EP0115038B1 - Process for the production of coloured decorative paper with a three-dimensional surface structure - Google Patents

Process for the production of coloured decorative paper with a three-dimensional surface structure Download PDF

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Publication number
EP0115038B1
EP0115038B1 EP83112899A EP83112899A EP0115038B1 EP 0115038 B1 EP0115038 B1 EP 0115038B1 EP 83112899 A EP83112899 A EP 83112899A EP 83112899 A EP83112899 A EP 83112899A EP 0115038 B1 EP0115038 B1 EP 0115038B1
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EP
European Patent Office
Prior art keywords
sheet
aqueous
binder
lacquer
printed
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Expired
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EP83112899A
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German (de)
French (fr)
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EP0115038A3 (en
EP0115038A2 (en
Inventor
Hans-Dieter Diesel
Hans-Joachim Schmidt
Burkhard Sauer
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Letron GmbH
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Letron GmbH
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Application filed by Letron GmbH filed Critical Letron GmbH
Priority to AT83112899T priority Critical patent/ATE41625T1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/06—Veined printings; Fluorescent printings; Stereoscopic images; Imitated patterns, e.g. tissues, textiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/18—Particular kinds of wallpapers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers

Definitions

  • the invention relates to a process for the production of colored decorative paper films with a 3-dimensional surface structure by printing the paper films with a pattern using an aqueous printing ink, drying the printed film, overpainting the printed film with an aqueous lacquer and curing the lacquered film, the Printing ink, which is printed on the areas where the lacquer layer is thinner than in the other areas, contains a lacquer-repellent.
  • the invention is based on the task of finding a simple and industrially easy to carry out process for producing the decorative paper foils described at the outset, which reliably leads to a 3-dimensional surface structure.
  • the object is achieved in accordance with the method of claim 1.
  • the paper foils are printed with a pattern as in the prior art. If only a two-color pattern is desired, it is sufficient if the paper film having a desired color is printed with a pattern with a different color.
  • multi-colored decorative paper foils can also be produced by printing the paper foils in succession with several colors in order to achieve the desired pattern. In any case, the last printing ink must be printed on the areas where the lacquer layer of the finished film is thinner than in the other areas. In order for this to be achieved, this last printed ink must contain a paint-repellent agent. As described in the abovementioned references, polysiloxanes based on silicone resins and oils can be used as paint repellants.
  • lower alkyl silicones such as dimethyl and diethyl silicone.
  • examples of such commercial products are Dri-Film 1040 from General Electric and silicone fluid 1107 from Dow Corning (registered trademarks).
  • Lower alkyl silicones which contain a certain proportion of phenyl groups, or ester waxes (waxes based on crude montan wax) can also be used.
  • a preferred feature of the process of the invention is that the paper film is printed with an aqueous gravure printing ink based on protein.
  • aqueous is understood to mean that the liquid phase essentially consists of water. Up to about 30% by volume, preferably up to 20% by volume, particularly preferably up to 10% by volume, based on the total amount, can be used as solubilizers the liquid phase, aliphatic monohydric or polyhydric alcohols can be contained in the printing ink.
  • methanol ethanol, ethyl glycol, propyl alcohols, glycerin, etc.
  • Preferred are ethanol and ethyl glycol or a mixture thereof, the proportion of ethyl glycol in the mixture of ethanol and ethyl glycol expediently being about 10 to 40% by volume, preferably about 15 to 30 Vol.%.
  • the printing ink contains an organic binder.
  • a preferred binder is casein.
  • the printing ink naturally contains the desired coloring pigments as well as any aforementioned paint additives such as silicone resins or oils and special waxes.
  • the printed decorative paper film is dried. It can be stored for a longer period of time, ie weeks, months or even years. The further processing can then take place at any place or at any time on a plant suitable for this.
  • An aqueous paint according to the definition above is used for painting.
  • the essential feature of the method of the invention in this regard is the use of an aqueous varnish.
  • the aqueous varnish contain small amounts, preferably up to 20 vol.%, particularly preferably up to 10 vol.%, of organic solvents as solubilizers. Suitable organic solvents for the varnish are ethanol, glycols, methoxybutanol.
  • aqueous paint have a processing viscosity in the range of 15-40 "AK 4/20 ° C, preferably 22-30".
  • the viscosity in the AK-4 cup is determined according to DIN 53211.
  • Such urea and melamine resins are cured in a known manner with an aqueous acid, as is known to the person skilled in the art.
  • Organic and inorganic acids can be used. Examples of organic acids are p-toluenesulfonic acid or blocked p-toluenesulfonic acid. Examples of suitable inorganic acids are phosphoric acid.
  • the mixture of urea and / or melamine resin and the hardener acid dissolved in water has a long pot life at room temperature (approx. 4 to 8 hours) and a short pot life at elevated temperature.
  • the catalyzed lacquer mixture must therefore harden at a temperature> 100 ° C. in less than 100 seconds, expediently in less than 80 seconds and preferably in less than about 60 seconds.
  • the paint contains the component B described above in the amount specified above as a binder.
  • At least about 10 parts by weight, preferably at least about 20 parts by weight, of binder B are preferably used per 100 parts by weight of solid-state binder A.
  • the upper limit for the proportion of binder B is expediently 250 parts by weight, preferably 150 parts by weight.
  • the product (registered trademark) is an example of acrylic resins and glycerol derivatives.
  • Worvonepol V 808 water-dilutable, low-viscosity, highly reactive polyester resin (Worlee-Chemie GmbH)
  • Acronal 240 D aqueous, plasticizer-free dispersion of a thermally crosslinkable copolymer based on an acrylic acid ester and styrene (BASF).
  • the commercial product is an example of ethoxylated glycerine derivatives
  • Plasticizer 9 oxyethylation product of glycerin (BASF).
  • the paint contains suitable paint additives, such as plasticizers, matting agents, defoamers, and anti-settling agents, as is known to the person skilled in the art.
  • the paint contains about 40 to 60 weight percent solids in binder. It is expediently applied in an amount of 10 to 50 grams of lacquer solution per m 2 of decorative paper film, preferably 25 to 35 grams per m 2 .
  • the film is cured by the action of air heated to more than 100 ° C. without the action of pressure.
  • the upper temperature limit for the heated air is determined by the prevention of undesirable properties that are common in paint technology, such as blistering and paint flow.
  • Aqueous impregnating resins such as are state of the art can be used here as urea, melamine, polyester or acrylate resins.
