EP0121179A2 - Backing for decalcomanias of the pull-off or the slide-off type - Google Patents

Backing for decalcomanias of the pull-off or the slide-off type Download PDF

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Publication number
EP0121179A2
EP0121179A2 EP84103093A EP84103093A EP0121179A2 EP 0121179 A2 EP0121179 A2 EP 0121179A2 EP 84103093 A EP84103093 A EP 84103093A EP 84103093 A EP84103093 A EP 84103093A EP 0121179 A2 EP0121179 A2 EP 0121179A2
Authority
EP
European Patent Office
Prior art keywords
separating layer
copolymer
water
layer
decals
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.)
Granted
Application number
EP84103093A
Other languages
German (de)
French (fr)
Other versions
EP0121179B1 (en
EP0121179A3 (en
Inventor
Henner Drum
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.)
Hoffmann & Engelmann AG
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Hoffmann & Engelmann AG
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Publication date
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Publication of EP0121179A2 publication Critical patent/EP0121179A2/en
Publication of EP0121179A3 publication Critical patent/EP0121179A3/en
Application granted granted Critical
Publication of EP0121179B1 publication Critical patent/EP0121179B1/en
Expired legal-status Critical Current

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Classifications

    • 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
    • B44C1/175—Transfer using solvent
    • 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
    • B44C1/175—Transfer using solvent
    • B44C1/1754—Decalcomanias provided with a layer being specially adapted to facilitate their release from a temporary carrier
    • 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
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851—Intermediate layer is discontinuous or differential
    • Y10T428/2486—Intermediate layer is discontinuous or differential with outer strippable or release layer
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24934—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer
    • 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
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • 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
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate
    • 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]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper

Definitions

  • the invention relates to a carrier for stripping - or Abschiebemul of absorbent paper with an applied barrier layer and a soluble separating layer by water for receiving a pressure and / or lacquer layer.
  • Carriers for decals or decals are known (DE-OS 25 51 860 corresponding to US Pat. No. 4,049,860 or also US Pat. No. 2,970,076). They contain a water- or heat-soluble separating layer, on which the decoration picture is printed by screen printing or offset printing. When transferring the decor image to the desired surface, either manually or mechanically, depending on the procedure, a residual amount of separating layer components is always transferred.
  • Components of the separating layer are usually gum arabic, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl acetate, polyglycols or oligosaccharides or polysaccharides.
  • Decals or decals are also known which are used outside the ceramic area. These images are transferred to glass, metal, enamel, plastic etc. at temperatures up to max. Fixed at 250 ° C on the base, while the paint mask surrounding the decor image is retained.
  • a significant drawback of the known separating layers is that go with- transferred release layer components at attack of water on the substrate into solution again and the adhesion of the D ekorsentes reduce or cancel.
  • Such images can also be produced in reverse printing, with the advantage that a heat-activatable adhesive is applied in the last working step. Such images then adhere permanently to the base after the heat treatment.
  • the solution to this problem is based on a support for decals or decals of the type mentioned above, and it is characterized in that the separating layer contains or consists of a homo- or copolymer of acrylic acid and / or a copolymer of alkyl vinyl ether and maleic anhydride.
  • the separating layer preferably consists of a mixture of a homo- or copolymer of acrylic acid or a copolymer of methyl vinyl ether and maleic anhydride, and a polysaccharide, in particular dextrin.
  • homopolymers or copolymers of acrylic acid have proven suitable as materials for the separating layer.
  • the homopolymers have molecular weights of 2,000 to 250,000.
  • suitable copolymers are those composed of acrylic acid / acrylic acid esters or methacrylic acid esters. Their molecular weights are in the range from 30,000 to 260,000. These products are commercially available.
  • the homopolymers or copolymers are preferably used in a mixture with customary substances known and suitable for the separating layer. These include the substances described at the beginning. Mixtures with polysaccharides, in particular dextrin, are very particularly preferably used. For the optimal configuration of the invention, it has proven to be advantageous if the separating layer contains at least 50 percent by weight of homo- or copolymer.
  • Separating layers consisting of homo- or copolymers of acrylic acid mixed with dextrin can be used to decorate unglazed ceramic substrates. After baking in the rapid firing process, no residues are visible in the non-image areas.
  • Copolymers of alkyl vinyl ether and maleic anhydride, in particular of methyl vinyl ether and maleic anhydride, have also proven to be very suitable as materials for the separating layer according to the invention.
  • Mixtures of homo- or copolymers of acrylic acid and of copolymers of alkyl vinyl ether and maleic anhydride can also be used for the separating layer according to the invention.
  • different dissolving and floating times of the images are achieved, which is particularly important in the case of machine application.
  • simple and relatively inexpensive separating layers can be achieved, which can be used for a wide variety of applications.
  • the invention achieves that a carrier for decals or decals can be provided, which meets both the requirements for , To suit decorative images after the residue-free decorations, may be used as well for a water soluble coating, with subsequent fixing of the D-e korsentes, by transferring the remainder of release layer components in a water-insoluble state.
  • the invention is explained in more detail with reference to the attached figure. It shows schematically a cross section of a carrier according to the invention for decals or decals. Position 1 of the paper carrier is specified therein, on average with a mass per unit area in the range from approximately 100 to 200 g / m 2 .
  • the paper carrier contains a barrier layer 2, which makes one surface of the paper carrier less porous. It can consist of pure surface sizing or of a sealable spread, for example starch, casein, glue, alkali metal silicate or water glass with and without clay filler. The presence of the barrier layer 2 prevents excessive penetration and absorption of the material according to the invention to be applied for the separating layer 3.
  • the separating layer 3 made of the materials described is applied over the barrier layer 2 by means of a suitable application method.
  • the dry weight to be applied is 6 to 15 g / m 2 . Drying takes place at approx. 80 ° C in a drying tunnel.
  • the individual components are first dissolved in water.
  • Dextrin is sprinkled in cold water and dissolved with moderate stirring.
  • Polyacrylic acid is commercially available as a solution.
  • copolymer of acrylic acid and acrylic acid ester (PAS / PAE) is dissolved in water at 70 ° C. by neutralization, for example by adding 23 parts of triethanolamine to 100 parts of copolymer.
  • dextrin can impair residue-free combustion, according to the invention a proportion of 50 percent by weight in the formulation should not be exceeded.
  • dextrin is also useful to the extent that its presence has a positive influence on the floating and peeling properties with regard to the separating layer and the decor.
  • dextrin is suitable as a reaction partner to PVE / MA.
  • the paper supports provided with the separating layers 1 to 9 are coated with a commercially available, residue-free burning acrylic varnish (varnish 83450 from Degussa) as a varnish mask and air-dried.
  • test specimens prepared in this way are briefly placed on the back with water.
  • the peeling paint film is pushed onto unglazed ceramic pieces after 1 minute and spread using a rubber squeegee.
  • the air-dry pieces are then heated to 550 ° C., the paint mask being completely burned, and then cooled again.
  • Recipes 1 and 2 clearly show traces of unburned interface.
  • Recipes 3 to 9 show no traces of clays, i.e. Even at a relatively low firing temperature, the residues of the separating layer that are also transferred are burned without residue, without leaving soot particles.
  • a lacquer mask applied to the separating layer according to recipe 4 instead of an applied decorative image with lacquer mask is transferred in the usual way to a plastic container (bottle) as a base and exposed to a temperature of approximately 200 ° C. for 15 minutes.
  • a plastic container is treated accordingly, a material according to recipe 1 being used as the separating layer.
  • both containers are exposed to water containing surfactants as a test solution. While the paint mask, transferred with the help of recipe 4, which withstands the action of water for 20 minutes, the paint mask, which was transferred with the help of recipe 1 for the separating layer, floats after the same time.

