EP2959058B1 - Substrate paper for decorative coating materials - Google Patents

Substrate paper for decorative coating materials Download PDF

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Publication number
EP2959058B1
EP2959058B1 EP14705096.7A EP14705096A EP2959058B1 EP 2959058 B1 EP2959058 B1 EP 2959058B1 EP 14705096 A EP14705096 A EP 14705096A EP 2959058 B1 EP2959058 B1 EP 2959058B1
Authority
EP
European Patent Office
Prior art keywords
base paper
paper
paper according
alkaline earth
decorative
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.)
Active
Application number
EP14705096.7A
Other languages
German (de)
French (fr)
Other versions
EP2959058A1 (en
Inventor
Thomas Leifert
Michael Krause
Rijk Van Der Zwan
Andreas FEHLKER
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.)
Schoeller Technocell GmbH and Co KG
Original Assignee
Schoeller Technocell GmbH and Co KG
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 Schoeller Technocell GmbH and Co KG filed Critical Schoeller Technocell GmbH and Co KG
Priority to PL14705096T priority Critical patent/PL2959058T3/en
Priority to EP14705096.7A priority patent/EP2959058B1/en
Publication of EP2959058A1 publication Critical patent/EP2959058A1/en
Application granted granted Critical
Publication of EP2959058B1 publication Critical patent/EP2959058B1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangementsĀ  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangementsĀ  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • 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
    • 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • 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
    • 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