  • the film impregnated with the resin solution can be passed over a co-rotating or counter-rotating water-carrying roller before it enters a drying zone. Then the wash water applied by the roller together with excess impregnating resin from the (printed) top of the impregnated film z. B. wiped off with a squeegee. In order to avoid an accumulation of impregnating resin in the washing water that is fed to the roller, fresh water must be continuously added and the water containing impregnating resin must be removed. The film impregnated in this way and washed out on the top is then dried. The drying causes the impregnation resin to harden. It can be cured in the same way as described for the painting above.
  • the heated air suitably has a temperature of at least about 100 ° C, preferably at least about 140 ° C, and the upper limit for the heated air is suitably about 180 ° C, preferably 170 ° C.
  • a particularly pronounced effect with regard to the 3-dimensional surface can be achieved in that the lacquered film is passed directly after the lacquer application before heating with air with the unprinted side over a heated roller with a roller surface temperature of 60 ° C to 100 ° C.
  • roller surface temperature is expediently at least about 80 ° C. A particularly strong formation of the pores is achieved by this process variant.
  • a particular advantage of the process of the invention is that decorative paper films with excellent mechanical and chemical properties can be obtained from very thin paper films.
  • paper foils with a square meter weight of 30 to 250 grams can be used.
  • So-called laminate papers can be used which have not yet been impregnated with any synthetic resins.
  • Laminate papers which are smooth on one side and which are printed on the smooth side are particularly preferably used.
  • the 3-dimensional surface structure appears particularly strongly on the smooth side.
  • the rougher side on the other hand, enables a better connection to the surface on which the decorative paper foils are applied.
  • the papers used for printing can also have a pre-impregnation, such as is already carried out in the paper mill in the manufacture of such papers to be printed.
  • Such papers are commercially available under the name "special papers gap-resistant".
  • paint solutions can be mixtures of the following components: Paint A satin gloss: parts by weight
  • a commercially available paper with a weight of 60 g / m 2 (commercial product special paper splitting-resistant 60 g / m 2 from the company Holtzmann & Cie. AG) is printed using the ink A in the 1st inking unit with a wood grain pattern in direct gravure printing and dried .
  • the film printed in this way is printed in the second inking unit with printing ink B, which contains a paint-repellent agent. Printing with this printing ink takes place only at the points at which pore formation is to be generated. This printing ink is colored darker than printing ink A.
  • Printing ink B therefore basically has the same composition as printing ink A, only with the modifications described above.
  • the paper film printed in this way is coated after 2 months with the coating solution A on the printed surface with an application amount of 12 g / m 2 on a conventional paper coating machine, the application amount being set by a circular doctor blade.
  • the lacquered film is passed through a drying tunnel in which the air temperature rises from 100 ° C at the entrance to 150 ° C at the exit of the drying tunnel.
  • the dwell time in the drying tunnel is about 40 seconds.
  • a paper with a weight of 70 g / m 2 is used for printing, which is commercially available under the name: decor paper satin from the company PWA Dekor GmbH + Co. This paper is printed as described in Example 1.
  • the printed paper is impregnated with impregnation solution A in a conventional paper impregnation system. Excess impregnating agent is removed by squeezing rollers, so that the paper is provided with an amount of 45 g / m 2 solid impregnating resin.
  • the paper sheet with the printed side is guided over a roller running in an ambient temperature water bath. As a result, the resin on the printed side that has not penetrated into the film is washed off.
  • the wash water coating is wiped off using a circular doctor blade. Then will the impregnated paper is dried in a drying tunnel with a rising air temperature from 100 ° C to 175 ° C. This paper film can be stored and shipped.
  • This paper film is coated as described in Example 1.
  • a laminate paper with a weight of 220 g / m 2 is used, as it is called smooth on one side by the company Holtzmann & Cie. AG is available.
  • This paper is equipped as 4-color printing. Finally, in the fourth printing unit, that is to say after the inks 1 to 3 have dried, the printing ink modified with ester wax is applied and dried.
  • the printed paper is subjected to an intensive core impregnation with impregnation solution B in a manner known per se, an impregnation of 70% by weight, based on the weight of the paper, being achieved before washing, as described in Example 2 ( calculated as solid impregnation resin).
  • the impregnated paper is then passed over a water-carrying roller as described in Example 2 and dried.
  • the painting is done with paint C (matt paint).
  • the amount of paint applied is 15 grams of binder of the paint per m 2 of the paper film.
  • the film provided with the varnish is then immediately passed over a heating roller which has a surface temperature of 90 ° C.
  • the film is then passed through a drying tunnel with an increasing temperature profile from 80 ° C to 170 ° C, the dwell time being 40 seconds.

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Vascular Medicine (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)

Abstract

1. A process for the production of colored decorative sheet-form paper having a three-dimensional surface structure by printing the paper sheets with a pattern using an aqueous printing ink, drying the printed sheet, lacquering the printed sheet with an aqueous lacquer and hardening the lacquered sheet, the printing ink applied in those areas where the lacquer film is thinner than in the other areas containing a lacquer repellent, characterized in that the printed sheet is coated with an aqueous lacquer having a viscosity of 15 to 40 sec. in an AK4 cup essentially containing as binder a mixture of A) a mixture of a urea and/or melamine resin dissolved in water an an aqueous acid as hardener, which hardens in less than 100 seconds at > 100 degrees C after mixing of the aqueous resin solution with the acid, B) a binder selected from the group consisting of a) water-dilutable polyester resin, b) acrylate resin c) ethoxylated glycerine derivative, binder B) containing 10 to 250 parts by weight solids to 100 parts by weight solids in binder A), and the lacquered sheet is hardened in the absence of pressure by exposure to air heated to beyond 100 degrees C.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von farbigen Dekorpapierfolien mit einer 3- dimensionalen Oberflächenstruktur durch Bedrucken der Papierfolien mit einem Muster unter Verwendung einer wäßrigen Druckfarbe, Trocknen der bedruckten Folie, Überlackieren der bedruckten Folie mit einem wäßrigen Lack und Härten der lackierten Folie, wobei die Druckfarbe, die an den Bereichen aufgedruckt wird, an denen die Lackschicht dünner als an den anderen Bereichen ist, ein lackabstoßendes Mittel enthält.The invention relates to a process for the production of colored decorative paper films with a 3-dimensional surface structure by printing the paper films with a pattern using an aqueous printing ink, drying the printed film, overpainting the printed film with an aqueous lacquer and curing the lacquered film, the Printing ink, which is printed on the areas where the lacquer layer is thinner than in the other areas, contains a lacquer-repellent.

