgeklebt werden.In practice it has been found that the carrier film provided with a silicone layer according to the invention can be used without any difficulty to produce a uniform, well adhering lacquer layer if it is provided with the adhesive layer before the lacquer layer is applied. A product is thus obtained in which the lacquer is present as the top layer. The layer of varnish together with the adhesive can be simple removed by hand from the carrier film and glued directly to the object to be treated with paint.
Zur Herstellung des neuen Lackfilmes wird vorgeschlagen, ein lösungsmittelhaltiges System, welches wenigstens eine Wasserstoff am Siliciumatom tragende Organosiliciumverbindung und wenigstens eine Alkenylgruppen tragende Organosiliciumverbindung sowie eine Platin- oder Iridiumkatalysator enthält, auf eine Seite eines bahnartigen Trägerfilms mit einer geeigneten Vorrichtung aufzuspritzen, oder, falls das lösungsmittelhaltige System höherviskos sein sollte, aufzurakeln. Wie bereits zuvor erwähnt, kommen dafür insbesondere Vinylgruppen tragende Organosiliciumverbindungen in Betracht. Hiermit ist bei Raumtemperatur innerhalb weniger Sekunden ein hochvernetztes Silikon erhältlich. Nach anschließender Trocknung liegt auf dem Trägerfilm eine gleichmäßige Silikonschicht vor. Die Trocknungstemperatur hängt dabei vom verwendeten Lösungsmittel und von der Art des Trägerfilms ab. Bei Polyäthylenterephtalatfilmen kann sie 150°C betragen. Während der Trocknung findet auch noch eine gewisse Vernetzung der Silikonschicht statt. Für die Herstellung eines erfindungsgemäßen Lackfilmes als besonders geeignet haben sich Silikonschichten von einem oder wenigen Mikrometern Dicke erwiesen.To produce the new lacquer film, it is proposed to spray a solvent-containing system, which contains at least one organosilicon compound carrying hydrogen on the silicon atom and at least one organosilicon compound bearing alkenyl groups, and a platinum or iridium catalyst, onto one side of a web-like carrier film using a suitable device, or, if that solvent-based system should be more viscous to apply. As already mentioned above, organosilicon compounds bearing vinyl groups are particularly suitable for this. This enables a highly cross-linked silicone to be obtained at room temperature within a few seconds. After subsequent drying, there is an even silicone layer on the carrier film. The drying temperature depends on the solvent used and the type of carrier film. For polyethylene terephthalate films it can be 150 ° C. A certain amount of crosslinking of the silicone layer also takes place during the drying. Silicone layers with a thickness of one or a few micrometers have proven to be particularly suitable for producing a paint film according to the invention.
Auf den mit einer erfindungsgemäßen Silikonschicht versehenen Trägerfilm läßt sich besonders leicht eine gleichmäßig dicke Klebstoffschicht erzeugen, wenn gemäß Anspruch 18 verfahren wird. Mit Hilfe des vorgeschlagenen Lösungsmittels ist eine einwandfreie Benetzung der Silikonschicht sowie eine relativ schnelle Trocknung der Klebstoffschicht möglich.A uniformly thick adhesive layer can be produced particularly easily on the carrier film provided with a silicone layer according to the invention if the procedure is as claimed in claim 18. With the help of the proposed solvent, a perfect wetting of the silicone layer and a relatively quick drying of the adhesive layer is possible.
Wenn die so hergestellte Folie nicht gleich weiterverarbeitet, d.h. mit einer oder mehreren Lackschichten versehen werden soll, wird vorgeschlagen, sie mit einem bahnartigen Abdeckfilm, welcher die Eigenschaft haben muß, daß er die Klebstoffschicht nicht beschädigt, abzudecken. So kann die Folie problemlos ein oder mehrlagig in Bögen oder aufgerollt gelagert werden, bis sie weiterverarbeitet wird. Eine weitere Möglichkeit ist, die Rückseite des Trägerfilms mit einer Ablösungsschicht zu versehen. So kann die Folie mehrlagig in Bögen oder aufgerollt gelagert werden, bis sie weiterverarbeitet wird.If the film thus produced is not to be further processed immediately, ie to be provided with one or more layers of lacquer, it is proposed that it be provided with a web-like cover film, which must have the property that it has the adhesive layer not damaged, cover. In this way, the film can be stored in one or more layers in sheets or rolled up without any problems until it is processed further. Another possibility is to provide the back of the carrier film with a release layer. The film can be stored in multiple layers in sheets or rolled up until it is processed further.