Definitions

  • the invention relates to a base paper for decorative coating materials, which can be impregnated with a thermally curable impregnating resin and printed by ink jet method, the use of the base paper for the production of decorative coating materials and a method for producing coating materials using the base paper.
  • Decorative papers are needed for the production of decorative laminates, which are used as building materials in furniture production and interior design.
  • the decorative laminates are mainly high pressure laminates (HPL) and low pressure laminates (LPL).
  • HPL high pressure laminates
  • LPL low pressure laminates
  • the decorative paper is impregnated in the unprinted or printed state with a resin and with one or more layers of kraft paper sheets, which were soaked in phenolic resin (core papers), in a laminating press at a temperature of about 110 to 170 Ā° C and a Pressed pressure of about 5.5 to 11 MPa.
  • core papers phenolic resin
  • the resulting laminate (HPL) is glued or glued with a carrier material such as HDF or chipboard.
  • a low pressure laminate is prepared by exposing the unprinted or printed decorative paper impregnated with a resin at a temperature of about 160 to 200 Ā° C and a pressure of about 1.25 to 3.5 MPa is pressed directly to the carrier plate.
  • the refinement of material surfaces may be of an optical nature (by appropriate coloring) and / or physical nature (by coating the plate surface with appropriate functionality and structure).
  • Decorative papers can be processed with or without a printed pattern.
  • the printed or unprinted decorative paper is usually soaked in one or more stages with synthetic resins, then dried, wherein the resin remains reactive, and then pressed in sheets or rolls with a carrier material irreversibly hot. When pressed, the resin hardens.
  • Suitable synthetic resins are the impregnating resins commonly used in this technical field, in particular melamine-formaldehyde resin, urea-formaldehyde resin, phenol-formaldehyde resin, polyacrylates, acrylic ester-styrene copolymers.
  • the impregnating resin may be used in an amount of 40 to 250%, preferably 80 to 125%, of the basis weight of the decorative base paper.
  • the application of the printing pattern is usually done by gravure printing. Particularly in the production of commercially available printing patterns, this printing technique has the advantage of being able to print on large quantities of paper at high machine speed.
  • the gravure process is not profitable for smaller amounts of decor paper and is insufficient in terms of print quality for complicated patterns. From the printing techniques that meet the requirements for flexibility and quality Withstand the ink-jet printing process (ink-jet printing) is therefore becoming increasingly important.
  • decorative base papers printable by the ink-jet printing process, they are coated with one or more functional layers for receiving the ink and fixing the dyes.
  • Such decorative base papers which can be printed by the ink-jet printing process are described, for example, in US Pat DE 199 16 546 A1 and the EP 1 044 822 A1 described.
  • the ink receiving layers generally contain pigments, water-soluble or water-dispersible polymers as binders, dye-fixing substances and other auxiliaries commonly used in such layers.
  • Decorative base papers differ in their properties, however, fundamentally different from normal commercial ink-jet papers. Decorative base papers should have an open surface, so that they can be impregnated quickly and evenly with an impregnating resin.
  • a decorative base paper provided with one of the above-described ink-receiving layers has good ink-jet printability, it has a largely covered paper structure at least on one side of the paper. The intermediate spaces between the fibers are largely closed and are thus available only to a limited extent for the absorption of impregnating resins.
  • the EP 1 749 626 A1 proposes, therefore, a method in which the base paper provided with an ink receiving layer is impregnated from the back side.
  • the WO 2009/097986 A1 Proposes the dye-receiving composition, whose main components are barium sulfate, titanium dioxide and silicates, as a pigment coating such that no closed flat layer is formed and thus the fiber spaces remain largely open.
  • the disadvantage of this procedure is that it is not possible to achieve a sufficiently good printing result.
  • the EP 2 537 981 A1 describes a process for the surface treatment of an ink-jet paper with a surface treatment medium containing magnesium sulfate and polydiallyldimethylammonium chloride polymer.
  • the ink jet paper contains between 0 and 50 wt .-%, in particular 10 and 30 wt .-% CaCO 3 as a filler.
  • the pores are largely closed after its application. The inclusion of an impregnating resin would thus be limited.
  • the papers would be the EP 2 537 981 after impregnation with an impregnating resin because of the calcium carbonate largely transparent.
  • the DE 698 04 233 T2 describes a composition for surface treating a substrate for inkjet printing, the composition consisting essentially of an aqueous sizing medium containing starch, sizing agent and a divalent metal salt.
  • the disadvantage is that the pores on the paper surface are largely closed by the application of the aqueous sizing medium and thus the impregnation of the paper is only possible to a limited extent.
  • Coating materials comprising a raw paper unsealed in the composition, the base paper having a surface coating containing an alkaline earth salt and an inorganic pigment having a specific surface area, measured by BET. from 100 to 400 cm 2 / g, the surface coating containing no polymeric binder.
  • the invention further relates to the use of the base paper according to the invention for the production of laminates and laminates of all kinds.
  • the invention also provides a process for the production of a decorative coating material in which a base paper unsized in size is provided with a surface coating containing an alkaline earth salt, the paper printed by a digital printing process, impregnated with a thermosetting resin and dried , The impregnated and dried paper can be varnished.
  • the surface application according to the invention even without a polymeric binder, provides good printability by digital printing processes, in particular the ink-jet printing process, and the problem of "dusting outā€ of pigments which can not be expected due to the absence of the binder does not occur.
  • the paper surface is
  • Another advantage of the omission of polymeric binders is a lower viscosity of the application liquid and thus a simplification of the application process and the cleaning of the application units.
  • alkaline earth metal salts are alkaline earth halides and alkaline earth metal nitrates having a water solubility of at least 400 g / l (measured at 20 Ā° C). These can also be used in a mixture. Particularly preferred is the use of calcium chloride, magnesium nitrate or mixtures thereof.
  • the surface application additionally contains an inorganic pigment having a specific surface area, measured by BET, of 100 to 400 cm 2 / g.
  • an inorganic pigment having a specific surface area measured by BET, of 100 to 400 cm 2 / g.
  • Particularly preferred are inorganic pigments having a specific surface area of 200 to 330 cm 2 / g.
  • Such preferred inorganic pigments are, for example, aluminum oxide, aluminum hydroxide, boehmite and / or silica.
  • silicas a cationized fumed silica is particularly preferred.
  • the mass ratio alkaline earth salt / pigment in the surface application may be 70:30 to 30:70, preferably 60:40 to 40:60.
  • the surface coating may also contain other auxiliaries, such as dispersing aids, dye-fixing agents, such as polyaluminum salts, Polyammonium salts, pH regulators and other auxiliaries customary in the paper industry.
  • auxiliaries such as dispersing aids, dye-fixing agents, such as polyaluminum salts, Polyammonium salts, pH regulators and other auxiliaries customary in the paper industry.
  • the surface application can be carried out with conventional application units used in the paper coating.
  • "inlineā€ can be applied in the paper machine with a size press.
  • the application weight may preferably be 1 to 10 g / m 2 , in particular 2 to 8 g / m 2 , based on the mass of the dry substance.
  • the surface of the base paper according to the invention may have a pH of 4.5 to 8, preferably 6 to 7.
  • a sufficient impregnating ability of the base paper is obtained and the paper is given very good printability by the ink-jet printing process.