Ein Verfahren der oben beschriebenen Art wird in der DE-A-3 024 393 beschrieben. Ein ähnliches Verfahren wird auch in der US-A-3 811 915 beschrieben; ein wesentlicher Nachteil dieses Verfahrens liegt darin, daß das bedruckte Papier spätestens innerhalb von 20 Stunden lackiert werden muß, da sonst ein 3-dimensionales Muster nicht mehr erhalten werden kann (vergleiche Spalte 3, Zeile 59-61). Es besteht jedoch ein Bedürfnis danach, zunächst die Papierfolien zu bedrucken und sie in einem getrennten Arbeitsgang nach Bedarf zu lackieren. Der Grund hierfür liegt u.a. darin, daß das Bedrucken von Papierfolien häufig in anderen Fabriken durchgeführt wird, als das Imprägnieren bzw. Lackieren mit Kunstharzbindemittel enthaltenden Lösungen. Die bedruckten Papiere können dann gelagert und versandt und zu einem beliebigen Zeitpunkt lackiert werden unter Herstellung der Dekorpapierfolien mit einer 3-dimensionalen Oberflächenstruktur.A method of the type described above is described in DE-A-3 024 393. A similar process is also described in US-A-3,811,915; A major disadvantage of this process is that the printed paper has to be coated within 20 hours at the latest, since otherwise a 3-dimensional pattern can no longer be obtained (see column 3, lines 59-61). However, there is a need to first print on the paper foils and to varnish them as required in a separate operation. One of the reasons for this is in that the printing of paper foils is often carried out in factories other than the impregnation or lacquering with solutions containing synthetic resin binders. The printed papers can then be stored and dispatched and varnished at any time to produce the decorative paper foils with a 3-dimensional surface structure.

Ein anderes Verfahren zur Herstellung derartiger Dekorpapierfolien. ist in der DE-A-3 024 391 beschrieben. Die Papierfolien werden gemäß diesem Verfahren durch ein aufeinanderfolgendes Aufbringen mehrerer Grundfarben bedruckt, wobei die letzte Grundfarbe ein lackabstoßendes Mittel enthält, und das Papier wird danach gegebenenfalls imprägniert und anschließend lackiert. Angaben über geeignete zu verwendende Lacke werden jedoch nicht gemacht.Another method for producing such decorative paper foils. is described in DE-A-3 024 391. According to this method, the paper foils are printed by successively applying a plurality of base colors, the last base color containing a paint-repelling agent, and the paper is then optionally impregnated and then coated. However, no information is given on suitable lacquers to be used.

Der Erfindung liegt die Aufgabenstellung zugrunde, ein einfaches und großtechnisch leicht durchzuführendes Verfahren zur Herstellung der eingangs beschriebenen Dekorpapierfolien zu finden, das zuverlässig zu einer 3-dimensionalen Oberflächenstruktur führt.The invention is based on the task of finding a simple and industrially easy to carry out process for producing the decorative paper foils described at the outset, which reliably leads to a 3-dimensional surface structure.

Die Lösung der Aufgabe erfolgt gemäß dem Verfahren von Anspruch 1. Die Papierfolien werden, wie gemäß dem Stand der Technik, mit einem Muster bedruckt. Wenn nur ein zweifarbiges Muster gewünscht wird, genügt es, wenn die eine gewünschte Farbe aufweisende Papierfolie mit einem Muster mit einer anderen Farbe bedruckt wird. Es können aber auch mehrfarbige Dekorpapierfolien dadurch hergestellt werden, daß die Papierfolien mit mehreren Farben nacheinander zur Erzielung des gewünschten Musters bedruckt werden. In jedem Fall muß die letzte Druckfarbe an den Bereichen aufgedruckt werden, an denen die Lackschicht der fertigen Folie dünner ist als an den anderen Bereichen. Damit dies erzielt wird, muß diese zuletzt aufgedruckte Druckfarbe ein lackabstoßendes Mittel enthalten. Als lackabsto- ßende Mittel können, wie in den oben genannten Literaturstellen beschrieben, Polysiloxane auf der Basis von Silikonharzen und -ölen sein. Spezielle Beispiele sind niedere Alkylsilikone wie Dimethyl-und Diethylsilikon. Beispiele für derartige Handelsprodukte sind Dri-Film 1040 der Firma General Electric und Silikonefluid 1107 der Firma Dow Corning (eingetragene Warenzeichen). Es können auch niedere Alkylsilikone, welche einen gewissen Anteil Phenylgruppen enthalten, oder Esterwachse (Wachse auf Basis Rohmontanwachs) verwendet werden.The object is achieved in accordance with the method of claim 1. The paper foils are printed with a pattern as in the prior art. If only a two-color pattern is desired, it is sufficient if the paper film having a desired color is printed with a pattern with a different color. However, multi-colored decorative paper foils can also be produced by printing the paper foils in succession with several colors in order to achieve the desired pattern. In any case, the last printing ink must be printed on the areas where the lacquer layer of the finished film is thinner than in the other areas. In order for this to be achieved, this last printed ink must contain a paint-repellent agent. As described in the abovementioned references, polysiloxanes based on silicone resins and oils can be used as paint repellants. Specific examples are lower alkyl silicones such as dimethyl and diethyl silicone. Examples of such commercial products are Dri-Film 1040 from General Electric and silicone fluid 1107 from Dow Corning (registered trademarks). Lower alkyl silicones, which contain a certain proportion of phenyl groups, or ester waxes (waxes based on crude montan wax) can also be used.