Eine Beschädigung der Klebstoffschicht wird vermieden und/oder eine einwandfreie Entfernbarkeit des Abdeckfilms wird gewährleistet, wenn einer der Ansprüche 19 bis 21 zur Anwendung kommt.Damage to the adhesive layer is avoided and / or perfect removal of the cover film is ensured if one of claims 19 to 21 is used.
Als Abdeckfilm kommen dabei insbesondere mit einer erfindungsgemäßen Silikonschicht gemäß Anspruch 21 beschichtete Polyesterfolien, speziell Polyäthylenterephtalatfolien in Betracht. Es genügt dabei, wenn als Abdeckfilm eine Folie geringerer Dicke als die des Trägerfilms eingesetzt wird, da ersterer einer geringeren mechanischen Beanspruchung ausgesetzt ist wie letzterer.Polyester films coated with a silicone layer according to the invention, in particular polyethylene terephthalate films, are particularly suitable as cover films. It is sufficient if a film of a smaller thickness than that of the carrier film is used as the cover film, since the former is subjected to less mechanical stress than the latter.
Weiterhin kommen als Abdeckfilm mit einer erfindungsgemäßen Silikonschicht gemäß Anspruch 21 beschichtete Papiere besonders in Betracht.Papers coated with a silicone layer according to the invention are also particularly suitable as cover films.
Auf die Klebstoffschicht wird der Lack in flüssiger Form aufgebracht und anschließend getrocknet. Bei Mehrschichtlacken wird der Vorgang wiederholt. Danach kann das Produkt entweder aufgerollt oder in Stücken geschnitten aufbewahrt werden. Bei Bedarf kann von dem Produkt ein der mit Lack zu bedeckenden Fläche entsprechend großes Stück abgeschnitten werden, die Lackschicht mitsamt der Klebstoffschicht vom dem siliconbeschichteten Trägerfilm von Hand abgezogen und auf die zu bedeckende Fläche nach Art eines Pflasters aufgeklebt werden.The lacquer is applied in liquid form to the adhesive layer and then dried. The process is repeated for multi-layer paints. The product can then either be rolled up or stored in pieces. If necessary, a large piece of the area to be covered with lacquer can be cut off from the product, the lacquer layer together with the adhesive layer can be pulled off from the silicon-coated carrier film by hand and stuck onto the surface to be covered in the manner of a plaster.
Der erfindungsgemäße Lackfilm kann auch gemäß Anspruch 25 aufbereitet sein. Das Freischneiden der einzelnen Bereiche kann dabei durch ein Stanzverfahren erfolgen. Auf diese Weise können auch scharf begrenzte, aus Lack bestehende, selbstklebende Symbole,Zahlen und Buchstaben auf rationelle Weise erzeugt werden.The paint film according to the invention can also be prepared according to claim 25. The individual areas can be cut free by a stamping process. That way you can sharp, self-adhesive symbols, numbers and letters made of lacquer can also be produced in a rational manner.
Nachstehend werden Ausführungsbeispiele für die Zusammensetzung und Gestalt der einzelnen Bestandteile des neuen Lackfilmes beschrieben.Exemplary embodiments for the composition and shape of the individual components of the new paint film are described below.