  • the base papers produced according to the invention have an air permeability according to Gurley of less than 25 s / hml, in particular 10 to 22 s / hml.
  • the base paper according to the invention can be rolled up or divided into sheets.
  • the base paper can then be printed in high quality using a wide variety of inkjet processes.
  • the printed paper can then preferably be impregnated with an impregnating resin, in particular with a melamine resin, and dried.
  • the base paper can then be applied in a coating press hot pressed onto a wood-based panel or to a laminate.
  • transparent, unprinted and resinated paper can be used as a further layer as a protective and / or adhesive layer. Alternatively, however, it is also possible to use a different adhesive layer.
  • the printed product can also be sealed with a varnish.
  • the decorative base papers which can be used according to the invention are those which have undergone neither sizing in the mass nor surface sizing. These consist essentially of celluloses, pigments and fillers and conventional additives. Common additives may be wet strength agents, retention aids and fixatives. Decorative base papers differ from conventional papers due to the much higher filler content or pigment content and the lack of standard paper sizing or surface sizing on paper.
  • the decorative base papers which can be used according to the invention usually contain a wet strength agent.
  • Softwood pulps, hardwood pulps or mixtures of both pulp types can be used to produce the decorative base papers. Preference is given to the use of 100% hardwood pulp. But mixtures of softwood / hardwood pulps in the ratio 5:95 to 50:50, in particular 10:90 to 30:70 can be used.
  • the base papers can be produced on a Fourdrinier paper machine or a Yankee paper machine. For this purpose, the pulp mixture can be ground at a consistency of 2 to 5 wt .-% to a freeness of 10 to 45 Ā° SR.
  • color pigments and / or dyes and wet strength agents such as polyamide / polyamine-epichlorohydrin resin, cationic polyacrylates, modified melamine-formaldehyde resin or cationized starches are added in customary amounts in the production of decorative papers and mixed well with the pulp mixture.
  • the fillers and / or pigments can be added in an amount of up to 55% by weight, in particular 10 to 45% by weight, based on the weight of the pulp.
  • Suitable pigments and fillers are, for example, titanium dioxide, talc, modified titanium dioxides and mixtures thereof.
  • the thick stock produced in the mixing chest can be diluted to a consistency of about 1%. If necessary, other auxiliaries such as retention aids, defoamers, dyes and other auxiliaries mentioned above or mixtures thereof may be added.
  • This thin material is fed to the wire section via the headbox of the paper machine. A non-woven fabric is formed and, after dewatering, the base paper is obtained, which is subsequently dried.
  • the basis weights of the papers produced can be 30 to 200 g / m 2 .
  • the decorative base paper according to the invention can be dyed.
  • inorganic color pigments such as metal oxides, metal hydroxides and metal oxide hydrates, metal sulfides, metal sulfates, metal chromates and Metallmolybdate or mixtures thereof
  • organic color pigments and / or dyes such as carbonyl colorants (quinones, quinacridones), cyanine colorants, azo colorants, azomethines and methines, phthalocyanines or dioxazines used become.
  • Particular preference is given to mixtures of inorganic color pigments and organic color pigments or substances.
  • the mass of the color pigment or color pigment mixture or dye or dye mixture may be from 0.0001 to 5 wt .-%, based on the mass of the pulp, depending on the type of dye.
  • the coloring of the base paper according to the invention is constantly adjustable. This is more complicated and more expensive in the case of a decorative base paper coated with a separate ink receiving layer.
  • the surface application liquid may contain coloring additives. These may be the same color pigments and / or dyes with which the raw paper is dyed.
  • the invention relates to a method for producing a decorative coating material or decorative paper.
  • we base paper according to the invention with a digital printing process, such as the ink-jet printing process printed.
  • the printed base paper can then be impregnated with a thermosetting resin and dried.
  • the drying can be carried out in such a way that the impregnating resin is completely cured or only partially cured.
  • Partially cured means that the cure of the thermosetting resin is 70% and more, 80% and more, or 90 and more.
  • the pulp suspension was added to a mixture of 40% by weight of titanium dioxide and 5% by weight of talc, 0.11% by weight of a retention aid and 0.03% by weight of a defoamer, and a decorative base paper having a basis weight of 90 g / m 2 and an ash content of about 32 wt .-% made The weights are based on the mass of the pulp.
  • the decorative base paper treated with the application liquid described below in the size press and then dried. The coating weight was 2 g / m 2 (dry).
  • the pH of the coating liquid had been adjusted to pH 5 with NaOH.
  • a pulp suspension of 100% by weight eucalyptus pulp was milled at a stock consistency of 5% to a freeness of 33 Ā° SR. This was followed by the addition of 1.8 wt .-% epichlorohydrin resin as a wet strength agent. This pulp suspension was adjusted to a pH of 6.5 to 7 with aluminum sulfate.
  • a mixture of 36 wt .-% titanium dioxide and 5 wt .-% talcum, 0.11 wt .-% of a retention aid and 0.03 wt .-% of a defoamer was added to the pulp suspension and from a decorative base paper with a basis weight of about Made 80 g / m 2 and an ash content of about 30 wt .-%. The weights are based on the mass of the pulp.
  • the decorative base paper was treated with the following application liquid in the size press and then dried. The coating weight was 6 g / m 2 (dry).
  • the pH of the coating liquid had previously been adjusted to 5 with NaOH.
  • a decorative base paper prepared according to Example 1 was impregnated with the following application liquid in the size press and then dried.
  • the coating weight was 8 g / m 2 (dry).
  • Application liquid for surface application water 80% by weight Magnesium nitrate (solid) 10% by weight Cationized pyrogens Silica (as a solid) 10% by weight
  • the pH of the coating liquid had previously been adjusted to pH 5 with NaOH.
  • a decorative base paper produced according to Example 1 was used as base paper without further application of glue liquor.
  • a decorative base paper prepared according to Example 1 was treated with the following application liquid in the size press and then dried.
  • the coating weight was 8 g / m 2 (dry).
  • the preparation of the cationized fumed silica starting from AerosilĀ® 300 (Evonik Industries AG) was carried out according to Example 3.
  • a decorative base paper prepared according to Example 1 was prepared according to the examples of EP 1 044 822 B1 coated with an ink receiving layer.
  • the application weight was 5 g / m 2 .
  • the base papers prepared according to the Examples and Comparative Examples were printed in an ink jet printer (EPSON 4800 with pigmented inks).
  • the impregnation ability was tested on the unprinted base papers.
  • the printed base papers were evaluated for image quality and ink penetration on the back of the paper.
  • the purpose of the test is the characterization of the porosity of the paper structure and thus for the impregnation ability. It measures the time taken for a given amount of air to flow through a paper surface at a constant pressure. The measurement is carried out on the basis of ISO 5636-5 with the help of the densometer 121D from Lorenzen & Wettre. The readings are given in Gurley seconds / 100 ml. Values less than 25 s / hml show papers with very good air permeability. Values higher than 60 s / hml indicate a compacted structure and thus poor permeability.
  • the image quality is evaluated by measuring the color density for the primary colors cyan, magenta, yellow and black.
  • the color densities are measured with the densitometer SpectroEye from x-rite.
  • Penetration of the ink is a punctiform or even partial penetration of the ink towards the back of the paper.
  • test results are summarized in the following table: color density Air resistance s / hml punch cyan magenta yellow black B1 0.40 0.55 0.63 0.99 18 ā‡ B2 0.41 0.57 0.64 1.02 22 + B3 0.41 0.57 0.62 1.00 22 + V1 0.38 0.34 0.50 0.52 14 - V2 0.40 0.58 0.63 1.07 28 + V3 0.40 0.71 0.68 1.30 50 +

