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EP2393670B1 - Method for producing decorative paper and decorative paper - Google Patents

Method for producing decorative paper and decorative paper Download PDF

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Publication number
EP2393670B1
EP2393670B1 EP10702622A EP10702622A EP2393670B1 EP 2393670 B1 EP2393670 B1 EP 2393670B1 EP 10702622 A EP10702622 A EP 10702622A EP 10702622 A EP10702622 A EP 10702622A EP 2393670 B1 EP2393670 B1 EP 2393670B1
Authority
EP
European Patent Office
Prior art keywords
paper
polycarbonate
aliphatic
polyurethane dispersion
anionic polyurethane
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.)
Not-in-force
Application number
EP10702622A
Other languages
German (de)
French (fr)
Other versions
EP2393670A1 (en
Inventor
Kimmo Suur-Nuuja
Heinz Kleinerüsskamp
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.)
Keeeper GmbH
Original Assignee
OKT Germany GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by OKT Germany GmbH filed Critical OKT Germany GmbH
Publication of EP2393670A1 publication Critical patent/EP2393670A1/en
Application granted granted Critical
Publication of EP2393670B1 publication Critical patent/EP2393670B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/66—Coatings characterised by a special visual effect, e.g. patterned, textured
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
    • D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
    • 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
    • Y10T428/24868—Translucent outer layer
    • Y10T428/24876—Intermediate layer contains particulate material [e.g., pigment, etc.]

Definitions

  • the present invention relates to a method for the production of decorative paper and a decorative paper.
  • Decorative coating materials are special papers for the surface refinement of wood-based materials. Due to the high optical standards, the highest demands are placed on decorative paper. For optimum printability, the paper requires particularly good formation, smoothness and dimensional stability.
  • the resin impregnation required during processing requires a uniform penetration of the resin into the paper.
  • the impregnation with subsequent compression serves primarily to reduce the sensitivity of the surface to mechanical, thermal and chemical stress (eg abrasion, scratching, water, solvents, water vapor and solvent vapors).
  • the latter technique is used only for papers that are not (yet) printed.
  • the printer must therefore decide before printing whether he wants to use a paper with reduced resin absorption capacity (resin-saving paper) or not.
  • the light fastness of the decor papers produced according to the invention is also improved.
  • overlays which are also exposed to acrylate dispersions, are placed on the decorative papers prior to pressing.
  • Another object of the present invention is to propose a decor paper which has increased light fastness and can be produced inexpensively.
  • a decorative paper with the characterizing features of claim 11. Characterized in that the decorative paper, at least one paper core, a printing layer, As well as an embedded in the paper core aliphatic polycarbonate anionic polyurethane dispersion, a decorative paper can be provided, which has an increased light fastness and can be produced equally well, since both "resin-saving paper” and “non-resin-saving” paper as starting material for the Paper core can be used.
  • an aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied to the printed paper.
  • This may be the product Bayhydrol® XP 2606 from Bayer or a comparable other product (Bayhydrol® is a registered trademark of Bayer AG, 51373 Leverkusen).
  • Bayhydrol® is a registered trademark of Bayer AG, 51373 Leverkusen.
  • the polyurethane dispersion lowers the capillary action, the polycarbonate leading to adhesion of the dispersion in the capillaries, which are thus somewhat narrowed.
  • the decisive for the further processing of the papers pH value is adjusted by the concentration of anions.
  • the aliphatics improve the light fastness.
  • the print product can thus be manufactured either in the setting resin-saving or standard, without a color adjustment is necessary. Color matching is inevitably necessary with the use of the known resin-saving papers due to the changing ink receptivity in printing.
  • the aliphatic, polycarbonate-containing anionic polyurethane dispersion in particular the product Bayhydrol® XP 2606, is mixed in a ratio of 25 parts to 75 parts (parts by weight) of water and applied at the pressure with a dry weight of about 5 g / qm. These parameters are indicative and may change for different papers.
  • the application is done either in gravure by means of rear cylinders in the last printing unit online or offline in another favorable process, eg in a coating plant.
  • Tables 1 to 8 contain safety data sheets or product data sheets of an aliphatic, polycarbonate-containing anionic polyurethane dispersion, in particular of a dispersion marketed under the brand name Bayhydrol®. From this it is possible to deduce the properties of an aliphatic, polycarbonate-containing anionic polyurethane dispersion which can preferably be used for the proposed process according to the invention. It should be noted that this is only a preferred dispersion. In principle, of course, any other aliphatic, polycarbonate-containing anionic polyurethane dispersion comes into question.
  • Fig. 1 the proposed method according to the invention is shown schematically here.
  • the decorative paper according to the invention comprises a paper core 1, a printing layer 2, an aliphatic, polycarbonate-containing anionic polyurethane dispersion 3 incorporated into the paper core 1, and in particular a resin layer or embedded resin particles 4.
  • the proposed method according to the invention can be used particularly advantageously for the following exemplary applications.
  • the degree of gloss depends essentially on the amount of applied nacreous pigments in the pearlescent color.
  • Mother-of-pearl pigments if printed as a uni-color, are usually fixed with an overprinted blend as a binder.
  • the amount of pigments can not be increased arbitrarily, since the paper must remain impregnable. Too high an amount results in a partial sealing of the surface and the resin can penetrate insufficiently into the paper, resulting in impregnation defects and thus high waste.
  • the degree of gloss depends on the flow behavior and curing of the resin. Too rapid curing results in low gloss since the resin does not sufficiently dissolve during the compression and takes on the (glossy) structure of the press plate. In the worst case, stains form, which is also broke.
  • an improvement in the gloss level can also be achieved by replacing the blend for fixing the pigments with an aliphatic, polycarbonate-containing anionic polyurethane dispersion.
  • the aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied (Process step ii).
  • the product can be compared to that in the EP 13 61 074 B1 described manner to be made less with a printing unit, which increases the flexibility and costs z. B. Energy costs lowers.
  • the gloss level of the surfaces thus produced is very high.
  • a higher gloss level than with the in the according EP 13 61 074 B1 be achieved substance described.
  • the paper is less sensitive to manufacturing variations during impregnation and compression.
  • the inventively proposed method or by the decorative paper according to the invention remedy can be provided by the inventively proposed method or by the decorative paper according to the invention remedy.
  • the asymmetry is reduced, at least for printed papers. Also, properties such as resin savings and increased flexibility, in particular due to the dispersion in the paper, are retained.
  • Decorative papers need sufficient opacity so that nothing of the chipboard shows through.
  • the opacity results from the amount of TiO 2 incorporated in the paper. If the opacity is to be increased, more Ti02 must be incorporated. However, this only succeeds in simultaneously increasing the basis weight, since the network of paper fibers can not hold any amount of TiO 2. The paper becomes more unstable, the tear strength decreases.
  • Ti02 can be printed as a color on an existing paper. This overprint is sealed by over-printing with aliphatic polycarbonate-containing anionic polyurethane dispersion. By curing the aliphatic, polycarbonate-containing anionic polyurethane dispersion after printing, the tear strength of the paper is increased. With the same basis weight, a paper can be produced that has a higher opacity and at the same time has the advantages outlined above.
  • the growth of the paper during impregnation is a central theme.
  • the individual panels must have the expected width; Tiles should remain square.
  • a particular challenge is represented by a pore structure compressed synchronously with the print image. According to the prior art, this is realized by empirically determining the growth of the paper web on the basis of the resin absorption and taking this into account in the print data. Fluctuations in growth behavior due to fluctuations in paper production lead to considerable rejection.
  • paper must be removed from the center of the paper machine so that it can not be used in its full width, since a paper machine can also be twice as wide as the further processing machines.
  • the paper growth can be reduced from currently 1.5% to almost zero.
  • the aliphatic, polycarbonate-containing anionic polyurethane dispersion cured after printing fixes the paper width. The paper does not grow during the impregnation.
  • the aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied to the pressure side.
  • the application “flatness” shows by way of example, an application on the back of the paper can also be advantageous.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Printing Methods (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Dekorpapier sowie ein Dekorpapier.The present invention relates to a method for the production of decorative paper and a decorative paper.