Landscapes

  • Decoration By Transfer Pictures (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Laminated Bodies (AREA)

Abstract

Es wird ein Träger für Abzieh- oder Abschiebebilder aus saugfähigem Papier mit aufgebrachter Sperrschicht und einer durch Wasser löslichen Trennschicht Zur Aufnahme einer Druck- und/oder Lackschicht beschrieben, dessen Trennschicht ein Homo- oder Copolymerisat der Acrylsäure und/oder ein Copolymerisat aus Alkylvinylether und Maleinsäureanhydrid enthält oder dessen Trennschicht daraus besteht.A support for decals or decals made of absorbent paper with an applied barrier layer and a water-soluble separation layer for receiving a printing and / or lacquer layer is described, the separation layer of which is a homo- or copolymer of acrylic acid and / or a copolymer of alkyl vinyl ether and maleic anhydride contains or whose separating layer consists of it.

Description

Die Erfindung betrifft einen Träger für Abzieh- oder Abschiebebilder aus saugfähigem Papier mit aufgebrachter Sperrschicht und einer durch Wasser löslichen Trennschicht zur Aufnahme einer Druck- und/oder Lackschicht.The invention relates to a carrier for stripping - or Abschiebebilder of absorbent paper with an applied barrier layer and a soluble separating layer by water for receiving a pressure and / or lacquer layer.

Träger für Abzieh-oder Abschiebebilder sind bekannt (DE-OS 25 51 860 entsprechend US-PS 4,049,860 oder auch US-PS 2,970,076). Sie enthalten eine wasser- oder wärmelösliche Trennschicht, auf die der Druck des Dekorbildes durch Siebdruck oder Offsetdruck erfolgt. Bei der Übertragung des Dekorbildes auf die gewünschte Unterlage, entweder auf manuelle oder maschinelle Art, wird, je nach Verfahrensweise, immer eine Restmenge an Trennschichtbestandteilen mit übertragen. Bestandteile der Trennschicht sind in der Regel Gummi arabicum, Polyvinylalkohol, Carboxymethylcellulose, Polyvinylacetat, Polyglykole oder Oligo- bzw. Polysaccharide.Carriers for decals or decals are known (DE-OS 25 51 860 corresponding to US Pat. No. 4,049,860 or also US Pat. No. 2,970,076). They contain a water- or heat-soluble separating layer, on which the decoration picture is printed by screen printing or offset printing. When transferring the decor image to the desired surface, either manually or mechanically, depending on the procedure, a residual amount of separating layer components is always transferred. Components of the separating layer are usually gum arabic, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl acetate, polyglycols or oligosaccharides or polysaccharides.

Ein wichtiges Merkmal solcher mitübertragener Trennschichtbestandteile ist ihr rückstandsfreies Verbrennen beim anschließenden Einbrennen des Dekorbildes, das meist aus Mischungen anorganischer Pigmente und einer Lackmaske besteht.An important feature of such transferred transfer layer components is their residue-free burning when the decor image is subsequently burned in, which usually consists of mixtures of inorganic pigments and a paint mask.