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Laminated Bodies (AREA)

Description

TECHNISCHES FELD DER ERFINDUNGTECHNICAL FIELD OF THE INVENTION

Die Erfindung betrifft ein Basispapier fĆ¼r dekorative Beschichtungswerkstoffe, das mit einem thermisch hƤrtbaren ImprƤgnierharz imprƤgnierbar und mittels Tintenstrahl-Verfahren bedruckbar ist, die Verwendung des Basispapiers zur Herstellung dekorativer Beschichtungswerkstoffe und ein Verfahren zur Herstellung von Beschichtungswerkstoffen unter Verwendung des Basispapiers.The invention relates to a base paper for decorative coating materials, which can be impregnated with a thermally curable impregnating resin and printed by ink jet method, the use of the base paper for the production of decorative coating materials and a method for producing coating materials using the base paper.

HINTERGRUND DER ERFINDUNGBACKGROUND OF THE INVENTION

Dekorpapiere werden zur Herstellung von dekorativen Laminaten benƶtigt, die als Baustoffe bei der Mƶbelherstellung und im Innenausbau Anwendung finden. Bei den dekorativen Laminaten handelt es sich hauptsƤchlich um sogenannte HochdruckLaminate (HPL) und Niederdruck-Laminate (LPL). Zur Herstellung eines Hochdruck-Laminats wird das Dekorpapier im unbedruckten oder bedruckten Zustand mit einem Harz imprƤgniert und mit einer oder mehreren Lagen Kraftpapierbƶgen, die in Phenolharz getrƤnkt wurden (Kernpapiere), in einer Laminierpresse bei einer Temperatur von etwa 110 bis 170Ā°C und einem Druck von etwa 5,5 bis 11 MPa verpresst. AnschlieƟend wird der so entstandene Schichtstoff (HPL) mit einem TrƤgermaterial wie HDF- oder Spanplatte verleimt oder verklebt. Ein Niederdruck-Laminat wird hergestellt, indem das unbedruckte oder bedruckte und mit einem Harz imprƤgnierte Dekorpapier bei einer Temperatur von etwa 160 bis 200Ā°C und einem Druck von etwa 1,25 bis 3,5 MPa direkt mit der TrƤgerplatte verpresst wird.
Die Veredelung von WerkstoffoberflƤchen kann optischer Natur (durch entsprechende Farbgebung) und/oder physikalischer Natur sein (durch Beschichtung der PlattenoberflƤche mit entsprechender FunktionalitƤt und Struktur). Dekorpapiere kƶnnen mit oder ohne aufgedrucktes Muster verarbeitet werden. Hierzu wird das bedruckte oder unbedruckte Dekorpapier Ć¼blicherweise einstufig oder mehrstufig mit Kunstharzen getrƤnkt, anschlieƟend getrocknet, wobei das Harz noch reaktiv bleibt, und dann in Bƶgen oder als Rollenware mit einem TrƤgermaterial irreversibel heiƟ verpresst. Beim Verpressen hƤrtet das Harz aus. Durch diese AushƤrtung kommt nicht nur der Verbund zur Platte zu Stande, sondern das Papier wird vollstƤndig chemischphysisch verschlossen. Geeignete Kunstharze sind die Ć¼blicherweise auf diesem technischen Gebiet verwendeten ImprƤgnierharze, insbesondere Melamin-Formaldehyd-Harz, Harnstoff-Formaldehyd-Harz, Phenol-Formaldehyd-Harz, Polyacrylate, AcrylsƤureester-Styrol-Copolymere. Das ImprƤgnierharz kann in einer Menge von 40 bis 250 %, vorzugsweise 80 bis 125 % des FlƤchengewichts des Dekorrohpapiers eingesetzt werden.Decorative papers are needed for the production of decorative laminates, which are used as building materials in furniture production and interior design. The decorative laminates are mainly high pressure laminates (HPL) and low pressure laminates (LPL). To produce a high-pressure laminate, the decorative paper is impregnated in the unprinted or printed state with a resin and with one or more layers of kraft paper sheets, which were soaked in phenolic resin (core papers), in a laminating press at a temperature of about 110 to 170 Ā° C and a Pressed pressure of about 5.5 to 11 MPa. Subsequently, the resulting laminate (HPL) is glued or glued with a carrier material such as HDF or chipboard. A low pressure laminate is prepared by exposing the unprinted or printed decorative paper impregnated with a resin at a temperature of about 160 to 200 Ā° C and a pressure of about 1.25 to 3.5 MPa is pressed directly to the carrier plate.
The refinement of material surfaces may be of an optical nature (by appropriate coloring) and / or physical nature (by coating the plate surface with appropriate functionality and structure). Decorative papers can be processed with or without a printed pattern. For this purpose, the printed or unprinted decorative paper is usually soaked in one or more stages with synthetic resins, then dried, wherein the resin remains reactive, and then pressed in sheets or rolls with a carrier material irreversibly hot. When pressed, the resin hardens. As a result of this hardening, not only does the composite bond to the plate, but the paper is completely chemically physically closed. Suitable synthetic resins are the impregnating resins commonly used in this technical field, in particular melamine-formaldehyde resin, urea-formaldehyde resin, phenol-formaldehyde resin, polyacrylates, acrylic ester-styrene copolymers. The impregnating resin may be used in an amount of 40 to 250%, preferably 80 to 125%, of the basis weight of the decorative base paper.

Das Aufbringen des Druckmusters erfolgt Ć¼blicherweise im Tiefdruckverfahren. Insbesondere bei der Erzeugung marktĆ¼blicher Druckmuster weist diese Drucktechnik den Vorteil auf, groƟe Papiermengen mit hoher Maschinengeschwindigkeit bedrucken zu kƶnnen.The application of the printing pattern is usually done by gravure printing. Particularly in the production of commercially available printing patterns, this printing technique has the advantage of being able to print on large quantities of paper at high machine speed.