Dekorative Beschichtungswerkstoffe, sogenannte Dekorpapiere, sind Spezialpapiere zur Oberflächenveredelung von Holzwerkstoffen. Aufgrund des hohen optischen Anspruchs werden höchste Anforderungen an das Dekorpapier gestellt. Zur optimalen Bedruckbarkeit erfordert das Papier eine besonders gute Formation, Glätte und Dimensionsstabilität. Die bei der Verarbeitung notwendige Kunstharzimprägnierung erfordert eine gleichmäßige Penetration des Harzes in das Papier. Die Imprägnierung mit anschließender Verpressung dient vor allem dazu, die Empfindlichkeit der Oberfläche gegenüber mechanischer, thermischer und chemischer Beanspruchung (z. B. Abrieb, Verkratzen, Wasser, Lösungsmittel, Wasserdampf und Lösungsmitteldämpfe) herabzusetzen.Decorative coating materials, so-called decorative papers, are special papers for the surface refinement of wood-based materials. Due to the high optical standards, the highest demands are placed on decorative paper. For optimum printability, the paper requires particularly good formation, smoothness and dimensional stability. The resin impregnation required during processing requires a uniform penetration of the resin into the paper. The impregnation with subsequent compression serves primarily to reduce the sensitivity of the surface to mechanical, thermal and chemical stress (eg abrasion, scratching, water, solvents, water vapor and solvent vapors).

Es besteht ein Interesse daran, die Harzaufnahmefähigkeit des Papiers zu reduzieren. Hierzu sind grundsätzlich zwei Wege bekannt geworden.There is an interest in reducing the resin receptivity of the paper. For this purpose, basically two ways have become known.

Es wurde einerseits versucht, die Dekorpapiere zu verdichten und so weniger Hohlräume im Papier zu belassen, in denen sich Harz einlagern kann. Auf diesen Effekt wird beispielsweise bereits in der Beschreibungseinleitung der DE 101 34 302 C1 hingewiesen. Dieses Verfahren hat sich allerdings nie am Markt breitflächig durchsetzen können.On the one hand, attempts have been made to densify the decorative papers and thus to leave fewer voids in the paper in which resin can be incorporated. For example, this effect is already described in the introduction to the DE 101 34 302 C1 pointed. However, this method has never been widely accepted on the market.

Auch ist ein weiterer Weg zur Reduzierung der Harzaufnahmefähigkeit von Dekorpapieren bekannt geworden. Nach der Papierherstellung ist es möglich, die Dekorpapiere mit einem sogenannten Leimstrich zu beaufschlagen. Hier werden vorzugsweise Acrylatdispersionen auf die Oberflächen offline oder online aufgebracht. Dadurch wird die Oberfläche des Papiers teilweise versiegelt und das Harz kann schlechter in die Papiere eindringen. Denkbar ist auch, dass dabei die Kapillarwirkung der Papierfasern reduziert wird.Also, another way to reduce the resin receptivity of decorative papers has become known. After papermaking it is possible to decorate the decor papers with a so-called glue stick apply. Here, acrylate dispersions are preferably applied to the surfaces offline or online. As a result, the surface of the paper is partially sealed and the resin can penetrate worse in the papers. It is also conceivable that the capillary action of the paper fibers is thereby reduced.