Der neue Lackfilm wird vorzugsweise mit einer kontinuierlich arbeitenden Vorrichtung hergestellt, wie sie in der EP-PS 50 794 beschrieben und schematisch dargestellt ist. Als Trägerfilm für den Lackfilm kommt eine Polyäthylenterephthalatfolie von etwa 50 bis 80 Mikrometern Dicke und etwa einem Meter Breite zum Einsatz, die zu einer Rolle aufgewickelt ist. Dieser Trägerfilm weist optimale Bedingungen zur Herstellung des erfindungsgemäßen Lackfilms auf, weil er oberflächenglatt ist und eine hervorragende mechanische, chemische und thermische Beständigkeit besitzt. Der Trägerfilm kann der Vorrichtung endlos von der Rolle oder in Bögen zugeführt werden. Dieser Trägerfilm ist in einem vorangegangenen Verfahren auf einer Seite mit einer etwa einem Mikrometer dicken Silikonschicht versehen worden, die hochvernetzt und vom alkenylgruppenhaltigen, speziell vom vinylgruppenhaltigen Polyadditionstyp ist. Der Trägerfilm ist dabei bei etwa 150°C getrocknet worden. Die Oberflächenspannung der Silikonschicht beträgt 22 dyn/cm. Als mittlerer Trennwert der Silikonschicht wurden 11,25 ⁺ 3,75 cN/cm ermittelt, wobei die nachfolgend aufgeführte Prüfmethode zur Anwendung kam:The new paint film is preferably produced with a continuously operating device, as described and shown schematically in EP-PS 50 794. A polyethylene terephthalate film of about 50 to 80 micrometers thick and about one meter wide is used as the carrier film for the lacquer film, which is wound into a roll. This carrier film has optimal conditions for producing the lacquer film according to the invention because it is smooth on the surface and has excellent mechanical, chemical and thermal resistance. The carrier film can be fed to the device endlessly from the roll or in sheets. In a previous process, this carrier film was provided on one side with an approximately one micrometer thick silicone layer which is highly crosslinked and of the alkenyl group-containing, especially of the vinyl group-containing, polyaddition type. The carrier film has been dried at about 150 ° C. The surface tension of the silicone layer is 22 dynes / cm. The average separation value of the silicone layer was determined to be 11.25 ⁺ 3.75 cN / cm, using the test method listed below:
Ein Trägerfilmstreifen vom 4 cm Breite und einer beliebigen, vorzugsweise einige zehn Zentimeter betragenden Länge wird auf der siliconbeschichteten Seite mit einem Stück Testklebeband gleicher Breite und etwa gleicher Länge bedeckt. Das Testklebeband ist ein Polyvinylchloridfilm, auf welchem eine Klebstoffschicht auf Kautschukbasis verankert ist. Ein solches Testklebeband ist beispielsweise unter der Bezeichnung Tesa 154 von der Firma Beiersdorf AG, Hamburg, erhältlich. Das Testklebeband wird mit der Klebstoffschicht auf die Silikonschicht gelegt und die Probe ungefähr 20 Stunden bei Raumtemperatur unter einem Druck von 8 bis 10 kPa gelagert. Anschließend wird der mittlere Trennwert durch Schälkraftmessung mehrerer Proben mit einer geeigneten Apparatur ermittelt.A carrier film strip of 4 cm in width and of any desired length, preferably a few tens of centimeters, is covered on the silicon-coated side with a piece of test adhesive tape of the same width and approximately the same length. The test adhesive tape is a polyvinyl chloride film on which an adhesive layer based on rubber is anchored. Such a test adhesive tape is available, for example, under the name Tesa 154 from Beiersdorf AG, Hamburg. The test tape is placed on the silicone layer with the adhesive layer and the sample is stored for about 20 hours at room temperature under a pressure of 8 to 10 kPa. The mean separation value is then determined by measuring the peel force of several samples using suitable equipment.
Bei einen Abzugswinkel von 180° und einer Abzugsgeschwindigkeit von 1000 mm/min ergab sich für 4 cm breite siliconbeschichtete Trägerfilmstreifen der oben genannten Art ein mittlerer Trennwert von 45 ⁺ 15 cN, was 11,25 ⁺ 3,75 cN/cm entspricht. Dabei verblieb die Klebstoffschicht vollständig auf dem Polyvinylchloridfilm und die Silikonschicht verblieb vollständig auf dem Trägerfilm. Ein derartig beschichteter Trägerfilm hat sich für den vorliegenden Anwendungsfall als optimal geeignet herausgestellt.At a take-off angle of 180 ° and a take-off speed of 1000 mm / min, a mean separation value of 45 ⁺ 15 cN, which corresponds to 11.25 ⁺ 3.75 cN / cm, resulted for 4 cm wide silicone-coated carrier film strips of the type mentioned above. The adhesive layer remained completely on the polyvinyl chloride film and the silicone layer remained completely on the carrier film. A carrier film coated in this way has proven to be optimally suitable for the present application.