Das Tiefdruck-Verfahren ist jedoch fĆ¼r geringere Mengen Dekorpapier nicht rentabel und hinsichtlich der DruckqualitƤt bei komplizierten Mustern nicht ausreichend. Von den Drucktechniken, die den Anforderungen an FlexibilitƤt und QualitƤt standhalten, gewinnt das Tintenstrahl-Druckverfahren (Ink-Jet-Druck) daher zunehmend an Bedeutung.
Um Dekorrohpapiere durch das Ink-Jet-Druckverfahren bedruckbar zu machen, werden diese mit einer oder mehreren Funktionsschichten zur Aufnahme der Tinte und Fixierung der Farbstoffe beschichtet. Solche durch das Ink-Jet-Druckverfahren bedruckbare Dekorrohpapiere sind beispielsweise in der DE 199 16 546 A1 und der EP 1 044 822 A1 beschrieben.
Die Tintenaufnahmeschichten enthalten in der Regel Pigmente, wasserlƶsliche oder wasserdispergierbare Polymere als Bindemittel, farbstofffixierende Substanzen und weitere in solchen Schichten Ć¼blicherweise verwendete Hilfsstoffe.However, the gravure process is not profitable for smaller amounts of decor paper and is insufficient in terms of print quality for complicated patterns. From the printing techniques that meet the requirements for flexibility and quality Withstand the ink-jet printing process (ink-jet printing) is therefore becoming increasingly important.
To make decorative base papers printable by the ink-jet printing process, they are coated with one or more functional layers for receiving the ink and fixing the dyes. Such decorative base papers which can be printed by the ink-jet printing process are described, for example, in US Pat DE 199 16 546 A1 and the EP 1 044 822 A1 described.
The ink receiving layers generally contain pigments, water-soluble or water-dispersible polymers as binders, dye-fixing substances and other auxiliaries commonly used in such layers.

Dekorrohpapiere unterscheiden sich in ihren Eigenschaften jedoch grundlegend von normalen handelsĆ¼blichen Ink-Jet-Papieren. Dekorrohpapiere sollen eine offene OberflƤche aufweisen, damit sie mit einem ImprƤgnierharz schnell und gleichmƤƟig durchtrƤnkt werden kƶnnen.Decorative base papers differ in their properties, however, fundamentally different from normal commercial ink-jet papers. Decorative base papers should have an open surface, so that they can be impregnated quickly and evenly with an impregnating resin.

Zwar weist ein mit einer der oben beschriebenen Tintenaufnahmeschichten versehenes Dekorrohpapier eine gute Ink-Jet-Bedruckbarkeit auf, es hat jedoch zumindest auf einer Seite des Papiers eine weitgehend abgedeckte Papierstruktur. Die zwischen den Fasern befindlichen ZwischenrƤume sind grĆ¶ĆŸtenteils verschlossen und stehen somit fĆ¼r die Aufnahme von ImprƤgnierharzen nur eingeschrƤnkt zur VerfĆ¼gung.Although a decorative base paper provided with one of the above-described ink-receiving layers has good ink-jet printability, it has a largely covered paper structure at least on one side of the paper. The intermediate spaces between the fibers are largely closed and are thus available only to a limited extent for the absorption of impregnating resins.

Die EP 1 749 626 A1 schlƤgt daher ein Verfahren vor, in dem das mit einer Tintenaufnahmeschicht versehene Rohpapier von der RĆ¼ckseite imprƤgniert wird. Die WO 2009/097986 A1 schlƤgt vor, die Farbaufnahmemasse, deren Hauptbestandteile Bariumsulfat, Titandioxid und Silikate sind, als Pigmentstrich derart aufzubringen, dass keine geschlossene ebene Schicht entsteht und somit die FaserzwischenrƤume weitgehend offen bleiben. Nachteilig an dieser Vorgehensweise ist, dass sich kein hinreichend gutes Druckergebnis erzielen lƤsst.The EP 1 749 626 A1 proposes, therefore, a method in which the base paper provided with an ink receiving layer is impregnated from the back side. The WO 2009/097986 A1 Proposes the dye-receiving composition, whose main components are barium sulfate, titanium dioxide and silicates, as a pigment coating such that no closed flat layer is formed and thus the fiber spaces remain largely open. The disadvantage of this procedure is that it is not possible to achieve a sufficiently good printing result.

Die EP 2 537 981 A1 beschreibt ein Verfahren zur OberflƤchenbehandlung eines Ink-Jet-Papiers mit einem OberflƤchenbehandlungsmedium enthaltend Magnesiumsulfat und Polydiallyldimethylammoniumchlorid-Polymer. Das Ink-Jet-Papier enthƤlt zwischen 0 und 50 Gew.-%, insbesondere 10 und 30 Gew.-% CaCO3 als FĆ¼llstoff. Durch die Verwendung des filmbildenden Polydiallyldimethylammoniumchlorid-Polymers im OberflƤchenbehandlungsmedium werden die Poren nach dessen Auftrag weitgehend verschlossen. Die Aufnahme eines ImprƤgnierharzes wƤre somit nur eingeschrƤnkt mƶglich. Ferner wƤren die Papiere der EP 2 537 981 nach ImprƤgnierung mit einem ImprƤgnierharz wegen des Calciumcarbonats weitgehend transparent.
Die DE 698 04 233 T2 beschreibt eine Zusammensetzung zur OberflƤchenbehandlung eines Substrats zum Tintenstrahldruck, wobei die Zusammensetzung im Wesentlichen aus einem wƤssrigen Leimungsmedium enthaltend StƤrke, ein Leimungsmittel und ein Salz eines zweiwertigen Metalls, besteht. Nachteilig ist, dass durch den Auftrag des wƤssrigen Leimungsmediums die Poren an der PapieroberflƤche grĆ¶ĆŸtenteils verschlossen werden und somit die ImprƤgnierung des Papiers nur eingeschrƤnkt mƶglich ist.The EP 2 537 981 A1 describes a process for the surface treatment of an ink-jet paper with a surface treatment medium containing magnesium sulfate and polydiallyldimethylammonium chloride polymer. The ink jet paper contains between 0 and 50 wt .-%, in particular 10 and 30 wt .-% CaCO 3 as a filler. By using the film-forming polydiallyldimethylammonium chloride polymer in the surface treatment medium, the pores are largely closed after its application. The inclusion of an impregnating resin would thus be limited. Furthermore, the papers would be the EP 2 537 981 after impregnation with an impregnating resin because of the calcium carbonate largely transparent.
The DE 698 04 233 T2 describes a composition for surface treating a substrate for inkjet printing, the composition consisting essentially of an aqueous sizing medium containing starch, sizing agent and a divalent metal salt. The disadvantage is that the pores on the paper surface are largely closed by the application of the aqueous sizing medium and thus the impregnation of the paper is only possible to a limited extent.