Auf Unterlagen aus Glas oder Keramik mit Unterglasur kann man bei üblicher Durchführung unter Anwesenheit wasserlöslicher Trennschichtbestandteile und hoher Brenntemperatur qualitativ einwandreie, d.h. absolut grundfreie, dekorative Endprodukte erhalten.On substrates made of glass or ceramic with underglaze, water can be carried out in the usual manner in the presence of soluble separating layer constituents and a high firing temperature. Obtain qualitatively perfect, ie absolutely bottom-free, decorative end products.

Im Falle der Mitübertragung größerer Mengen wasserlöslicher Trennschichtbestandteile erweisen sich diese als hinderlich, vor allem bei der Übertragung auf unglasierte Keramikstücke, aber auch bei Anwendung kritischer Brennverfahren, wie Schnellbrand, oder bei Anwendung niederer Einbrenntemperaturen. In solchen Fällen hinterlassen mitgeführte Trennschichtbestandteile dauerhaft sichtbare, unerwünschte Rückstände nach dem Einbrennen.If larger amounts of water-soluble separating layer constituents are also transferred, these prove to be a hindrance, especially when transferring to unglazed ceramic pieces, but also when using critical firing processes, such as rapid firing, or when using low baking temperatures. In such cases, carried-along separating layer components leave permanently visible, undesirable residues after baking.

Es sind auch Abzieh- oder Abschiebebilder bekannt, die außerhalb des keramischen Bereichs eingesetzt werden. Diese Bilder werden nach dem Übertragen auf Glas, Metall, Email, Kunststoff etc. bei Temperaturen bis max. 250 °C auf der Unterlage fixiert, wobei die das Dekorbild umgebende Lackmaske erhalten bleibt. Ein wesentlicher Nachteil der bekannten Trennschichten liegt darin, daß mit- übertragene Trennschichtbestandteile bei Angriff von Wasser auf die Unterlage wieder in Lösung gehen und die Haftung des Dekorbildes mindern oder aufheben. Selbstverständlich können solche Bilder auch im Konterdruck hergestellt werden, mit dem Vorteil, daß im letzten Arbeitsgang ein wärmeaktivierbarer Kleber aufgebracht wird. Solche Bilder haften dann nach der Wärmebehandlung permanent auf der Unterlage. Nachteilig ist jedoch, daß das Bild nach der übertragung manuell nicht mehr positionierbar ist, da zwischen Dekorbild und Unterlage die wasserlösliche, gleitfähige Trennschicht fehlt. Dies hat besonders für unregelmäßig geformte Unterlagen große Bedeutung.Decals or decals are also known which are used outside the ceramic area. These images are transferred to glass, metal, enamel, plastic etc. at temperatures up to max. Fixed at 250 ° C on the base, while the paint mask surrounding the decor image is retained. A significant drawback of the known separating layers is that go with- transferred release layer components at attack of water on the substrate into solution again and the adhesion of the D ekorbildes reduce or cancel. Of course, such images can also be produced in reverse printing, with the advantage that a heat-activatable adhesive is applied in the last working step. Such images then adhere permanently to the base after the heat treatment. However, it is disadvantageous that the image is no longer positioned manually after the transfer bar, as between D and ekorbild pad lacks the water-soluble lubricious release layer. This is particularly important for irregularly shaped documents.

Es war Aufgabe der vorliegenden Erfindung, einen Träger für Abzieh- oder Abschiebebilder mit einer durch Wasser löslichen Trennschicht zu schaffen, der sowohl zum Aufbringen eines Dekorbildes auf Gegenstände, wie Email, Glas, Edelstahl, poröse Keramik, bei denen das Einbrennen bei niederen Einbrenntemperaturen oder im Schnellbrand erfolgen kann, als auch zum Aufbringen eines Dekorbildes auf zum Beispiel Kunststoffoberflächen, bei denen lediglich ein Fixieren des Dekorbildes erfolgt, geeignet ist.It was an object of the present invention to provide a support for decals or decals with a water-soluble separating layer, which is used both for applying a decorative image to objects such as enamel, glass, stainless steel, porous ceramics, in which baking at low baking temperatures or can be carried out in rapid firing, and is also suitable for applying a decorative image to, for example, plastic surfaces in which only the decorative image is fixed.

Die Lösung dieser Aufgabe geht aus von einem Träger für Abzieh- oder Abschiebebilder der eingangs genannten Art, und sie ist dadurch gekennzeichnet, daß die Trennschicht ein Homo- oder Copolymerisat der Acrylsäure und/oder ein Copolymerisat aus Alkylvinylether und Maleinsäureanhydrid enthält oder daraus besteht. Vorzugsweise besteht die Trennschicht aus einem Gemisch aus einem Homo- oder Copolymerisat der Acrylsäure oder einem Copolymerisat aus Methylvinylether und Maleinsäureanhydrid, und einem Polysaccharid, insbesondere Dextrin.The solution to this problem is based on a support for decals or decals of the type mentioned above, and it is characterized in that the separating layer contains or consists of a homo- or copolymer of acrylic acid and / or a copolymer of alkyl vinyl ether and maleic anhydride. The separating layer preferably consists of a mixture of a homo- or copolymer of acrylic acid or a copolymer of methyl vinyl ether and maleic anhydride, and a polysaccharide, in particular dextrin.