Auf die siliconbeschichtete Seite des Trägerfilms wird ein hochviskoses, trichloräthylenhaltiges Styrol-Isopren-Styrol-Blockpolymersystem zur Erzeugung einer Klebstoffschicht aufgerakelt.A highly viscous, trichlorethylene-containing styrene-isoprene-styrene block polymer system is knife-coated onto the silicon-coated side of the carrier film to produce an adhesive layer.
Dabei wird der Kleber in einer solchen Menge aufgerakelt, daß sich nach dessen Trocknen eine Kleberschicht von 10 bis 14 g/m² ergibt. Anschließend wird der Trägerfilm bei einer Temperatur, die oberhalb 85°C liegt, getrocknet. Die so hergestellte Klebstoffschicht ist selbstklebend und besitzt eine große Haftfähigkeit, z.B. gegenüber Metall-, Kunststoff- und Glasoberflächen, die auch lakkiert sein können, sowie ein hohes Maß an Kohäsion.The adhesive is applied in such an amount that an adhesive layer of 10 to 14 g / m² is obtained after it has dried. The carrier film is then dried at a temperature which is above 85 ° C. The adhesive layer thus produced is self-adhesive and has great adhesiveness, e.g. compared to metal, plastic and glass surfaces, which can also be painted, as well as a high degree of cohesion.
Auf die Klebstoffseite des so vorbereiteten, abgekühlten Trägerfilms wird Kraftfahrzeuglack aufgebracht. Wenn ein Unifarbton gewünscht wird, wird ein lösungsmittelhaltiges Zweikomponenten-Acryl-Isocyanatsystem gleichmäßig aufgespritzt und getrocknet. Das System vernetzt dabei gut haftend auf der Klebstoffschicht. Das Verfahren wird so lange durchgeführt, bis ei ne Lackschichtdicke von etwa 20 bis 40 Mikrometern erreicht ist. Der so hergestellte Lackfilm ist stark, sehr flexibel, farbecht und wetterbeständig.Automotive paint is applied to the adhesive side of the cooled carrier film prepared in this way. If a solid color is desired, a solvent-containing two-component acrylic isocyanate system is sprayed on evenly and dried. The system networks well with the adhesive layer. The process is continued until ei ne layer thickness of about 20 to 40 microns is reached. The paint film produced in this way is strong, very flexible, colourfast and weatherproof.
Wenn ein Metallicfarbton gewünscht wird, wird dafür als erste Schicht eine physikalisch trocknender Acryllack gleichmäßig auf die Klebstoffschicht aufgespritzt und getrocknet. Der Lack haftet einwandfrei auf der Klebstoffschicht. Danach wird ein Zweikomponenten-Acryl-Isocyanat-Klarlack aufgespritzt und getrocknet. Der Klarlack haftet einwandfrei auf der ersten Lackschicht. Die gesamte Lackschichtdicke beträgt auch hier etwa 25 bis 45 Mikrometer. Dieser Lackfilm entspricht im Lackschichtaufbau und damit in der optischen Wirkung dem von Original-Metallic-Kraftfahrzeugeinbrennlack, ist stark, sehr flexibel, farbecht und wetterbeständig.If a metallic color is desired, a physically drying acrylic lacquer is sprayed evenly onto the adhesive layer and dried as the first layer. The paint adheres perfectly to the adhesive layer. Then a two-component acrylic isocyanate clear lacquer is sprayed on and dried. The clear coat adheres perfectly to the first coat of paint. The total lacquer layer thickness is also about 25 to 45 micrometers here. This paint film corresponds to the paint layer structure and thus the optical effect of original metallic automotive stove enamels, is strong, very flexible, colourfast and weatherproof.