ZUSAMMENFASSUNG DER ERFINDUNGSUMMARY OF THE INVENTION

Folglich ist es Aufgabe der Erfindung, ein Basispapier fĆ¼r dekorative Beschichtungswerkstoffe bereitzustellen, das die oben beschriebenen Nachteile nicht zeigt und eine ausreichende ImprƤgnierfƤhigkeit trotz einer einseitig guten Bedruckbarkeit durch ein digitales Druckverfahren, insbesondere InkJet-Druckverfahren, aufweist.Consequently, it is an object of the invention to provide a base paper for decorative coating materials, which does not show the disadvantages described above and sufficient impregnability despite one-sided good printability by a digital printing method, in particular inkjet printing method has.

Gelƶst wird diese Aufgabe mit einem Basispapier fĆ¼r dekorativeThis task is solved with a base paper for decorative

Beschichtungswerkstoffe mit einem in der Masse ungeleimten Rohpapier, wobei das Rohpapier einen OberflƤchenauftrag aufweist, der ein Erdalkalisalz enthƤlt und ein anorganisches Pigment mit einer spezifischen OberflƤche, gemessen nach BET. von 100 bis 400 cm2/g enthƤlt, wobei der OberflƤchenauftrag kein polymeres Bindemittel enthƤlt.Coating materials comprising a raw paper unsealed in the composition, the base paper having a surface coating containing an alkaline earth salt and an inorganic pigment having a specific surface area, measured by BET. from 100 to 400 cm 2 / g, the surface coating containing no polymeric binder.

Gegenstand der Erfindung ist ferner die Verwendung des erfindungsgemƤƟen Basispapiers zur Herstellung von Schichtpressstoffen und Laminaten aller Art.The invention further relates to the use of the base paper according to the invention for the production of laminates and laminates of all kinds.

Gegenstand der Erfindung ist auch ein Verfahren zur Herstel-lung eines dekorativen Beschichtungswerkstoffs, in dem man ein in der Masse ungeleimtes Rohpapier mit einem OberflƤchenauftrag versieht, der ein Erdalkalisalz enthƤlt, das Papier mittels eines digitalen Druckverfahrens bedruckt, mit einem thermisch hƤrtbaren Harz imprƤgniert und trocknet. Das imprƤgnierte und getrocknete Papier kann lackiert sein.The invention also provides a process for the production of a decorative coating material in which a base paper unsized in size is provided with a surface coating containing an alkaline earth salt, the paper printed by a digital printing process, impregnated with a thermosetting resin and dried , The impregnated and dried paper can be varnished.

Ɯberraschend hat sich gezeigt, dass der erfindungsgemƤƟe OberflƤchenauftrag auch ohne ein polymeres Bindemittel, eine gute Bedruckbarkeit durch digitale Druckverfahren, insbesondere das Ink-Jet-Druckverfahren, liefert und das wegen des Fehlen des Bindemittels zu erwartende Problem des "Abmehlens" von Pigmenten nicht auftritt. Die PapieroberflƤche aber istSurprisingly, it has been found that the surface application according to the invention, even without a polymeric binder, provides good printability by digital printing processes, in particular the ink-jet printing process, and the problem of "dusting out" of pigments which can not be expected due to the absence of the binder does not occur. But the paper surface is

weitgehend frei und offen fĆ¼r die Aufnahme des ImprƤgniermittels.largely free and open for receiving the impregnating agent.

Vorteilhaft beim Weglassen von polymeren Bindemitteln ist ferner eine niedrigere ViskositƤt der AuftragsflĆ¼ssigkeit und damit eine Vereinfachung des Auftragsverfahrens und der Reinigung der Auftragsaggregate.Another advantage of the omission of polymeric binders is a lower viscosity of the application liquid and thus a simplification of the application process and the cleaning of the application units.

BESCHREIBUNG DER BEVORZUGTEN AUSFƜHRUNGSFORMENDESCRIPTION OF THE PREFERRED EMBODIMENTS

Besonders gut geeignete Erdalkalisalze sind Erdalkalihalogenide und Erdalkalinitrate mit einer Wasserlƶslichkeit von wenigstens 400 g/l (gemessen bei 20Ā°C). Diese kƶnnen auch im Gemisch eingesetzt werden. Besonders bevorzugt ist der Ein-satz von Calciumchlorid, Magnesiumnitrat oder deren Gemische.Particularly suitable alkaline earth metal salts are alkaline earth halides and alkaline earth metal nitrates having a water solubility of at least 400 g / l (measured at 20 Ā° C). These can also be used in a mixture. Particularly preferred is the use of calcium chloride, magnesium nitrate or mixtures thereof.