Hierdurch wird erreicht, daß durch die Übertragung des Dekorbildes von seinem Träger auf poröse keramische Unterlagen zum Beispiel unter folgender Anwendung kritischer Brennverfahren oder auf Unterlagen, die lediglich einem anschließenden Fixierprozeß unterworfen werden, das Aussehen des Endproduktes und die endgültige Haftung des Dekorbildes nicht mehr schädigend beeinflußt werden. Die sich ergebenden Dekorbilder auf den Unterlagen zeigen keine Tonererscheinungen, sie sind auch nicht durch Feuchtigkeit oder Wasserangriff ohne weiteres ablösbar. Nach dem übertragen etwa auf unglasierte Keramikstücke und nach dem Einbrennen, bei dem die Lackmaske verbrennt, ergeben sich saubere Dekorbilder, auch dann, wenn ein großer Anteil an Trennschichtbestandteilen mitübertragen wurde. Im Falle, daß das Dekorbild auf eine Unterlage übertragen wird, a!:f der es lediglich fixiert wird, d.h. unter Trhaltung der Lackmaske, bei der normalerweise die Gefahr besteht, daß das Dekorbild sich durch wäßrigen Angriff löst, da wasserlösliche Bestandteile der Trennschicht mitübertragen wurden, kann dieser Effekt erfindungsgemäß verhindert werden.This ensures that by transferring the decorative image from its support to porous ceramic substrates, for example, using the following application shear burning process or on documents that are only subjected to a subsequent fixing process, the appearance of the end product and the final liability of the decorative image are no longer adversely affected. The resulting decorative images on the documents do not show any signs of toner, nor are they easily removable by moisture or water attack. After transferring, for example, to unglazed ceramic pieces and after baking, in which the paint mask burns, clean decorative images result, even if a large proportion of separating layer components have also been transferred. In the event that the decor image is transferred to a base, a ! : f it is only fixed, ie while keeping the lacquer mask, in which there is normally a risk that the decorative image will dissolve due to aqueous attack, since water-soluble constituents of the separating layer have also been transferred, this effect can be prevented according to the invention.

Als Materialien für die Trennschicht haben sich Homo-oder Copolymerisate der Acrylsäure allein oder in Mischung als geeignet erwiesen. Die Homopolymerisate besitzen Molekulargewichte von 2.000 bis 250.000. Als Copolymerisate kommen beispielsweise solche aus Acrylsäure/ Acrylsäure- bzw. Methacrylsäureestern in Betracht. Ihre Molekulargewichte liegen im Bereich von 30.000 bis 260.000. Diese Produkte sind im Handel erhältlich.Homopolymers or copolymers of acrylic acid, alone or as a mixture, have proven suitable as materials for the separating layer. The homopolymers have molecular weights of 2,000 to 250,000. Examples of suitable copolymers are those composed of acrylic acid / acrylic acid esters or methacrylic acid esters. Their molecular weights are in the range from 30,000 to 260,000. These products are commercially available.

Es hat sich gezeigt, daß die Homo- oder Copolymerisate der Acrylsäure vorzügliche Brenneigenschaften besitzen und vornehmlich schon in niederen Temperaturbereichen verbrennen oder sich zersetzen, ohne daß die Verbrennung mit übermäßig starkem Rußniederschlag erfolgt.It has been shown that the homopolymers or copolymers of acrylic acid have excellent burning properties and primarily burn or decompose even in low temperature ranges without the combustion taking place with excessive soot precipitation.

Die Homo- oder Copolymerisate werden vorzugsweise im Gemisch mit üblichen, für die Trennschicht geeigneten und bekannten Substanzen eingesetzt. Hierzu gehören die eingangs beschriebenen Stoffe. Ganz besonders bevorzugt werden Mischungen eingesetzt mit Polysacchariden, insbesondere Dextrin. Zur optimalen Ausgestaltung der Erfindung hat es sich als günstig erwiesen, wenn die Trennschicht mindestens 50 Gewichtsprozent an Homo- oder Copolymerisat enthält.The homopolymers or copolymers are preferably used in a mixture with customary substances known and suitable for the separating layer. These include the substances described at the beginning. Mixtures with polysaccharides, in particular dextrin, are very particularly preferably used. For the optimal configuration of the invention, it has proven to be advantageous if the separating layer contains at least 50 percent by weight of homo- or copolymer.

Trennschichten, die aus Homo- oder Copolymerisaten der Acrylsäure im Gemisch mit Dextrin bestehen, können für die Dekoration von unglasierten Keramikunterlagen eingesetzt werden. Nach dem Einbrennen im Schnellbrandverfahren sind keinerlei Rückstände in den Nichtbildbereichen zu erkennen.Separating layers consisting of homo- or copolymers of acrylic acid mixed with dextrin can be used to decorate unglazed ceramic substrates. After baking in the rapid firing process, no residues are visible in the non-image areas.

Als Materialien für die erfindungsgemäße Trennschicht haben sich auch Copolymerisate aus Alkylvinylether und Maleinsäureanhydrid, insbesondere aus Methylvinylether und Maleinsäureanhydrid, als gut geeignet erwiesen.Copolymers of alkyl vinyl ether and maleic anhydride, in particular of methyl vinyl ether and maleic anhydride, have also proven to be very suitable as materials for the separating layer according to the invention.