Durch den Gehalt der zuletzt aufgedruckten Druckfarbe an derartigen lackabstoßenden Mitteln wird erreicht, daß dann, wenn man in der beschriebenen geeigneten Weise lackiert, an den mit dieser Druckfarbe bedruckten Stellen der Lack abgestoßen wird und deshalb dünner ausgebildet ist, als in den anderen Bereichen. Man erzielt so auf einer eine glatte Oberfläche aufweisenden Dekorpapierfolie eine deutlich 3-dimensionale Oberflächenstruktur, wie sie eine Holzoberfläche (Furnier) aufweist. Die Dekorpapierfolien gemäß der Erfindung sind, wenn sie mit einem Holzmuster bedruckt wurden, von einem künstlichen Holzfurnier praktisch nicht zu unterscheiden.The content of such paint-repelling agents in the last-printed printing ink ensures that when painting in the appropriate manner described, the paint is repelled at the points printed with this printing ink and is therefore thinner than in the other areas. In this way, a clearly 3-dimensional surface structure, such as that which has a wooden surface (veneer), is achieved on a decorative paper film having a smooth surface. The decorative paper foils according to the invention, when printed with a wood pattern, are practically indistinguishable from an artificial wood veneer.

Ein bevorzugtes Merkmal des Verfahrens der Erfindung besteht darin, daß die Papierfolie mit einer wäßrigen Tiefdruckfarbe auf Proteinbasis bedruckt wird. Unter dem Begriff «wäßrig" wird verstanden, daß die flüssige Phase im wesentlichen aus Wasser besteht. Als Lösungsvermittler können bis zu etwa 30 Volum%, vorzugsweise bis zu 20 Vol.%, besonders bevorzugt bis zu 10 Vol.%, bezogen auf die Gesamtmenge der flüssigen Phase, aliphatische einwertige oder mehrwertige Alkohole in der Druckfarbe enthalten sein.A preferred feature of the process of the invention is that the paper film is printed with an aqueous gravure printing ink based on protein. The term “aqueous ” is understood to mean that the liquid phase essentially consists of water. Up to about 30% by volume, preferably up to 20% by volume, particularly preferably up to 10% by volume, based on the total amount, can be used as solubilizers the liquid phase, aliphatic monohydric or polyhydric alcohols can be contained in the printing ink.

Beispiele hierfür sind Methanol, Ethanol, Ethylglycol, Propylalkohole, Glyzerin usw. Bevorzugt sind Ethanol und Ethylglycol oder ein Gemisch davon, wobei in dem Gemisch aus Ethanol und Ethylglycol der Anteil an Ethylglycol zweckmäßig etwa 10 bis 40 Vol.%, vorzugsweise etwa 15 bis 30 Vol.% beträgt.Examples of these are methanol, ethanol, ethyl glycol, propyl alcohols, glycerin, etc. Preferred are ethanol and ethyl glycol or a mixture thereof, the proportion of ethyl glycol in the mixture of ethanol and ethyl glycol expediently being about 10 to 40% by volume, preferably about 15 to 30 Vol.%.

Die Druckfarbe enthält ein organisches Bindemittel. Ein bevorzugtes Bindemittel ist Casein. Außerdem enthält die Druckfarbe naturgemäß die gewünschten farbgebenden Pigmente sowie gegebenenfalls vorgenannte lacktechnische Zusatzmittel wie Silikonharze bzw. -öle und spezielle Wachse.The printing ink contains an organic binder. A preferred binder is casein. In addition, the printing ink naturally contains the desired coloring pigments as well as any aforementioned paint additives such as silicone resins or oils and special waxes.

Ein weiteres wesentliches Merkmal des Verfahrens der Erfindung besteht darin, daß die bedruckte Dekorpapierfolie getrocknet wird. Sie kann so längere Zeit, d.h. Wochen, Monate oder sogar Jahre gelagert werden. Die Weiterverarbeitung kann dann an einem beliebigen Ort bzw. zu einem beliebigen Zeitpunkt auf einer hierfür geeigneten Anlage erfolgen. Zum Lackieren wird ein wäßriger Lack gemäß der obigen Definition verwendet. Das wesentliche Merkmal des Verfahrens der Erfindung in dieser Beziehung besteht in der Verwendung eines wäßrigen Lackes. Auch hier kann, wie bereits in Zusammenhang mit der Druckfarbe beschrieben, der wäßrige Lack geringe Mengen, vorzugsweise bis zu 20 Vol.%, besonders bevorzugt bis zu 10 Vol.%, organische Lösungsmittel als Lösungsvermittler enthalten. Geeignete organische Lösungsmittel für den Lack sind Ethanol, Glycole, Methoxybutanol.Another essential feature of the method of the invention is that the printed decorative paper film is dried. It can be stored for a longer period of time, ie weeks, months or even years. The further processing can then take place at any place or at any time on a plant suitable for this. An aqueous paint according to the definition above is used for painting. The essential feature of the method of the invention in this regard is the use of an aqueous varnish. Here too, as already in connection with the printing ink wrote that the aqueous varnish contain small amounts, preferably up to 20 vol.%, particularly preferably up to 10 vol.%, of organic solvents as solubilizers. Suitable organic solvents for the varnish are ethanol, glycols, methoxybutanol.

Es ist wichtig, daß der wäßrige Lack eine Verarbeitungsviskosität im Bereich von 15-40" AK 4/ 20°C aufweist, vorzugsweise 22-30". Die Bestimmung der Viskosität im AK-4 Becher erfolgt nach DIN 53211.It is important that the aqueous paint have a processing viscosity in the range of 15-40 "AK 4/20 ° C, preferably 22-30". The viscosity in the AK-4 cup is determined according to DIN 53211.