Bei beiden Ausführungsbeispielen liegt bei dem Lackfilm zunächst eine durchgehende Lackschicht vor. Durch Ausstanzen werden nun einzelne, handlich große Bereiche der Lackschicht von seitlich an sie angrenzenden Lackschichtbereichen freigeschnitten, wobei die darunterliegende Klebstoffschichtbereiche mit erfaßt und ebenfalls freigeschnitten werden. Anschließend wird der Lackfilm in Teilstücke zerschnitten und verpackt. Von den Teilstücken können vom Verbraucher bei Bedarf trockene Lackschichtstückchen von Hand abgezogen und durch Andrücken mit ihrer Klebstoffschichtseite auf auszubessernde Flächen aufgeklebt werden. Dabei spielt es keine Rolle, wenn beim vorher beschriebenen Stanzverfahren die Silikonschicht auch noch bereichsweise freigeschnitten worden ist. Die Silikonschicht haftet so wenig an der Klebstoffschicht, daß sie auf keinen Fall abgezogen wird.In both exemplary embodiments, the lacquer film initially has a continuous lacquer layer. Punching out individual, handy, large areas of the lacquer layer is now cut free from lacquer layer regions adjoining them laterally, the adhesive layer regions underneath also being detected and also cut free. The lacquer film is then cut into pieces and packaged. If necessary, dry pieces of lacquer layer can be peeled off from the sections by the consumer and glued onto their surfaces to be repaired with their adhesive layer side. It does not matter if the silicone layer has also been cut free in some areas in the previously described stamping process. The silicone layer adheres so little to the adhesive layer that it is never peeled off.
Selbstverständlich ist es auch möglich, den Lackfilm ohne vorheriges Stanzverfahren direkt in Teilstücke zu zerschneiden und zu verpacken. Der Verbraucher kann sich dann bei Bedarf Abschnitte in der gewünschten Größe zurechtschneiden.Of course, it is also possible to cut and package the paint film directly into sections without prior punching. The consumer can then cut sections of the desired size if necessary.
Claims (26)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3527609 | 1985-08-01 | ||
DE19853527609 DE3527609A1 (en) | 1985-08-01 | 1985-08-01 | TRANSFERABLE LACQUER FILM AND METHOD FOR THEIR PRODUCTION |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0213327A2 true EP0213327A2 (en) | 1987-03-11 |
EP0213327A3 EP0213327A3 (en) | 1988-11-17 |
Family
ID=6277394
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86109296A Withdrawn EP0213327A3 (en) | 1985-08-01 | 1986-07-08 | Lacquer transfer film and process for preparing it |
Country Status (6)
Country | Link |
---|---|
US (1) | US4766038A (en) |
EP (1) | EP0213327A3 (en) |
JP (1) | JPS6233635A (en) |
AU (1) | AU566661B2 (en) |
DD (1) | DD251527A5 (en) |
DE (1) | DE3527609A1 (en) |
Cited By (4)
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WO1991003381A1 (en) * | 1989-08-31 | 1991-03-21 | Juergen Eissele | Self-adhesive dry-transfer images, process for their manufacture and method of use |
EP0541103A1 (en) * | 1991-11-07 | 1993-05-12 | Diafoil Hoechst Co., Ltd. | Laminated polyester film |
WO2003020528A3 (en) * | 2001-08-29 | 2003-10-09 | Wipak Walsrode Gmbh & Co Kg | Coloured decoration transfer system |
EP1470933A2 (en) * | 2003-04-24 | 2004-10-27 | Aluminium Féron GmbH & Co. KG | Protective layer comprising lacquer |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3527609A1 (en) * | 1985-08-01 | 1987-02-05 | Nordipa Ag | TRANSFERABLE LACQUER FILM AND METHOD FOR THEIR PRODUCTION |
US4832991A (en) * | 1987-11-03 | 1989-05-23 | Eastman Kodak Company | Coating process |
JPH02150988A (en) * | 1988-12-01 | 1990-06-11 | Kubota Ltd | Automatic vending machine with change dispensing device |
DE19628966C1 (en) * | 1996-07-18 | 1997-12-18 | Daimler Benz Ag | Process for applying a lacquer film on three-dimensional curved surfaces of dimensionally stable substrates |