Die erfindungsgemƤƟe Wirkung wird erzielt, wenn der OberflƤchenauftrag zusƤtzlich ein anorganisches Pigment mit einer spezifischen OberflƤche, gemessen nach BET, von 100 bis 400 cm2/g enthƤlt. Besonders bevorzugt sind anorganische Pigmente mit einer spezifischen OberflƤche von 200 bis 330 cm2/g. Solche bevorzugten anorganischen Pigmente sind beispielsweise Aluminiumoxid, Aluminiumhydroxid, Bƶhmit und/oder KieselsƤure. Von den KieselsƤuren wird eine kationisierte pyrogene KieselsƤure besonders bevorzugt.The effect according to the invention is achieved if the surface application additionally contains an inorganic pigment having a specific surface area, measured by BET, of 100 to 400 cm 2 / g. Particularly preferred are inorganic pigments having a specific surface area of 200 to 330 cm 2 / g. Such preferred inorganic pigments are, for example, aluminum oxide, aluminum hydroxide, boehmite and / or silica. Of the silicas, a cationized fumed silica is particularly preferred.

Das MassenverhƤltnis Erdalkalisalz/Pigment in dem OberflƤchenauftrag kann 70:30 bis 30:70, vorzugsweise 60:40 bis 40:60, betragen.The mass ratio alkaline earth salt / pigment in the surface application may be 70:30 to 30:70, preferably 60:40 to 40:60.

Die OberflƤchenbeschichtung kann noch weitere Hilfsmittel wie Dispergierhilfsmittel, Farbfixierstoffe wie Polyaluminiumsalze, Polyammoniumsalze, pH-Regulierungsmittel und andere in der Papierindustrie Ć¼bliche Hilfsstoffe enthalten.The surface coating may also contain other auxiliaries, such as dispersing aids, dye-fixing agents, such as polyaluminum salts, Polyammonium salts, pH regulators and other auxiliaries customary in the paper industry.

Der OberflƤchenauftrag kann mit Ć¼blichen in der Papierbeschichtung eingesetzten Auftragsaggregaten erfolgen. Insbesondere kann "inline" in der Papiermaschine mit einer Leimpresse aufgetragen werden. Das Auftragsgewicht kann vorzugsweise 1 bis 10 g/m2, insbesondere 2 bis 8 g/m2, bezogen auf die Masse der Trockensubstanz, betragen.The surface application can be carried out with conventional application units used in the paper coating. In particular, "inline" can be applied in the paper machine with a size press. The application weight may preferably be 1 to 10 g / m 2 , in particular 2 to 8 g / m 2 , based on the mass of the dry substance.

Die OberflƤche des erfindungsgemƤƟen Basispapiers kann einen pH-Wert von 4,5 bis 8, vorzugsweise 6 bis 7, aufweisen. Durch die Behandlung der OberflƤche des Dekorrohpapiers mit dem erfindungsgemƤƟen OberflƤchenauftrag wird eine ausreichende ImprƤgnierfƤhigkeit des Basispapiers erhalten und dem Papier eine sehr gute Bedruckbarkeit durch das Ink-Jet-Druckverfahren verliehen. Die erfindungsgemƤƟ hergestellten Basispapiere weisen eine LuftdurchlƤssigkeit nach Gurley von weniger als 25 s/hml, insbesondere 10 bis 22 s/hml, auf.The surface of the base paper according to the invention may have a pH of 4.5 to 8, preferably 6 to 7. By treating the surface of the decorative base paper with the surface application according to the invention, a sufficient impregnating ability of the base paper is obtained and the paper is given very good printability by the ink-jet printing process. The base papers produced according to the invention have an air permeability according to Gurley of less than 25 s / hml, in particular 10 to 22 s / hml.

Das erfindungsgemƤƟe Basispapier kann aufgerollt oder in Bƶgen aufgeteilt werden. Das Basispapier kann anschlieƟend in hoher QualitƤt mit den unterschiedlichsten Ink-Jet-Verfahren bedruckt werden. In einem nachfolgenden Schritt kann das bedruckte Papier dann vorzugsweise mit einem TrƤnkharz, insbesondere mit einem Melaminharz, getrƤnkt und getrocknet werden. Das Basispapier kann anschlieƟend in einer Beschichtungspresse heiƟ auf eine Holzwerkstoffplatte oder zu einem Schichtstoff verpresst werden. Hierbei kƶnnen optional als weitere Lagen transparentes, unbedrucktes und beharztes Papier (Overlay oder Underlay)im Verbund als Schutz- und/oder Klebeschicht verwendet werden. Es kann aber alternativ auch eine andere Klebeschicht verwendet werden. Das bedruckte Produkt kann auch mit einem Lack versiegelt werden.The base paper according to the invention can be rolled up or divided into sheets. The base paper can then be printed in high quality using a wide variety of inkjet processes. In a subsequent step, the printed paper can then preferably be impregnated with an impregnating resin, in particular with a melamine resin, and dried. The base paper can then be applied in a coating press hot pressed onto a wood-based panel or to a laminate. Optionally, transparent, unprinted and resinated paper (overlay or underlay) can be used as a further layer as a protective and / or adhesive layer. Alternatively, however, it is also possible to use a different adhesive layer. The printed product can also be sealed with a varnish.

Die erfindungsgemƤƟ einsetzbaren Dekorrohpapiere sind solche, die weder eine Leimung in der Masse noch eine OberflƤchenleimung erfahren haben. Diese bestehen im Wesentlichen aus Zellstoffen, Pigmenten und FĆ¼llstoffen und Ć¼blichen Additiven. Ɯbliche Additive kƶnnen Nassfestmittel, Retentionsmittel und Fixiermittel sein. Dekorrohpapiere unterscheiden sich von Ć¼blichen Papieren durch den sehr viel hƶheren FĆ¼llstoffanteil oder Pigmentgehalt und das Fehlen einer beim Papier Ć¼blichen Masseleimung oder OberflƤchenleimung. Ɯblicherweise enthalten die erfindungsgemƤƟ einsetzbaren Dekorrohpapiere ein Nassfestmittel.The decorative base papers which can be used according to the invention are those which have undergone neither sizing in the mass nor surface sizing. These consist essentially of celluloses, pigments and fillers and conventional additives. Common additives may be wet strength agents, retention aids and fixatives. Decorative base papers differ from conventional papers due to the much higher filler content or pigment content and the lack of standard paper sizing or surface sizing on paper. The decorative base papers which can be used according to the invention usually contain a wet strength agent.