Insbesondere die letztgenannte Technik wird nur für Papiere eingesetzt, die (noch) nicht bedruckt sind. Der Drucker muss demnach vor dem Drucken entscheiden, ob er ein Papier mit reduzierter Harzaufnahmefähigkeit (Harz sparendes Papier) einsetzen will oder nicht.In particular, the latter technique is used only for papers that are not (yet) printed. The printer must therefore decide before printing whether he wants to use a paper with reduced resin absorption capacity (resin-saving paper) or not.

Hier setzt die vorliegende Erfindung an und macht es sich zur Aufgabe, ein Verfahren zur Herstellung von Dekorpapier vorzuschlagen, bei dem eine Vorauswahl des Papiers, insbesondere eines "Harz sparenden Papiers" (sogenannte "resin saving papers") oder eines "nicht Harz sparenden" Papiers, nicht erforderlich ist.This is where the present invention is based and proposes a process for the production of decor paper, in which a preselection of the paper, in particular a "resin-saving paper" or a "non-resin-saving paper" Papiers, not required.

Erfindungsgemäß wird diese Aufgabe durch ein Verfahren mit den kennzeichnenden Merkmalen des Anspruchs 1 gelöst. Dadurch, dass auf das Papier nach dem Bedrucken eine aliphatische, polycarbonathaltige anionische Polyurethandispersion aufgebracht wird, kann sowohl herkömmliches, als auch Harz sparendes Papier für die Herstellung von Dekorpapier verwendet werden. Entsprechend und insbesondere neu ist demnach, dass die Einstellung der Harzersparnis in dem hier beschriebenen Verfahren nach dem Drucken geschieht und dass hierzu eine aliphatische, polycarbonathaltige anionische Polyurethandispersion verwendet wird. Derartige Dispersionen werden bislang im Zusammenhang mit Dekorpapieren nicht eingesetzt. Durch das Aufbringen nach dem Drucken erhöht sich die Flexibilität des Druckers in der Auswahl der Druckbasispapiere. Die Papierfertigung bedingt immer eine Mindestmenge jeweils einer Einstellung. Hieraus ergeben sich Mindestabnahmemengen, die die Flexibilität des Druckers einschränken.According to the invention this object is achieved by a method having the characterizing features of claim 1. Characterized in that an aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied to the paper after printing, both conventional, and resin-saving paper can be used for the production of decorative paper. It is accordingly and in particular novel that the setting of the resin savings in the process described here takes place after printing and that an aliphatic, polycarbonate-containing anionic polyurethane dispersion is used for this purpose. Such dispersions have hitherto not been used in connection with decorative papers. Post-print application increases the flexibility of the printer in the selection of print base papers. Paper production always requires one Minimum quantity of one setting each. This results in minimum purchase quantities, which limit the flexibility of the printer.

Zwar ist bekannt, dass Polyurethane als Lacksysteme auf bedruckten oder nicht bedruckten Papieren eingesetzt werden. Im Gegensatz zu der hier beschriebenen Erfindung handelt es sich jedoch um Lacke, denen ein Härter zugegeben werden muss. Diese Lackoberflächen stellen die Barriere zur Umwelt dar; die Papiere werden nicht weiter imprägniert oder anders veredelt, sondern auf Werkstoffe aufkaschiert. Eine derartige Maßnahme wird hier nicht vorgeschlagen.Although it is known that polyurethanes are used as coating systems on printed or non-printed papers. In contrast to the invention described here, however, these are paints to which a hardener must be added. These paint surfaces are the barrier to the environment; The papers are not further impregnated or otherwise refined, but laminated on materials. Such a measure is not proposed here.

Als weiterer vorteilhafter Nebeneffekt des vorgeschlagenen Verfahrens wird ebenfalls die Lichtechtheit der erfindungsgemäß hergestellten Dekorpapiere verbessert. Zur Verbesserung der Lichtechtheit von Dekorpapieren werden gemäß dem Stand der Technik beispielsweise Overlays, die auch mit Acrylatdispersionen beaufschlagt sind, auf die Dekorpapiere vor dem Verpressen aufgelegt. Diese Maßnahmen sind mit dem vorgeschlagenen Verfahren nicht notwendig.As a further advantageous side effect of the proposed method, the light fastness of the decor papers produced according to the invention is also improved. To improve the light fastness of decorative papers, for example, according to the prior art, overlays, which are also exposed to acrylate dispersions, are placed on the decorative papers prior to pressing. These measures are not necessary with the proposed method.

Weitere vorteilhafte Ausgestaltungen des vorgeschlagenen Verfahrens ergeben sich insbesondere aus den Merkmalen der Unteransprüche.Further advantageous embodiments of the proposed method emerge in particular from the features of the subclaims.

Eine weitere Aufgabe der vorliegenden Erfindung liegt darin, ein Dekorpapier vorzuschlagen, welches eine erhöhte Lichtechtheit aufweist und kostengünstig hergestellt werden kann.Another object of the present invention is to propose a decor paper which has increased light fastness and can be produced inexpensively.