Diese Produkte sind im Handel erhältlich. Sie weisen Molekulargewichte im Bereich von etwa 50.000 bis 200.000 auf und sind wasserlöslich. Sie eignen sich im Gemisch mit Substanzen, die reaktive Gruppen tragen, wie etwa Oligo- oder,Polysaccharide, Vinylpyrrolidon enthaltende Polymerisate, Polyvinylalkohol, Alkylamin, Polyalkylpolyamin oder andere Substanzen mit polyfunktionellen Gruppen, hervorragend für Trennschichten mit aufgebrachten Dekorbildern, die wäßrig gelöst auf Unterlagen übertragen werden, die man einem anschließenden Einbrennprozeß nicht unterwerfen kann. Es hat sich gezeigt, daß die übertragenen Trennschichtbestandteile bei den herrschenden Fixiertemperaturen miteinander vernetzen und einen wasserunlöslichen oder -schwerlöslichen Zustand herbeiführen. Hierdurch wird eine Unempfindlichkeit des Dekorbildes auf der Unterlage gegen Feuchtigkeit oder Wasserangriff erzielt. Gemische mit mindestens 50 Gewichtsprozent an erfindungsgemäßem Polymerisat oder Copolymerisat für die Trennschicht haben sich besonders bewährt.These products are commercially available. They have molecular weights in the range of approximately 50,000 to 200,000 and are water-soluble. They are suitable in a mixture with substances that carry reactive groups, such as Oligo- or, polysaccharides, vinylpyrrolidone-containing polymers, polyvinyl alcohol, alkylamine, polyalkylpolyamine or other substances with polyfunctional groups, excellent for separating layers with applied decorative images, which are transferred in aqueous solution to substrates which cannot be subjected to a subsequent baking process. It has been shown that the transferred separating layer components cross-link with one another at the prevailing fixing temperatures and bring about a water-insoluble or difficultly soluble state. As a result, the decor image on the base is insensitive to moisture or water attack. Mixtures with at least 50 percent by weight of the polymer or copolymer according to the invention for the separating layer have proven particularly useful.

Für die erfindungsgemäße Trennschicht können auch Mischungen von Homo- oder Copolymerisaten der Acrylsäure und von Copolymerisaten aus Alkylvinylether und Maleinsäueanhydrid eingesetzt werden. Hierdurch erreicht man, je nach Mischungsverhältnis, in Verbindung mit vorzugsweise Dextrin, unterschiedliche Löse- und Abschwimmzeiten der Bilder, was besonders bei maschineller Applikation von Bedeutung ist. Hierdurch erreicht man auch einfache und relativ preiswerte Trennschichten, die für die unterschiedlichsten Anwendungen einsetzbar sind.Mixtures of homo- or copolymers of acrylic acid and of copolymers of alkyl vinyl ether and maleic anhydride can also be used for the separating layer according to the invention. In this way, depending on the mixing ratio, in connection with preferably dextrin, different dissolving and floating times of the images are achieved, which is particularly important in the case of machine application. In this way, simple and relatively inexpensive separating layers can be achieved, which can be used for a wide variety of applications.

Durch die Erfindung wird insgesamt ereicht, daß ein Träger für Abzieh- oder Abschiebebilder zur Verfügung gestellt werden kann, der sowohl den Forderungen für Dekorbilder ,nach rückstandsfreien Dekorationen gerecht wird, als auch für eine wasserlösliche Beschichtung eingesetzt werden kann, mit anschließendem Fixieren des De-korbildes, unter Überführung der Resttrennschichtbestandteile in einen wasserunlöslichen Zustand.Overall, the invention achieves that a carrier for decals or decals can be provided, which meets both the requirements for , To suit decorative images after the residue-free decorations, may be used as well for a water soluble coating, with subsequent fixing of the D-e korbildes, by transferring the remainder of release layer components in a water-insoluble state.

Die Erfindung wird anhand der beigefügten Figur näher erläutert. Sie zeigt schematisch einen Querschnitt eines erfindungsgemäßen Trägers für Abzieh- oder Abschiebebilder. Hierin ist mit Position 1 der Papierträger angegeben, durchschnittlich mit einer Flächenmasse im Bereich von etwa 100 bis 200 g/m2. Der Papierträger enthält eine Sperrschicht 2, die die eine Oberfläche des Pa_ierträgers weniger porös macht. Sie kann aus riner Oberflächenleimung oder aus einem verschließbaren Aufstrich, zum Beispiel aus Stärke, Kasein, Leim, Alkalimetallsilikat oder Wasserglas mit und ohne Tonfüllstoff bestehen. Das Vorhandensein der Sperrschicht 2 verhütet das übermäßige Eindringen und Aufsaugen des für die Trennschicht 3 aufzubringenden erfindungsgemäßen Materials.The invention is explained in more detail with reference to the attached figure. It shows schematically a cross section of a carrier according to the invention for decals or decals. Position 1 of the paper carrier is specified therein, on average with a mass per unit area in the range from approximately 100 to 200 g / m 2 . The paper carrier contains a barrier layer 2, which makes one surface of the paper carrier less porous. It can consist of pure surface sizing or of a sealable spread, for example starch, casein, glue, alkali metal silicate or water glass with and without clay filler. The presence of the barrier layer 2 prevents excessive penetration and absorption of the material according to the invention to be applied for the separating layer 3.