GB2330795B (en) * | 1997-11-04 | 1999-10-13 | Ici Plc | Facilitation of the choice of paint according to the visual appearance of a dried coat when on a surface |
US6033762A (en) * | 1998-05-08 | 2000-03-07 | Decker Tape Products, Co., Inc. | Self-adhesive resealable tamper-evident tape |
DE19837774A1 (en) * | 1998-08-20 | 2000-02-24 | Waldemar Sturn | Colored film to touch-up slight vehicle paintwork damage carries a dry paint and an adhesive layer to be bonded over the damaged paintwork area |
US7332046B2 (en) * | 2003-09-26 | 2008-02-19 | Eastman Chemical Company | Methods of blocking stains on a substrate to be painted, and composites suitable for use in such methods |
NL1024933C2 (en) * | 2003-12-03 | 2005-06-06 | Visker Beheer B V | Method for applying a bonded cover layer to a substrate, method for manufacturing a coating package and a coating package. |
US20060177649A1 (en) * | 2005-02-07 | 2006-08-10 | Clark Mark D | Methods of blocking stains on a substrate to be painted, and composites suitable for use in such methods |
WO2007048141A2 (en) | 2005-10-21 | 2007-04-26 | Entrotech Composites, Llc | Composite articles comprising protective sheets and related methods |
US10035932B2 (en) | 2007-09-25 | 2018-07-31 | Aero Advanced Paint Technology, Inc. | Paint replacement films, composites therefrom, and related methods |
US10981371B2 (en) | 2008-01-19 | 2021-04-20 | Entrotech, Inc. | Protected graphics and related methods |
US8434283B1 (en) | 2009-02-14 | 2013-05-07 | Michelee Bartolo-Howell | Extreme edge |
EP3419826A4 (en) | 2016-09-20 | 2019-12-18 | Entrotech, Inc. | Paint film appliques with reduced defects, articles, and methods |
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DE3527609A1 (en) * | 1985-08-01 | 1987-02-05 | Nordipa Ag | TRANSFERABLE LACQUER FILM AND METHOD FOR THEIR PRODUCTION |
-
1985
- 1985-08-01 DE DE19853527609 patent/DE3527609A1/en active Granted
-
1986
- 1986-07-08 EP EP86109296A patent/EP0213327A3/en not_active Withdrawn
- 1986-07-21 US US06/887,787 patent/US4766038A/en not_active Expired - Fee Related
- 1986-07-24 AU AU60495/86A patent/AU566661B2/en not_active Ceased
- 1986-07-29 DD DD86293058A patent/DD251527A5/en not_active IP Right Cessation
- 1986-07-31 JP JP61178977A patent/JPS6233635A/en active Pending
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EP0018624A2 (en) * | 1979-05-05 | 1980-11-12 | Th. Goldschmidt AG | Process for the preparation of crosslinked organopolysiloxanes and their use as agent for abhesive coating compositions for sheetlike carriers |
EP0050794A1 (en) * | 1980-10-29 | 1982-05-05 | Nordipa AG | Transfer lacquer film and method of making it |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1991003381A1 (en) * | 1989-08-31 | 1991-03-21 | Juergen Eissele | Self-adhesive dry-transfer images, process for their manufacture and method of use |
US5322708A (en) * | 1989-08-31 | 1994-06-21 | Juergen Eissele | Self-adhesive dry-transfer decals, process for their manufacture and method of use |
EP0541103A1 (en) * | 1991-11-07 | 1993-05-12 | Diafoil Hoechst Co., Ltd. | Laminated polyester film |
WO2003020528A3 (en) * | 2001-08-29 | 2003-10-09 | Wipak Walsrode Gmbh & Co Kg | Coloured decoration transfer system |
EP1470933A2 (en) * | 2003-04-24 | 2004-10-27 | Aluminium Féron GmbH & Co. KG | Protective layer comprising lacquer |
EP1470933A3 (en) * | 2003-04-24 | 2006-04-05 | Aluminium Féron GmbH & Co. KG | Protective layer comprising lacquer |
Also Published As
Publication number | Publication date |
---|---|
DE3527609A1 (en) | 1987-02-05 |
JPS6233635A (en) | 1987-02-13 |
DD251527A5 (en) | 1987-11-18 |
AU566661B2 (en) | 1987-10-29 |
US4766038A (en) | 1988-08-23 |
AU6049586A (en) | 1987-02-05 |
DE3527609C2 (en) | 1988-05-26 |
EP0213327A3 (en) | 1988-11-17 |
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