Erfindungsgemäß wird diese Aufgabe durch ein Dekorpapier mit den kennzeichnenden Merkmalen des Anspruchs 11 gelöst. Dadurch, dass das Dekorpapier, mindestens einen Papierkern, eine Druckschicht, sowie eine in den Papierkern eingelagerte aliphatische, polycarbonathaltige anionische Polyurethandispersion aufweist, kann ein Dekorpapier bereitgestellt werden, welches eine erhöhte Lichtechtheit aufweist und gleichermaßen günstig hergestellt werden kann, da sowohl "Harz sparendes Papier" als auch "nicht Harz sparendes" Papier als Ausgangsmaterial für den Papierkern verwendet werden kann.According to the invention this object is achieved by a decorative paper with the characterizing features of claim 11. Characterized in that the decorative paper, at least one paper core, a printing layer, As well as an embedded in the paper core aliphatic polycarbonate anionic polyurethane dispersion, a decorative paper can be provided, which has an increased light fastness and can be produced equally well, since both "resin-saving paper" and "non-resin-saving" paper as starting material for the Paper core can be used.

Weitere vorteilhafte Ausgestaltungen des vorgeschlagenen Dekorpapiers ergeben sich insbesondere aus den Merkmalen der Unteransprüche.Further advantageous embodiments of the proposed decorative paper result in particular from the features of the subclaims.

Weitere Merkmale und Vorteile der vorliegenden Erfindung werden deutlich anhand der nachfolgenden Beschreibung bevorzugter Ausführungsbeispiele unter Bezugnahme auf die beiliegenden Tabellen und Abbildungen. Darin zeigen

Tab. 1
ein Sicherheitsdatenblatt betreffend BAYHYDROL® XP 2606 (Seite 1 von 5);
Tab. 2
ein Sicherheitsdatenblatt betreffend BAYHYDROL® XP 2606 (Seite 2 von 5);
Tab. 3
ein Sicherheitsdatenblatt betreffend BAYHYDROL® XP 2606 (Seite 3 von 5);
Tab. 4
ein Sicherheitsdatenblatt betreffend BAYHYDROL® XP 2606 (Seite 4 von 5);
Tab. 5
ein Sicherheitsdatenblatt betreffend BAYHYDROL® XP 2606 (Seite 5 von 5);
Tab. 6
ein Produktdatenblatt betreffend Bayhydrol® (Seite 1 von 3);
Tab. 7
ein Produktdatenblatt betreffend Bayhydrol® (Seite 2 von 3);
Tab. 8
ein Produktdatenblatt betreffend Bayhydrol® (Seite 3 von 3).
Fig. 1
eine schematische Darstellung des erfindungsgemäßen Verfahrens;
Fig. 2
eine schematische Querschnittdarstellung eines erfindungsgemäßen Dekorpapiers.
Further features and advantages of the present invention will become apparent from the following description of preferred embodiments with reference to the accompanying tables and figures. Show in it
Tab. 1
a safety data sheet concerning BAYHYDROL® XP 2606 (page 1 of 5);
Tab. 2
a safety data sheet concerning BAYHYDROL® XP 2606 (page 2 of 5);
Tab. 3
a safety data sheet concerning BAYHYDROL® XP 2606 (page 3 of 5);
Tab. 4
a safety data sheet regarding BAYHYDROL® XP 2606 (page 4 of 5);
Tab. 5
a safety data sheet regarding BAYHYDROL® XP 2606 (page 5 of 5);
Tab. 6
a product data sheet concerning Bayhydrol® (page 1 of 3);
Tab. 7
a product data sheet concerning Bayhydrol® (page 2 of 3);
Tab. 8
a product data sheet concerning Bayhydrol® (page 3 of 3).
Fig. 1
a schematic representation of the method according to the invention;
Fig. 2
a schematic cross-sectional view of a decorative paper according to the invention.

Erfindungsgemäß wird eine aliphatische, polycarbonathaltige anionische Polyurethandispersion auf das bedruckte Papier aufgebracht. Dies kann das Produkt Bayhydrol® XP 2606 der Firma Bayer oder ein vergleichbares anderes Produkt sein (Bayhydrol® ist eine eingetragene Marke der Bayer AG, 51373 Leverkusen). Die Polyurethandispersion setzt die Kapillarwirkung herab, wobei das Polycarbonat zu einer Haftung der Dispersion in den Kapillaren führt, die dadurch gewissermaßen verengt werden. Der für die Weiterverarbeitung der Papiere entscheidende pH-Wert wird durch die Konzentration der Anionen eingestellt. Die Aliphate verbessern die Lichtechtheit.According to the invention, an aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied to the printed paper. This may be the product Bayhydrol® XP 2606 from Bayer or a comparable other product (Bayhydrol® is a registered trademark of Bayer AG, 51373 Leverkusen). The polyurethane dispersion lowers the capillary action, the polycarbonate leading to adhesion of the dispersion in the capillaries, which are thus somewhat narrowed. The decisive for the further processing of the papers pH value is adjusted by the concentration of anions. The aliphatics improve the light fastness.

Nach dem Aufbringen tritt keine sichtbare Farbverschiebung des bedruckten Basispapiers auf. Das Druckprodukt kann somit wahlweise in der Einstellung Harz sparend oder Standard gefertigt werden, ohne dass eine Farbanpassung notwendig wird. Eine Farbanpassung ist bei dem Einsatz der bekannten Harz sparenden Papiere auf Grund der sich verändernden Farbaufnahme im Druck zwangsläufig notwendig.After application no visible color shift of the printed base paper occurs. The print product can thus be manufactured either in the setting resin-saving or standard, without a color adjustment is necessary. Color matching is inevitably necessary with the use of the known resin-saving papers due to the changing ink receptivity in printing.