Die Trennschicht 3 aus den beschriebenen Materialien wird mittels geeigneter Auftragsverfahren über der Sperrschicht 2 aufgebracht. Die aufzutragende Trockenmasse beträgt 6 bis 15 g/m2. Die Trocknung erfolgt bei ca. 80 °C in einem Trockenkanal.The separating layer 3 made of the materials described is applied over the barrier layer 2 by means of a suitable application method. The dry weight to be applied is 6 to 15 g / m 2 . Drying takes place at approx. 80 ° C in a drying tunnel.

Zur Herstellung der Trennschichtlösung werden die Einzelkomponenten zunächst in Wasser gelöst.To prepare the interface solution, the individual components are first dissolved in water.

Dextrin wird in kaltes Wasser eingestreut und unter mäßigem Rühren aufgelöst.Dextrin is sprinkled in cold water and dissolved with moderate stirring.

Polyacrylsäure ist als Lösung im Handel erhältlich.Polyacrylic acid is commercially available as a solution.

Das Copolymerisat aus Acrylsäure und Acrylsäureester (PAS/PAE) löst man in 70 °C warmem Wasser durch Neutralisieren, indem man zum Beispiel 23 Teile Triethanolamin auf 100 Teile Copolymerisat zusetzt.The copolymer of acrylic acid and acrylic acid ester (PAS / PAE) is dissolved in water at 70 ° C. by neutralization, for example by adding 23 parts of triethanolamine to 100 parts of copolymer.

Das Copolymerisat aus Methylvinylether und Maleinsäureanhydrid (PVE/MA) löst man unter Rühren in 95 °C heißem Wasser. Man verfährt dabei wie folgt:

  • In 70 Teile kochendes Wasser werden 15 Teile des Copolymerisates mit einem Molekulargewicht von etwa 125.000 und einer spezifischen Viskosität von 0,1 bis 0,5 mPa s (Gantrez R AN 119 der GAF, USA) bei großer Geschwindigkeit eingerührt. Die vollständige Auflösung zeigt sich im plötzlichen Aufklaren der milchigen Aufschlämmung. Parallel erfolgt ein Absinken der Viskosität. Zur abgekühlten Lösung gibt man unter Rühren 15 Teile Dextringranulat und rührt bis zum völligen Auflösen. Die so erhaltene Lösung kann nun mit den üblichen Auftragsverfahren auf den Papierträger aufgebracht werden, wobei ein Auftrag von mindestens 6 g/m2 bis etwa 15 g/m2 angebracht ist. Vorzugsweise beträgt das Trockenschichtgewicht 8 bis 12 g/m2.
The copolymer of methyl vinyl ether and maleic anhydride (PVE / MA) is dissolved in hot water at 95 ° C. with stirring. The procedure is as follows:
  • 15 parts of the copolymer having a molecular weight of about 125,000 and a specific viscosity of 0.1 to 0.5 mPas (Gantrez R AN 119 from GAF, USA) are stirred into 70 parts of boiling water at high speed. Complete dissolution is shown by the sudden clearing of the milky slurry. At the same time, the viscosity drops. 15 parts of dextrin granules are added to the cooled solution with stirring and the mixture is stirred until completely dissolved. The solution thus obtained can now be applied to the paper support using the customary application methods, with an application of at least 6 g / m 2 to about 15 g / m 2 being appropriate. The dry layer weight is preferably 8 to 12 g / m 2 .

Die vorgenannten Komponenten sind nun untereinander beliebig mischbar.The aforementioned components can now be mixed with one another as desired.

Da Dextrin rückstandsfreie Verbrennung beeinträchtigen kann, soll erfindungsgemäß im Gemisch ein Anteil von 50 Gewichtsprozent in der Rezeptur nicht überschritten werden. Andererseits ist Dextrin auch insofern von Nutzen, da durch seine Anwesenheit die Abschwimm- und Ablöseeigenschaften bezüglich Trennschicht und Dekorbild positiv beeinflußt werden. Bei der Anwendung eines durch Wärme zu fixierenden Abziehbildes ist Dextrin als Reaktionspartner zu PVE/MA geeignet.Since dextrin can impair residue-free combustion, according to the invention a proportion of 50 percent by weight in the formulation should not be exceeded. On the other hand, dextrin is also useful to the extent that its presence has a positive influence on the floating and peeling properties with regard to the separating layer and the decor. When using a decal to be fixed by heat, dextrin is suitable as a reaction partner to PVE / MA.

Die in der nachfolgenden Tabelle angeführten Rezepturen werden auf einen mit einer Sperrschicht versehenen Papierträger zu 10 g/m2 (Trockengewicht) aufgetragen und getrocknet.The formulations listed in the table below are applied to a paper support provided with a barrier layer at 10 g / m 2 (dry weight) and dried.

Anhand der Beispiele werden die Einflüsse der verschiedenen Komponenten auf die Sauberkeit des Dekorbildes bzw. seine Wärmefixierbarkeit dargestellt.