Eine wesentliche Bindemittelkomponente ist das unter a) definierte Harnstoff- und/oder Melaminharz. Es handelt sich hier um im Handel erhältliche wäßrige Lösungen solcher Harze. Beispiele für derartige Handelsprodukte sind

  • 1) Maprenal MF 900 = nichtplastifiziertes Hexamethoxymethylmelaminharz (Hoechst AG) (eingetragenes Warenzeichen)
  • 2) Maprenal MF 920 = hochreaktives, nicht plastifiziertes Melaminharz (Hoechst AG) (eingetragenes Warenzeichen)
  • 3) Methanolverätherte Harnstoff- bzw. Melaminharze der Plastopal- und Luwipal-Reihe (BASF) (eingetragenes Warenzeichen).
An essential binder component is the urea and / or melamine resin defined under a). These are commercially available aqueous solutions of such resins. Examples of such commercial products are
  • 1) Maprenal MF 900 = non-plasticized hexamethoxymethyl melamine resin (Hoechst AG) (registered trademark)
  • 2) Maprenal MF 920 = highly reactive, non-plasticized melamine resin (Hoechst AG) (registered trademark)
  • 3) Methanol-etherified urea or melamine resins from the Plastopal and Luwipal series (BASF) (registered trademark).

Derartige Harnstoff- und Melaminharze werden in bekannter Weise mit einer wäßrigen Säure gehärtet, wie dies dem Fachmann bekannt ist. Es können organische und anorganische Säuren eingesetzt werden. Beispiele für organische Säuren sind p-Toluolsulfonsäure, bzw. geblockte p-Toluolsulfonsäure. Beispiel für geeignete anorganische Säuren ist Phosphorsäure.Such urea and melamine resins are cured in a known manner with an aqueous acid, as is known to the person skilled in the art. Organic and inorganic acids can be used. Examples of organic acids are p-toluenesulfonic acid or blocked p-toluenesulfonic acid. Examples of suitable inorganic acids are phosphoric acid.

Wichtig ist, daß das Gemisch aus in Wasser gelöstem Harnstoff- und/oder Melaminharz und der Härtersäure ein langes potlife bei Raumtemperatur (ca. 4 bis 8 Stunden), und ein kurzes potlife bei erhöhter Temperatur aufweist. Das katalysierte Lackgemisch muß also, bei Temperatur > 100°C, in weniger als 100 Sekunden, zweckmäßig in weniger als 80 Sekunden und vorzugsweise in weniger als etwa 60 Sekunden härten.It is important that the mixture of urea and / or melamine resin and the hardener acid dissolved in water has a long pot life at room temperature (approx. 4 to 8 hours) and a short pot life at elevated temperature. The catalyzed lacquer mixture must therefore harden at a temperature> 100 ° C. in less than 100 seconds, expediently in less than 80 seconds and preferably in less than about 60 seconds.

Um einen guten 3-dimensionalen Effekt zu erzielen, ist es erforderlich, daß der Lack als Bindemittel die oben beschriebene Komponente B in der oben angegebenen Menge enthält. Bevorzugt werden auf 100 Gewichtsteile Festkörperbindemittel A mindestens etwa 10 Gewichtsteile, vorzugsweise mindestens etwa 20 Gewichtsteile Bindemittel B eingesetzt. Andererseits liegt die obere Grenze für den Anteil an Bindemittel B zweckmäßig bei 250 Gewichtsteilen, bevorzugt bei 150 Gewichtsteilen.In order to achieve a good 3-dimensional effect, it is necessary that the paint contains the component B described above in the amount specified above as a binder. At least about 10 parts by weight, preferably at least about 20 parts by weight, of binder B are preferably used per 100 parts by weight of solid-state binder A. On the other hand, the upper limit for the proportion of binder B is expediently 250 parts by weight, preferably 150 parts by weight.

Beispiel für Acrylharze und Glycerinderivate ist das Produkt (eingetragenes Warenzeichen)The product (registered trademark) is an example of acrylic resins and glycerol derivatives.

Worläepol V 808 = wasserverdünnbares, niedrigviskoses, hochreaktives Polyesterharz (Worlee-Chemie GmbH)Worläepol V 808 = water-dilutable, low-viscosity, highly reactive polyester resin (Worlee-Chemie GmbH)

Beispiel für geeignetes Acrylharz ist (eingetragenes Warenzeichen)An example of a suitable acrylic resin is (registered trademark)

Acronal 240 D = wäßrige, weichmacherfreie Dispersion eines thermisch vernetzbaren Copolymerisates auf Basis eines Acrylsäureester und Styrol (BASF).Acronal 240 D = aqueous, plasticizer-free dispersion of a thermally crosslinkable copolymer based on an acrylic acid ester and styrene (BASF).

Beispiel für äthoxylierte Glyzerinderivate ist das HandelsproduktThe commercial product is an example of ethoxylated glycerine derivatives

Weichmachungsmittel 9 = Oxäthylierungsprodukt des Glyzerins (BASF).Plasticizer 9 = oxyethylation product of glycerin (BASF).

Auch hier gilt das Gleiche. Der Lack enthält außer den Bindemitteln geeignete lacktechnische Zusatzstoffe wie Weichmacher, Mattierungsmittel, Entschäumer, das Absetzen verhindernde Mittel, wie dies dem Fachmann bekannt ist.The same applies here too. In addition to the binders, the paint contains suitable paint additives, such as plasticizers, matting agents, defoamers, and anti-settling agents, as is known to the person skilled in the art.

Der Lack enthält an Bindemittel etwa 40 bis 60 Gewichtsprozente Festkörper. Er wird zweckmäßig in einer Menge von 10 bis 50 Gramm Lacklösung pro m2 Dekorpapierfolie, vorzugsweise 25 bis 35 Gramm pro m2 aufgetragen.The paint contains about 40 to 60 weight percent solids in binder. It is expediently applied in an amount of 10 to 50 grams of lacquer solution per m 2 of decorative paper film, preferably 25 to 35 grams per m 2 .