Die aliphatische, polycarbonathaltige anionische Polyurethandispersion, insbesondere das Produkt Bayhydrol® XP 2606, wird im Verhältnis 25 Teile zu 75 Teile (Gewichtsteile) Wasser gemischt und auf dem Druck mit einem Trockengewicht von etwa 5 g /qm aufgebracht. Diese Parameter sind Richtwerte und können sich für unterschiedliche Papiere noch verändern. Das Aufbringen geschieht entweder im Tiefdruck mittels Fondzylindern im letzten Druckwerk online oder offline in einem anderen günstigen Verfahren, z.B. in einem Lackierwerk.The aliphatic, polycarbonate-containing anionic polyurethane dispersion, in particular the product Bayhydrol® XP 2606, is mixed in a ratio of 25 parts to 75 parts (parts by weight) of water and applied at the pressure with a dry weight of about 5 g / qm. These parameters are indicative and may change for different papers. The application is done either in gravure by means of rear cylinders in the last printing unit online or offline in another favorable process, eg in a coating plant.

In den Tabellen 1 bis 8 sind Sicherheitsdatenblätter bzw. Produktdatenblätter einer aliphatischen, polycarbonathaltigen anionischen Polyurethandispersion, insbesondere einer unter dem Markennamen Bayhydrol® vertriebenen Dispersion, beigefügt. Hieraus lassen sich die Eigenschaften einer bevorzugt für das vorgeschlagene erfindungsgemäße Verfahren einsetzbaren aliphatischen, polycarbonathaltigen anionischen Polyurethandispersion entnehmen. Es ist anzumerken, dass es sich hierbei nur um eine bevorzugte Dispersion handelt. Grundsätzlich kommt selbstverständlich jede andere aliphatische, polycarbonathaltige anionische Polyurethandispersion in Frage.Tables 1 to 8 contain safety data sheets or product data sheets of an aliphatic, polycarbonate-containing anionic polyurethane dispersion, in particular of a dispersion marketed under the brand name Bayhydrol®. From this it is possible to deduce the properties of an aliphatic, polycarbonate-containing anionic polyurethane dispersion which can preferably be used for the proposed process according to the invention. It should be noted that this is only a preferred dispersion. In principle, of course, any other aliphatic, polycarbonate-containing anionic polyurethane dispersion comes into question.

In Fig. 1 ist das hier vorgeschlagene erfindungsgemäße Verfahren schematisch dargestellt.In Fig. 1 the proposed method according to the invention is shown schematically here.

In Fig. 2 ist ein mit dem erfindungsgemäßen Verfahren hergestelltes erfindungsgemäßes Dekorpapier in einer schematischen Querschnittdarstellung dargestellt. Im Wesentlichen umfasst das erfindungsgemäße Dekorpapier einen Papierkern 1, eine Druckschicht 2, eine in den Papierkern 1 eingelagerte aliphatische, polycarbonathaltige anionische Polyurethandispersion 3, sowie insbesondere eine Harzschicht bzw. eingelagerte Harzpartikel 4.In Fig. 2 a decorative paper according to the invention produced by the method according to the invention is shown in a schematic cross-sectional representation. Essentially, the decorative paper according to the invention comprises a paper core 1, a printing layer 2, an aliphatic, polycarbonate-containing anionic polyurethane dispersion 3 incorporated into the paper core 1, and in particular a resin layer or embedded resin particles 4.

Das vorgeschlagene erfindungsgemäße Verfahren kann besonders vorteilhaft für nachfolgende beispielhafte Anwendungsfälle eingesetzt werden.The proposed method according to the invention can be used particularly advantageously for the following exemplary applications.

Besondere Vorteile ergeben sich im Zusammenhang mit dem erfindungsgemäßen Verfahren bzw. einem erfindungsgemäßen Dekorpapier und Metalleffektfarben, insbesondere sogenannten Perlmuttfarben.Particular advantages arise in connection with the method according to the invention or a decorative paper and metallic effect paints according to the invention, in particular so-called mother-of-pearl colors.

Eine wichtige ästhetische Eigenschaft von Dekoren, die mit Perlmuttfarben gedruckt werden, besteht in dem dadurch erzielten Glanzgrad. Der Glanzgrad hängt wesentlich von der Menge der aufgebrachten Perlmuttpigmente in der Perlmuttfarbe ab. Perlmuttpigmente werden, falls sie als Uni-Farbton gedruckt werden, üblicherweise mit einem darüber gedruckten Verschnitt als Bindemittel fixiert. Die Menge der Pigmente kann nicht beliebig gesteigert werden, da das Papier imprägnierfähig bleiben muss. Eine zu hohe Menge führt zu einer partiellen Versiegelung der Oberfläche und das Harz kann nur ungenügend in das Papier penetrieren, was zu Imprägnierfehlern und somit zu einer hohen Makulatur führt. Andererseits hängt der Glanzgrad von dem Fließverhalten und Aushärten des Harzes ab. Ein zu schnelles Aushärten führt zu einem geringen Glanz, da das Harz während des Verpressens nicht ausreichend zerfließt und die (glänzende) Struktur des Pressbleches annimmt. Im schlimmsten Fall bilden sich Flecken, was ebenfalls Ausschuss ist.An important aesthetic feature of decors printed with pearlescent colors is the degree of gloss achieved thereby. The degree of gloss depends essentially on the amount of applied nacreous pigments in the pearlescent color. Mother-of-pearl pigments, if printed as a uni-color, are usually fixed with an overprinted blend as a binder. The amount of pigments can not be increased arbitrarily, since the paper must remain impregnable. Too high an amount results in a partial sealing of the surface and the resin can penetrate insufficiently into the paper, resulting in impregnation defects and thus high waste. On the other hand, the degree of gloss depends on the flow behavior and curing of the resin. Too rapid curing results in low gloss since the resin does not sufficiently dissolve during the compression and takes on the (glossy) structure of the press plate. In the worst case, stains form, which is also broke.