Figure imgb0001
Die mit den Trennschichten 1 bis 9 versehenen Papierträger werden mit einem handelsüblichen, rückstandsfrei verbrennenden Acrylatlack (Lack 83450 der Degussa) als Lackmaske beschichtet und an der Luft getrocknet.Using the examples, the influences of the various components on the cleanliness of the decor or its heat fixability are shown.
Figure imgb0001
 The paper supports provided with the separating layers 1 to 9 are coated with a commercially available, residue-free burning acrylic varnish (varnish 83450 from Degussa) as a varnish mask and air-dried.

Zur Prüfung werden die so vorbereiteten Prüflinge kurz mit der Rückseite auf Wasser gelegt. Der sich ablösende Lackfilm wird nach 1 Minute auf unglasierte Keramikstücke abgeschoben und mittels Gummirakel ausgestrichen. Die lufttrockenen Stücke werden dann auf 550 °C aufgeheizt, wobei die Lackmaske vollständig verbrennt, und wieder abgekühlt.For the test, the test specimens prepared in this way are briefly placed on the back with water. The peeling paint film is pushed onto unglazed ceramic pieces after 1 minute and spread using a rubber squeegee. The air-dry pieces are then heated to 550 ° C., the paint mask being completely burned, and then cooled again.

Bei den Rezepturen 1 und 2 sind deutlich erkennbar Spuren von unverbrannter Trennschicht festzustellen. Die Rezepturen 3 bis 9 zeigen dagegen keinerlei Spuren von Tonen, d.h. selbst bei relativ niederer Brenntemperatur werden die mitübertragenen Reste der Trennschicht rückstandsfrei, ohne Hinterlassung von Rußpartikeln, verbrannt.Recipes 1 and 2 clearly show traces of unburned interface. Recipes 3 to 9, on the other hand, show no traces of clays, i.e. Even at a relatively low firing temperature, the residues of the separating layer that are also transferred are burned without residue, without leaving soot particles.

Eine auf die Trennschicht nach Rezeptur 4 aufgebrachte Lackmaske anstelle eines aufgebrachten Dekorbildes mit Lackmaske wird auf übliche Art auf ein Kunststoffbehältnis (Flasche) als Unterlage übertragen und 15 Minuten einer Temperatur von etwa 200 °C ausgesetzt. Vergleichsweise wird ein Kunststoffbehältnis entsprechend behandelt, wobei als Trennschicht ein Material nach Rezeptur 1 verwendet wurde.A lacquer mask applied to the separating layer according to recipe 4 instead of an applied decorative image with lacquer mask is transferred in the usual way to a plastic container (bottle) as a base and exposed to a temperature of approximately 200 ° C. for 15 minutes. For comparison, a plastic container is treated accordingly, a material according to recipe 1 being used as the separating layer.

Nach Abkühlen werden beide Behältnisse Tenside enthaltendem Wasser als Prüflösung ausgesetzt. Während die Lackmaske, mit Hilfe der Rezeptur 4 übertragen, der Wassereinwirkung 20 Minuten standhält, schwimmt die Lackmaske, die mit Hilfe der Rezeptur 1 für die Trennschicht übertragen wurde, nach der gleichen Zeit ab.After cooling, both containers are exposed to water containing surfactants as a test solution. While the paint mask, transferred with the help of recipe 4, which withstands the action of water for 20 minutes, the paint mask, which was transferred with the help of recipe 1 for the separating layer, floats after the same time.

Claims (5)

1. Träger für Abzieh- oder Abschiebebilder aus saugfähigem Papier mit aufgebrachter Sperrschicht und einer durch Wasser löslichen Trennschicht zur Aufnahme einer Druck- und/oder Lackschicht, dadurch gekennzeichnet, daß die Trennschicht ein Homo- oder Copolymerisat der Acrylsäure und/oder ein Copolymerisat aus Alkylvinylether und Maleinsäureanhydrid enthält oder daraus besteht.1. Carrier for decals or decals made of absorbent paper with an applied barrier layer and a water-soluble separating layer for receiving a printing and / or lacquer layer, characterized in that the separating layer is a homo- or copolymer of acrylic acid and / or a copolymer of alkyl vinyl ether and contains or consists of maleic anhydride. 2. Papierträger nach Anspruch .1, dadurch gekennzeichnet, daß die Trennschicht aus einem Gemisch aus einem Homo- oder Copolymerisat der Acrylsäure und einem Polysaccharid besteht.2. Paper support according to claim .1, characterized in that the separating layer consists of a mixture of a homo- or copolymer of acrylic acid and a polysaccharide. 3. Papierträger nach Anspruch 1, dadurch gekennzeichnet, daß die Trennschicht aus einem Gemisch von einem Copolymerisat aus Methylvinylether und Maleinsäureanhydrid und einem Polysaccharid besteht.3. Paper support according to claim 1, characterized in that the separating layer consists of a mixture of a copolymer of methyl vinyl ether and maleic anhydride and a polysaccharide. 4. Papierträger nach Ansprüchen 2 und 3, dadurch gekennzeichnet, daß das Polysaccharid Dextrin ist.4. Paper support according to claims 2 and 3, characterized in that the polysaccharide is dextrin. 5. Papierträger nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Trennschicht mindestens 50 Gewichtsprozent an Homo- oder Copolymerisat enthält.5. Paper support according to claims 1 to 4, characterized in that the separating layer contains at least 50 percent by weight of homo- or copolymer.
EP84103093A 1983-03-30 1984-03-21 Backing for decalcomanias of the pull-off or the slide-off type Expired EP0121179B1 (en)