Unmittelbar nach dem Lackieren wird die Folie durch Einwirkung von auf mehr als 100°C erwärmte Luft ohne Einwirkung von Druck gehärtet. Die obere Temperaturgrenze für die erwärmte Luft wird bestimmt durch die Verhinderung von auf lacktechnischem Gebiet üblichen unerwünschten Eigenschaften wie Blasenbildung, Lackverlauf.Immediately after painting, the film is cured by the action of air heated to more than 100 ° C. without the action of pressure. The upper temperature limit for the heated air is determined by the prevention of undesirable properties that are common in paint technology, such as blistering and paint flow.

Zweckmäßig wird in einem Hängetrockner getrocknet, wobei die Temperatur der erwärmten Luft ansteigt bis auf etwa 160°C. Zur Herstellung einer Dekorpapierfolie mit besonders guten mechanischen Eigenschaften ist es zweckmäßig, daß nach dem im Anspruch 2 beschriebenen Verfahren gearbeitet wird.It is expedient to dry in a hanging dryer, the temperature of the heated air rising to about 160.degree. To produce a decorative paper film with particularly good mechanical properties, it is advantageous that the process described in claim 2 is used.

Als Harnstoff-, Melamin-, Polyester- oder Acrylatharze können hier wäßrige Imprägnierharze eingesetzt werden, wie sie Stand der Technik sind.Aqueous impregnating resins such as are state of the art can be used here as urea, melamine, polyester or acrylate resins.

Zur Durchführung dieser Verfahrensstufe kann die mit der Harzlösung imprägnierte Folie vor dem Einlauf in eine Trockenzone über eine gleichlaufende oder gegenläufige wasserführende Walze geführt werden. Danach wird das durch die Walze aufgetragene Waschwasser zusammen mit überschüssigem Imprägnierharz von der (bedruckten) Oberseite der imprägnierten Folie z. B. mittels eines Rakels abgestrichen. Um eine Anreicherung von Imprägnierharz im Waschwasser, das der Walze zugeführt wird, zu vermeiden, muß ständig Frischwasser zugeführt und das imprägnierharzhaltige Wasser abgeführt werden. Die so imprägnierte und an der Oberseite ausgewaschene Folie wird anschließend getrocknet. Die Trocknung bewirkt eine Härtung des Imprägnierharzes. Es kann in gleicher Weise gehärtet werden, wie dies oben bei der Lackierung beschrieben wurde. Zweckmäßig wird jedoch die Härtung dieses Imprägnierharzes bei etwas höheren Temperaturen vorgenommen, d.h. die erwärmte Luft hat zweckmäßig eine Temperatur von mindestens etwa 100°C, vorzugsweise mindestens etwa 140°C, und die obere Grenze für die erwärmte Luft liegt zweckmäßig bei etwa 180°C, vorzugsweise bei 170 °C.To carry out this process step, the film impregnated with the resin solution can be passed over a co-rotating or counter-rotating water-carrying roller before it enters a drying zone. Then the wash water applied by the roller together with excess impregnating resin from the (printed) top of the impregnated film z. B. wiped off with a squeegee. In order to avoid an accumulation of impregnating resin in the washing water that is fed to the roller, fresh water must be continuously added and the water containing impregnating resin must be removed. The film impregnated in this way and washed out on the top is then dried. The drying causes the impregnation resin to harden. It can be cured in the same way as described for the painting above. However, this impregnating resin is expediently cured at somewhat higher temperatures, i.e. the heated air suitably has a temperature of at least about 100 ° C, preferably at least about 140 ° C, and the upper limit for the heated air is suitably about 180 ° C, preferably 170 ° C.

Ein besonders ausgeprägter Effekt hinsichtlich der 3-dimensionalen Oberfläche kann dadurch erzielt werden, daß die lackierte Folie unmittelbar nach dem Lackauftrag vor dem Erwärmen mit Luft mit der unbedruckten Seite über eine geheizte Walze mit einer Walzenoberflächentemperatur von 60°C bis 100°C geführt wird.A particularly pronounced effect with regard to the 3-dimensional surface can be achieved in that the lacquered film is passed directly after the lacquer application before heating with air with the unprinted side over a heated roller with a roller surface temperature of 60 ° C to 100 ° C.

Zweckmäßig beträgt die Walzenoberflächentemperatur mindestens etwa 80°C. Durch diese Verfahrensvariante wird eine besonders starke Ausbildung der Poren erzielt.The roller surface temperature is expediently at least about 80 ° C. A particularly strong formation of the pores is achieved by this process variant.

Ein besonderer Vorteil des Verfahrens der Erfindung liegt darin, daß aus sehr dünnen Papierfolien Dekorpapierfolien mit ausgezeichneten mechanischen und chemischen Eigenschaften erhalten werden können. Gemäß der Erfindung können Papierfolien mit einem Quadratmetergewicht von 30 bis 250 Gramm eingesetzt werden. Es können sogenannte Laminatpapiere verwendet werden, die noch keine Imprägnierung mit irgendwelchen Kunstharzen aufweisen.A particular advantage of the process of the invention is that decorative paper films with excellent mechanical and chemical properties can be obtained from very thin paper films. According to the invention, paper foils with a square meter weight of 30 to 250 grams can be used. So-called laminate papers can be used which have not yet been impregnated with any synthetic resins.

Besonders bevorzugt werden einseitig glatte Laminatpapiere eingesetzt, die auf der glatten Seite bedruckt werden. Auf der glatten Seite tritt die 3-dimensionale Oberflächenstruktur besonders stark in Erscheinung. Die rauhere Seite ermöglicht andererseits eine bessere Verbindung mit dem Untergrund, auf den die Dekorpapierfolien appliziert werden.Laminate papers which are smooth on one side and which are printed on the smooth side are particularly preferably used. The 3-dimensional surface structure appears particularly strongly on the smooth side. The rougher side, on the other hand, enables a better connection to the surface on which the decorative paper foils are applied.