Ein Ansatz zur Steigerung des Glanzes und Vermeidung von Imprägnierfehlern wird bereits in dem Patent EP 13 61 074 B1 beschrieben. Durch das Aufbringen einer alkalischen Lösung wird das Fließverhalten des Harzes positiv beeinflusst. Die Substanz muss jedoch separat aufgetragen werden.One approach to increasing the gloss and avoiding impregnation defects is already described in the patent EP 13 61 074 B1 described. By applying an alkaline solution, the flow behavior of the resin is positively influenced. However, the substance must be applied separately.

Eine Verbesserung des Glanzgrades kann jedoch auch dadurch erzielt werden, dass der Verschnitt zur Fixierung der Pigmente durch eine aliphatische, polycarbonathaltige anionische Polyurethandispersion ersetzt wird. Bezogen auf die gemäß Anspruch 1 skizzierten Verfahrensschritte bedeutet dies, dass das Bedrucken des Papiers (Verfahrensschritt i) mit einer perlmuttpigmenthaltigen Farbe durchgeführt wird. Anschließend wird die aliphatische, polycarbonathaltige anionische Polyurethandispersion aufgebracht (Verfahrensschritt ii). Das Produkt kann, gegenüber der in der EP 13 61 074 B1 beschriebenen Weise, mit einem Druckwerk weniger hergestellt werden, was die Flexibilität erhöht und Kosten z. B. Energiekosten senkt.However, an improvement in the gloss level can also be achieved by replacing the blend for fixing the pigments with an aliphatic, polycarbonate-containing anionic polyurethane dispersion. Based on the outlined in claim 1 process steps, this means that the printing of the paper (step i) is carried out with a pearlescent pigment-containing color. Subsequently, the aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied (Process step ii). The product can be compared to that in the EP 13 61 074 B1 described manner to be made less with a printing unit, which increases the flexibility and costs z. B. Energy costs lowers.

Der Glanzgrad, der so hergestellten Oberflächen ist sehr hoch. Gegebenenfalls kann ein höherer Glanzgrad als mit der in der gemäß EP 13 61 074 B1 beschriebenen Substanz erreicht werden. Zudem wird das Papier unempfindlicher gegenüber Fertigungsschwankungen während der Imprägnierung und Verpressung.The gloss level of the surfaces thus produced is very high. Optionally, a higher gloss level than with the in the according EP 13 61 074 B1 be achieved substance described. In addition, the paper is less sensitive to manufacturing variations during impregnation and compression.

Besondere Vorteile ergeben sich auch im Zusammenhang mit dem erfindungsgemäßen Verfahren bzw. einem erfindungsgemäßen Dekorpapier und der sogenannten PlanlageParticular advantages also arise in connection with the method according to the invention or a decor paper according to the invention and the so-called flatness

Ein Problem bei der Weiterverarbeitung von imprägnierten Papieren besteht darin, dass sich die Seiten des Papiers aufrichten. Der Fachmann nennt dieses Verhalten Schüsseln oder Curling. Es entsteht dadurch, dass ein Papier nicht vollständig symmetrisch gefertigt werden kann. Die Asymmetrie wird durch einseitiges Bedrucken verstärkt. Das Schüsseln hängt zudem auch von dem Umweltbedingungen speziell der Luftfeuchtigkeit des Raumes, in dem das Papier verarbeitet wird, ab. Erwünscht ist jedoch eine Planlage des Papiers, d.h. ein geringes Schüsseln.A problem with the further processing of impregnated papers is that the sides of the paper straighten up. The skilled person calls this behavior bowls or curling. It results from the fact that a paper can not be made completely symmetrical. The asymmetry is reinforced by one-sided printing. Dishes also depend on the environmental conditions, especially the humidity of the room where the paper is being processed. However, what is desired is a flatness of the paper, i. a little bowls.

Aus dem Stand der Technik sind dem Fachmann verschiedene Methoden zur Verminderung des Schüsselns bekannt. Um das Schüsseln zu minimieren wird falls notwendig entweder das Raumklima feuchter gehalten oder das Papier rückseitig bereits vor dem Aufwickeln oder nach dem Abwickeln mit Wasser befeuchtet.From the state of the art, various methods for reducing bowls are known to the person skilled in the art. In order to minimize the bowls, if necessary, either the room climate is kept moister or the paper already moistened with water before winding or after unwinding.

Auch hier können durch das erfindungsgemäß vorgeschlagene Verfahren bzw. durch das erfindungsgemäße Dekorpapier Abhilfe geschaffen werden. Durch ein Aufbringen von aliphatischer, polycarbonathaltiger anionischer Polyurethandispersion auf der Rückseite des Papiers wird die Asymmetrie zumindest bei bedruckten Papieren herabgesetzt. Auch bleiben Eigenschaften wie Harzersparnis und erhöhte Flexibilität, insbesondere durch die Dispersion im Papier, erhalten.Again, can be provided by the inventively proposed method or by the decorative paper according to the invention remedy. By applying aliphatic, polycarbonate-containing anionic polyurethane dispersion on the back of the paper, the asymmetry is reduced, at least for printed papers. Also, properties such as resin savings and increased flexibility, in particular due to the dispersion in the paper, are retained.