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DE19833311728 DE3311728A1 (en) 1983-03-30 1983-03-30 CARRIER FOR PULLING OR SCREWING IMAGES
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0665263A1 (en) * 1994-01-26 1995-08-02 Kureha Kagaku Kogyo Kabushiki Kaisha Gas barrier laminate and production process thereof

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3337023A1 (en) * 1983-10-12 1985-04-25 Hoffmann & Engelmann Ag, 6730 Neustadt PAPER CARRIER
US5372669A (en) 1985-02-05 1994-12-13 Avery Dennison Corporation Composite facestocks and liners
US4946532A (en) * 1985-02-05 1990-08-07 Avery International Corporation Composite facestocks and liners
AU599586B2 (en) * 1985-02-05 1990-07-26 Avery International Corporation Composite facestocks and liners
US4888075A (en) * 1985-02-05 1989-12-19 Avery International Corporation Composite facestocks and liners
US5143570A (en) * 1985-02-05 1992-09-01 Avery Dennison Corporation Composite facestocks and liners
US5186782A (en) * 1990-10-17 1993-02-16 Avery Dennison Corporation Method for high speed labelling of deformable substrates
JP2593754B2 (en) * 1991-08-05 1997-03-26 名古屋パルプ株式会社 Painting transfer paper
DE4210976C2 (en) * 1991-10-17 1997-05-22 Buelent Oez Process for transferring images on print templates to fabrics and paper to carry out the process
US5516393A (en) * 1993-04-29 1996-05-14 Avery Dennison Corporation Labelling of substrates
EP0814952A4 (en) * 1995-03-20 1999-06-09 Richard S Zemel Graphic transfer and method
CN1088426C (en) * 1995-06-05 2002-07-31 艾弗里·丹尼森公司 Heat resistant pressure sensitive adhesive constructions
US6264786B1 (en) 1998-05-28 2001-07-24 Mattel, Inc. User-created temporary tattoos
US6524675B1 (en) 1999-05-13 2003-02-25 3M Innovative Properties Company Adhesive-back articles
DE19927758B4 (en) * 1999-06-17 2005-09-22 Ugt Limited, Tuen Mun Method for transferring an image to a surface
GB2351038B (en) * 1999-06-18 2003-03-12 Tam Chit Ho Process for transferring an image onto a surface
US20030039826A1 (en) 2000-03-20 2003-02-27 Sun Edward I. Conformable and die-cuttable biaxially oriented films and labelstocks
CN100387360C (en) * 2001-04-11 2008-05-14 国际纸业公司 Paper articles exhibiting long term storageability
DE10125681C1 (en) 2001-05-25 2003-02-20 Buelent Oez Process for transferring images on print templates to colored documents as well as suitable template material
FI111922B (en) * 2002-05-31 2003-10-15 Perlos Oyj Three dimensional surface e.g. mobile phone cover patterning method, involves fixing coloring agent, and placing two dimensional film having fixed pattern and auxiliary agent on three dimensional surface of object
CN101107398B (en) * 2004-07-06 2015-10-21 国际纸业公司 Comprise the paper substrate of antimicrobial compound and manufacture method thereof and using method
CN1318695C (en) * 2005-10-13 2007-05-30 中国制浆造纸研究院<Del/> Production method of coated water transferal base paper for water transfer ceramic applique bottom paper
WO2010148156A1 (en) * 2009-06-16 2010-12-23 International Paper Company Anti-microbial paper substrates useful in wallboard tape applications
US9996789B2 (en) * 2015-09-21 2018-06-12 Cutaneous Information Technologies Llc Method and apparatus for manufacturing cutaneous information devices
US10406830B2 (en) 2017-03-29 2019-09-10 Xerox Corporation Decal print process

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2970076A (en) * 1957-01-14 1961-01-31 Meyercord Co Vitreous decalcomania and method of decorating ceramic articles
US3128197A (en) * 1961-07-11 1964-04-07 Buntpapierfabrik A G Ceramic underglaze decalcomania and method of making same
US3669704A (en) * 1969-11-28 1972-06-13 Thomas L Reiling Non-curling decalcomania paper comprising a discontinuous polymer-starch particlebarrier layer
DE2551860A1 (en) * 1975-11-19 1977-06-02 Hoffmann & Engelmann Ag PAPER CARRIER

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2729288C2 (en) * 1977-06-29 1979-06-13 Fa. F. Xaver Leipold, 8502 Zirndorf Decal and process for its manufacture

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2970076A (en) * 1957-01-14 1961-01-31 Meyercord Co Vitreous decalcomania and method of decorating ceramic articles
US3128197A (en) * 1961-07-11 1964-04-07 Buntpapierfabrik A G Ceramic underglaze decalcomania and method of making same
US3669704A (en) * 1969-11-28 1972-06-13 Thomas L Reiling Non-curling decalcomania paper comprising a discontinuous polymer-starch particlebarrier layer
DE2551860A1 (en) * 1975-11-19 1977-06-02 Hoffmann & Engelmann Ag PAPER CARRIER

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0665263A1 (en) * 1994-01-26 1995-08-02 Kureha Kagaku Kogyo Kabushiki Kaisha Gas barrier laminate and production process thereof
US5897960A (en) * 1994-01-26 1999-04-27 Kureha Kagaku Kogyo K.K. Laminate and production process thereof

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