Die für den Druck eingesetzten Papiere können auch schon eine Vorimprägnierung aufweisen, wie sie bei der Herstellung derartiger zu bedrukkender Papiere in der Papierfabrik bereits durchgeführt wird. Solche Papiere sind im Handel erhältlich unter der Bezeichnung «Spezialpapiere spaltfest".The papers used for printing can also have a pre-impregnation, such as is already carried out in the paper mill in the manufacture of such papers to be printed. Such papers are commercially available under the name "special papers gap-resistant".

Um eine besonders glatte Oberfläche auf der zu bedruckenden Seite zu erhalten, ist es möglich, die Papiere vor dem Bedrucken mit der zu bedruckenden Seite über sogenannte Superkalander zu führen.In order to obtain a particularly smooth surface on the side to be printed, it is possible to pass the papers over so-called super calenders before printing with the side to be printed.

In den nachfolgenden Beispielen wird die Erfindung erläutert. Bei den angegebenen Mengen handelt es sich um Gewichtsteile, sofern nichts anderes angegeben ist.The invention is explained in the following examples. The stated amounts are parts by weight, unless stated otherwise.

Beispiel für Druckfarben: Druckfarbe A: Gew.Teile

Figure imgb0001
Example of printing inks: Printing ink A: parts by weight
Figure imgb0001

Beispiele für Lacklösungen können Gemische folgender Komponenten sein: Lack A seidenglänzend: Gew.Teile

Figure imgb0002
Examples of paint solutions can be mixtures of the following components: Paint A satin gloss: parts by weight
Figure imgb0002

Lack B seidenmatt:Lacquer B semi-gloss:

Maprenal MF 900/95% (Hoechst AG) 32.0

Figure imgb0003
Beispiele für lmprägnierlösungen:
Figure imgb0004
 Maprenal MF 900/95% (Hoechst AG) 32.0
Figure imgb0003
 Examples of impregnation solutions:
Figure imgb0004

Beispiel 1example 1

Ein im Handel erhältliches Papier mit einem Gewicht von 60 g/m2 (Handelsprodukt Spezialpapier spaltfest 60 g/m2 der Firma Holtzmann & Cie. AG) wird unter Verwendung der Druckfarbe A im 1. Farbwerk mit einem Holzmaserungsmuster im direkten Tiefdruck bedruckt und getrocknet. Die so bedruckte Folie wird im 2. Farbwerk mit der Druckfarbe B bedruckt, die ein lackabstoßendes Mittel enthält. Der Druck mit dieser Druckfarbe erfolgt lediglich an den Stellen, an denen eine Porenbildung erzeugt werden soll. Diese Druckfarbe ist dunkler eingefärbt als die Druckfarbe A. Die Druckfarbe B hat also grundsätzlich die gleiche Zusammensetzung wie die Druckfarbe A, lediglich mit den vorstehend beschriebenen Abänderungen.A commercially available paper with a weight of 60 g / m 2 (commercial product special paper splitting-resistant 60 g / m 2 from the company Holtzmann & Cie. AG) is printed using the ink A in the 1st inking unit with a wood grain pattern in direct gravure printing and dried . The film printed in this way is printed in the second inking unit with printing ink B, which contains a paint-repellent agent. Printing with this printing ink takes place only at the points at which pore formation is to be generated. This printing ink is colored darker than printing ink A. Printing ink B therefore basically has the same composition as printing ink A, only with the modifications described above.

Die so bedruckte Papierfolie wird nach 2 Monaten mit der Lacklösung A auf der bedruckten Oberfläche mit einer Auftragsmenge von 12 g/m2 auf einer üblichen Papierlackiermaschine lackiert, wobei durch einen Rundrakel die Auftragsmenge eingestellt wird. Die lackierte Folie wird durch einen Trockenkanal geleitet, in dem die Lufttemperatur von 100 °C am Eingang bis 150 °C am Ausgang des Trockenkanals ansteigt. Die Verweilzeit im Trockenkanal beträgt etwa 40 Sekunden.The paper film printed in this way is coated after 2 months with the coating solution A on the printed surface with an application amount of 12 g / m 2 on a conventional paper coating machine, the application amount being set by a circular doctor blade. The lacquered film is passed through a drying tunnel in which the air temperature rises from 100 ° C at the entrance to 150 ° C at the exit of the drying tunnel. The dwell time in the drying tunnel is about 40 seconds.

Beispiel 2Example 2

Es wird zum Bedrucken ein Papier mit einem Gewicht von 70 g/m2 verwendet, das im Handel unter der Bezeichnung: Dekorpapier satiniert der Firma PWA Dekor GmbH + Co. erhältlich ist. Dieses Papier wird wie im Beispiel 1 beschrieben bedruckt.A paper with a weight of 70 g / m 2 is used for printing, which is commercially available under the name: decor paper satin from the company PWA Dekor GmbH + Co. This paper is printed as described in Example 1.

Das bedruckte Papier wird mit der Imprägnierlösung A in einer üblichen Papierimprägnieranlage imprägniert. Überschüssiges Imprägniermittel wird durch Quetschwalzen entfernt, so daß das Papier mit einer Menge von 45 g/m2 Festkörperimprägnierharz versehen ist. Unmittelbar anschließend wird die Papierfolie mit der bedruckten Seite über eine in einem Umweltstemperatur aufweisenden Wasserbad laufende Walze geführt. Dadurch wird das an der bedruckten Seite befindliche, in die Folie nicht eingedrungene Harz abgewaschen. Der Waschwasserüberzug wird durch einen Rundrakel abgestrichen. Anschließend wird das imprägnierte Papier in einem Trockenkanal mit ansteigender Umlufttemperatur von 100 °C bis 175°C getrocknet. Diese Papierfolie kann gelagert und versandt werden.The printed paper is impregnated with impregnation solution A in a conventional paper impregnation system. Excess impregnating agent is removed by squeezing rollers, so that the paper is provided with an amount of 45 g / m 2 solid impregnating resin. Immediately afterwards, the paper sheet with the printed side is guided over a roller running in an ambient temperature water bath. As a result, the resin on the printed side that has not penetrated into the film is washed off. The wash water coating is wiped off using a circular doctor blade. Then will the impregnated paper is dried in a drying tunnel with a rising air temperature from 100 ° C to 175 ° C. This paper film can be stored and shipped.