Besondere Vorteile ergeben sich auch im Zusammenhang mit dem erfindungsgemäßen Verfahren bzw. einem erfindungsgemäßen Dekorpapier und der sogenannten Opazität.Particular advantages also arise in connection with the method according to the invention or a decor paper according to the invention and the so-called opacity.

Dekorpapiere benötigen eine ausreichende Opazität, damit nichts von der Spanplatte durchscheint. Die Opazität ergibt sich aus der Menge des Ti02, das in das Papier eingearbeitet ist. Soll die Opazität erhöht werden, muss mehr Ti02 eingearbeitet werden. Dies gelingt aber nur bei gleichzeitiger Erhöhung des Flächengewichtes, da das Netzwerk der Papierfasern nicht beliebig viel Ti02 halten kann. Das Papier wird instabiler, die Reißfestigkeit nimmt ab.Decorative papers need sufficient opacity so that nothing of the chipboard shows through. The opacity results from the amount of TiO 2 incorporated in the paper. If the opacity is to be increased, more Ti02 must be incorporated. However, this only succeeds in simultaneously increasing the basis weight, since the network of paper fibers can not hold any amount of TiO 2. The paper becomes more unstable, the tear strength decreases.

Auch hier können durch das erfindungsgemäß vorgeschlagene Verfahren bzw. das erfindungsgemäße Dekorpapier Vorteile erzielt werden. Ti02 kann als Farbe auf ein bestehendes Papier aufgedruckt werden. Dieser Aufdruck wird durch ein Überdrucken mit aliphatischer, polycarbonathaltiger anionischer Polyurethandispersion versiegelt. Durch das Aushärten der aliphatischen, polycarbonathaltigen anionischen Polyurethandispersion nach dem Drucken wird die Reißfestigkeit des Papiers erhöht. Bei gleichem Flächengewicht kann ein Papier produziert werden, dass eine höhere Opazität hat und zugleich die oben skizzierten Vorteile aufweist.Here, too, advantages can be achieved by the method proposed according to the invention or the decorative paper according to the invention. Ti02 can be printed as a color on an existing paper. This overprint is sealed by over-printing with aliphatic polycarbonate-containing anionic polyurethane dispersion. By curing the aliphatic, polycarbonate-containing anionic polyurethane dispersion after printing, the tear strength of the paper is increased. With the same basis weight, a paper can be produced that has a higher opacity and at the same time has the advantages outlined above.

Besondere Vorteile ergeben sich ferner im Zusammenhang mit dem erfindungsgemäßen Verfahren bzw. einem erfindungsgemäßen Dekorpapier und dem Papierwachstum.Particular advantages also arise in connection with the method according to the invention or a decor paper according to the invention and paper growth.

Insbesondere bei der Herstellung von Laminatfußboden ist das Wachstum des Papiers während der Imprägnierung ein zentrales Thema. Die einzelnen Panellen müssen die erwartete Breite haben; Kacheln sollen quadratisch bleiben. Eine besondere Herausforderung stellt eine synchron zum Druckbild verpresste Porenstruktur dar. Dies wird gemäß dem Stand der Technik dadurch realisiert, dass das Wachstum der Papierbahn auf Grund der Harzaufnahme empirisch ermittelt und dies in den Druckdaten berücksichtigt wird. Schwankungen in dem Wachstumsverhalten bedingt durch Schwankungen in der Papierfertigung führen zu erheblichem Ausschuss. Um ein symmetrisches Papierwachstum zu garantieren, muss Papier aus der Mitte der Papiermaschine entnommen werden, sodass diese nicht in der vollen Breite genutzt werden kann, da eine Papiermaschine auch doppelt so breit sein kann wie die weiterverarbeitenden Maschinen.Particularly in the production of laminate flooring, the growth of the paper during impregnation is a central theme. The individual panels must have the expected width; Tiles should remain square. A particular challenge is represented by a pore structure compressed synchronously with the print image. According to the prior art, this is realized by empirically determining the growth of the paper web on the basis of the resin absorption and taking this into account in the print data. Fluctuations in growth behavior due to fluctuations in paper production lead to considerable rejection. To guarantee symmetric paper growth, paper must be removed from the center of the paper machine so that it can not be used in its full width, since a paper machine can also be twice as wide as the further processing machines.

Auch hier können durch das erfindungsgemäß vorgeschlagene Verfahren bzw. das erfindungsgemäße Dekorpapier Vorteile erzielt werden. Durch das Aufbringen einer geeigneten Menge der aliphatischen, polycarbonathaltigen anionischen Polyurethandispersion kann das Papierwachstum von aktuell 1,5 % auf nahezu 0 reduziert werden. Die nach dem Drucken ausgehärtet aliphatische, polycarbonathaltige anionische Polyurethandispersion fixiert die Papierbreite. Das Papier wächst während der Imprägnierung nicht mehr.Here, too, advantages can be achieved by the method proposed according to the invention or the decorative paper according to the invention. By applying a suitable amount of the aliphatic, polycarbonate-containing anionic polyurethane dispersion, the paper growth can be reduced from currently 1.5% to almost zero. The aliphatic, polycarbonate-containing anionic polyurethane dispersion cured after printing fixes the paper width. The paper does not grow during the impregnation.

In der Regel wird die aliphatische, polycarbonathaltige anionische Polyurethandispersion auf der Druckseite aufgebracht. Wie die Anwendung "Planlage" beispielhaft zeigt, kann auch ein Aufbringen auf der Rückseite des Papiers vorteilhaft sein.As a rule, the aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied to the pressure side. As the application "flatness" shows by way of example, an application on the back of the paper can also be advantageous.

Claims (15)

  1. Method for producing decorative paper, characterized by the following steps:
    i) printing a paper;
    ii) applying an aliphatic, polycarbonate-containing anionic polyurethane dispersion.
  2. Method according to Claim 1, characterized in that a resin is applied to the printed paper after applying the aliphatic, polycarbonate-containing anionic polyurethane dispersion.
  3. Method according to any preceding claim, characterized in that applying the aliphatic, polycarbonate-containing anionic polyurethane dispersion results in a pH of 7-7.2 on the paper.
  4. Method according to any preceding claim, characterized in that the aliphatic, polycarbonate-containing anionic polyurethane dispersion is mixed in a ratio of 25 parts to 75 parts of water.
  5. Method according to any preceding claim, characterized in that the aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied atop the print at a dry weight of about 5 g/m2 .
  6. Method according to any preceding claim, characterized in that applying the aliphatic, polycarbonate-containing anionic polyurethane dispersion is effected in gravure printing using background cylinders.
  7. Method according to any preceding claim, characterized in that applying the aliphatic, polycarbonate-containing anionic polyurethane dispersion is effected in a varnishing factory.
  8. Method according to any preceding claim, characterized in that the paper is printed with metal effect paint.
  9. Method according to any preceding claim, characterized in that the aliphatic, polycarbonate-containing anionic polyurethane dispersion is applied to the unprinted side of the paper.
  10. Method according to any preceding claim, characterized in that the paper is printed with a TiO2-containing paint.
  11. Decorative paper comprising at least
    - a paper core (1),
    - a printed layer (2), and also
    - an aliphatic, polycarbonate-containing anionic polyurethane dispersion (3) embedded in the paper core (1).
  12. Decorative paper according to claim 11, characterized in that the decorative paper is saturated with aminoplastic resins (4).
  13. Decorative paper according to either claim 11 or 12, characterized in that it has been produced by a method according to at least one of claims 1 to 10.
  14. Decorative paper according to at least one preceding claim, characterized in that the printed layer is formed of a paint comprising mother-of-pearl pigment or TiO2.
  15. Decorative paper according to at least one preceding claim, characterized in that the paper core (1) is coated with an aliphatic, polycarbonate-containing anionic polyurethane dispersion layer on the side opposite the printed layer (2).
EP10702622A 2009-02-04 2010-02-03 Method for producing decorative paper and decorative paper Not-in-force EP2393670B1 (en)

Applications Claiming Priority (2)

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DE102009007544A DE102009007544B3 (en) 2009-02-04 2009-02-04 Process for the production of decorative paper and decorative paper
PCT/EP2010/000639 WO2010089086A1 (en) 2009-02-04 2010-02-03 Method for producing decorative paper and decorative paper

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EP2393670A1 EP2393670A1 (en) 2011-12-14
EP2393670B1 true EP2393670B1 (en) 2012-11-21

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EP (1) EP2393670B1 (en)
BR (1) BRPI1008225A2 (en)
DE (1) DE102009007544B3 (en)
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WO (1) WO2010089086A1 (en)

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DE102012207845A1 (en) * 2012-05-10 2013-11-14 Surface Technologies Gmbh & Co. Kg Method for producing a decorated sheet and its use
WO2017015749A1 (en) * 2015-07-24 2017-02-02 Robert Clausi Pressed laminate panel with a single layer elastomeric treated paper
EP3352202A4 (en) * 2015-09-18 2019-01-09 Japan Advanced Institute of Science and Technology Composite member, method for producing composite member, and layer containing aliphatic polycarbonate
EP3168363A1 (en) * 2015-11-12 2017-05-17 Interprint GmbH Method for producing an impregnate and a composite material, and use of polyurethane as impregnation agent
PL3754109T3 (en) 2019-06-18 2022-12-27 Schoeller Technocell Gmbh & Co. Kg Pre-impregnate with improved flatness
BE1029240B1 (en) * 2021-03-24 2022-10-24 Flooring Ind Ltd Sarl Panels and method of producing panels

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JPH081895A (en) * 1994-06-21 1996-01-09 Dainippon Printing Co Ltd Decorative sheet and production thereof
WO1996028610A1 (en) * 1995-03-13 1996-09-19 Portals Limited Security paper
DE10134302C1 (en) * 2001-07-14 2002-12-12 Technocell Dekor Gmbh & Co Kg Pre-impregnate obtained by impregnation of crude paper with a thermally hardenable formaldehyde-free resin useful in the production of decorative impregnates or coatings, and surface treatment of printed and unprinted papers
DK1361074T3 (en) * 2002-04-26 2005-08-29 Okt Kunststofftechnik Gmbh Process for improving the metal effects, further processing criteria and the flexibility of resin coated decor paper
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DE102009007544B3 (en) 2010-08-12
US20110300351A1 (en) 2011-12-08
BRPI1008225A2 (en) 2016-03-08
RU2011136712A (en) 2013-03-10
WO2010089086A1 (en) 2010-08-12
RU2519970C2 (en) 2014-06-20

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