Die Lackierung dieser Papierfolie erfolgt wie im Beispiel 1 beschrieben.This paper film is coated as described in Example 1.

Beispiel 3Example 3

Es wird ein Laminatpapier mit einem Gewicht von 220 g/m2 verwendet, wie es unter der Bezeichnung Kantenkarton einseitig glatt von der Firma Holtzmann & Cie. AG erhältlich ist.A laminate paper with a weight of 220 g / m 2 is used, as it is called smooth on one side by the company Holtzmann & Cie. AG is available.

Dieses Papier wird als 4-Farbendruck ausgerüstet. Als Letzte wird im 4. Druckwerk, also nach der Trocknung der Farben 1. bis 3. die mit Esterwachs modifizierte Druckfarbe aufgebracht und getrocknet.This paper is equipped as 4-color printing. Finally, in the fourth printing unit, that is to say after the inks 1 to 3 have dried, the printing ink modified with ester wax is applied and dried.

Das bedruckte Papier wird nach 2 Monaten in an sich bekannter Weise einer intensiven Kernimprägnierung mit der Imprägnierlösung B unterworfen, wobei vor dem Waschen, wie es in Beispiel 2 beschrieben wurde, eine Imprägnierung von 70 Gewichtsprozent, bezogen auf das Gewicht des Papiers, erzielt wird (gerechnet als Festkörperimprägnierharz). Anschließend wird das imprägnierte Papier wie in Beispiel 2 beschrieben über eine wasserführende Walze geleitet und getrocknet.After 2 months, the printed paper is subjected to an intensive core impregnation with impregnation solution B in a manner known per se, an impregnation of 70% by weight, based on the weight of the paper, being achieved before washing, as described in Example 2 ( calculated as solid impregnation resin). The impregnated paper is then passed over a water-carrying roller as described in Example 2 and dried.

Die Lackierung erfolgt mit dem Lack C (Mattlack).The painting is done with paint C (matt paint).

Die Lackauftragsmenge beträgt 15 Gramm Bindemittel des Lackes pro m2 der Papierfolie. Die mit dem Lackauftrag versehene Folie wird unmittelbar anschließend über eine Heizwalze geführt, die eine Oberflächentemperatur von 90°C aufweist. Anschließend wird die Folie durch einen Trockenkanal mit ansteigendem Temperaturprofil von 80°C bis 170°C geführt, wobei die Verweildauer 40 Sekunden beträgt.The amount of paint applied is 15 grams of binder of the paint per m 2 of the paper film. The film provided with the varnish is then immediately passed over a heating roller which has a surface temperature of 90 ° C. The film is then passed through a drying tunnel with an increasing temperature profile from 80 ° C to 170 ° C, the dwell time being 40 seconds.

Claims (3)

1. A process for the production of colored decorative sheet-form paper having a three-dimensional surface structure by printing the paper sheets with a pattern using an aqueous printing ink, drying the printed sheet, lacquering the printed sheet with an aqueous lacquer and hardening the lacquered sheet, the printing ink applied in those areas where the lacquer film is thinner than in the other areas containing a lacquer repellent, characterized in that the printed sheet is coated with an aqueous lacquer having a viscosity of 15 to 40 sec. in an AK4 cup essentially containing as binder a mixture of
A) a mixture of a urea and/or melamine resin dissolved in water an an aqueous acid as hardener, which hardens in less than 100 seconds at > 100°C after mixing of the aqueous resin solution with the acid,
B) a binder selected from the group consisting of
a) water-dilutable polyester resin,
b) acrylate resin
c) ethoxylated glycerine derivative, binder B) containing 10 to 250 parts by weight solids to 100 parts by weight solids in binder A), and
the lacquered sheet is hardened in the absence of pressure by exposure to air heated to beyond 100°C.
2. A process as claimed in claim 1, characterized in that, before lacquering, the printed sheet is impregnated with an aqueous impregnating solution having a viscosity of 15 to 30 seconds in an AK4 cup and containing a binder selected from the group consisting of
i) urea resins
ii) melamine resins
iii) polyester resins
iv) acrylate resins
and, immediately after impregnation, the impregnated sheet is passed with the printed side face down over a roller of which the surface is coated with water, the coating of washing water is removed from the sheet and the sheet is hardened in the absence of pressure by exposure to air heated to beyond 100°C.
3. A process as claimed in claim 2, characterized in that, immediately after lacquering and before heating with air, the sheet impregnated in accordance with claim 2 is passed with the unprinted side face down over a heated roller having a surface temperature of 60 to 100°C.
EP83112899A 1982-12-23 1983-12-21 Process for the production of coloured decorative paper with a three-dimensional surface structure Expired EP0115038B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83112899T ATE41625T1 (en) 1982-12-23 1983-12-21 PROCESS FOR MANUFACTURING COLORED DECORATIVE PAPER FOILS WITH A 3-DIMENSIONAL SURFACE STRUCTURE.

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DE3247677 1982-12-23
DE19823247677 DE3247677A1 (en) 1982-12-23 1982-12-23 METHOD FOR PRODUCING COLORED DECORATION PAPER FILMS WITH A 3-DIMENSIONAL SURFACE STRUCTURE

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CA2071029A1 (en) * 1991-06-24 1992-12-25 Yoshihide Ozaki Printed laminate
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EP3240694A1 (en) 2014-12-30 2017-11-08 Merck Patent GmbH Method for producing a pattern that appears three-dimensional in a coating
WO2018228963A1 (en) 2017-06-12 2018-12-20 Merck Patent Gmbh Method for producing a virtual three-dimensional pattern in a coating
RU2644856C1 (en) * 2017-06-26 2018-02-14 Олег Савельевич Кочетов Nozzle divider
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DE3024391A1 (en) * 1980-06-28 1982-01-28 Letron GmbH, 8750 Aschaffenburg METHOD FOR PRODUCING FILMS FROM PRINTED DECORATION PAPERS
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DE3247677A1 (en) 1984-06-28

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