Zur Herstellung der Dekorrohpapiere kƶnnen Nadelholz-Zellstoffe, Laubholz-Zellstoffe oder Mischungen beider Zellstoffarten verwendet werden. Bevorzugt wird der Einsatz von 100% Laubholzzellstoff. Aber auch Mischungen aus Nadelholz-/Laubholz-Zellstoffen im VerhƤltnis 5:95 bis 50:50, insbesondere 10:90 bis 30:70 kƶnnen verwendet werden. Die Rohpapiere kƶnnen auf einer Fourdrinier-Papiermaschine oder einer Yankee-Papiermaschine hergestellt werden. Dazu kann das Zellstoffgemisch bei einer Stoffdichte von 2 bis 5 Gew.-% bis zu einem Mahlgrad von 10 bis 45Ā°SR gemahlen werden. In einer MischbĆ¼tte kƶnnen FĆ¼llstoffe und/oder Pigmente, Farbpigmente und/oder Farbstoffe sowie Nassfestmittel wie Polyamid/Polyamin-Epichlorhydrin-Harz, kationische Polyacrylate, modifiziertes Melamin-Formaldehyd-Harz oder kationisierte StƤrken in bei der Herstellung von Dekorpapieren Ć¼blichen Mengen zugesetzt und mit dem Zellstoffgemisch gut vermischt werden.Softwood pulps, hardwood pulps or mixtures of both pulp types can be used to produce the decorative base papers. Preference is given to the use of 100% hardwood pulp. But mixtures of softwood / hardwood pulps in the ratio 5:95 to 50:50, in particular 10:90 to 30:70 can be used. The base papers can be produced on a Fourdrinier paper machine or a Yankee paper machine. For this purpose, the pulp mixture can be ground at a consistency of 2 to 5 wt .-% to a freeness of 10 to 45 Ā° SR. In a mixer chest fillers and / or pigments, color pigments and / or dyes and wet strength agents such as polyamide / polyamine-epichlorohydrin resin, cationic polyacrylates, modified melamine-formaldehyde resin or cationized starches are added in customary amounts in the production of decorative papers and mixed well with the pulp mixture.

Die FĆ¼llstoffe und/oder Pigmente kƶnnen in einer Menge bis zu 55 Gew.-%, insbesondere 10 bis 45 Gew.-%, bezogen auf das Gewicht des Zellstoffs, zugegeben werden. Geeignete Pigmente und FĆ¼llstoffe sind beispielsweise Titandioxid, Talkum, modifizierte Titandioxide und deren Gemische.The fillers and / or pigments can be added in an amount of up to 55% by weight, in particular 10 to 45% by weight, based on the weight of the pulp. Suitable pigments and fillers are, for example, titanium dioxide, talc, modified titanium dioxides and mixtures thereof.

Der in der MischbĆ¼tte erzeugte Dickstoff kann bis zu einer Stoffdichte von etwa 1 % verdĆ¼nnt werden. Soweit erforderlich kƶnnen weitere Hilfsstoffe wie Retentionshilfsmittel, EntschƤumer, Farbstoffe und andere zuvor genannte Hilfsstoffe oder deren Gemische zugesetzt werden. Dieser DĆ¼nnstoff wird Ć¼ber den Stoffauflauf der Papiermaschine auf die Siebpartie gefĆ¼hrt. Es wird ein Faservlies gebildet und nach EntwƤsserung das Rohpapier erhalten, welches anschlieƟend noch getrocknet wird. Die FlƤchengewichte der erzeugten Papiere kƶnnen 30 bis 200 g/m2 betragen.The thick stock produced in the mixing chest can be diluted to a consistency of about 1%. If necessary, other auxiliaries such as retention aids, defoamers, dyes and other auxiliaries mentioned above or mixtures thereof may be added. This thin material is fed to the wire section via the headbox of the paper machine. A non-woven fabric is formed and, after dewatering, the base paper is obtained, which is subsequently dried. The basis weights of the papers produced can be 30 to 200 g / m 2 .

In AbhƤngigkeit von der geplanten Anwendung und den QualitƤtsanforderungen fĆ¼r diese Anwendung kƶnnen die erfindungsgemƤƟ verwendeten Dekorrohpapiere folgende Eigenschaften aufweisen:

  • glatt, d.h. mit GlƤtte nach Bekk Ć¼ber 80 s,
  • alternativ ungeglƤttet mit einer GlƤtte nach Beck < 80 s,
  • mit einem Yankeezylinder oder mit einem Kalander geglƤttet,
  • sehr luftdurchlƤssig mit Gurley-Werten unter 20 s/hml oder dichter mit Gurley-Werten Ć¼ber 20 s/hml.
Depending on the intended application and the quality requirements for this application, the decorative base papers used according to the invention may have the following properties:
  • smooth, ie with Bekk smoothness over 80 s,
  • alternatively unsmoothed with a smoothness of Beck <80 s,
  • smoothed with a Yankee cylinder or with a calender,
  • very air permeable with Gurley values below 20 s / hml or denser with Gurley values above 20 s / hml.

Das erfindungsgemƤƟe Dekorrohpapier kann eingefƤrbt werden. Zur EinfƤrbung kƶnnen anorganische Farbpigmente wie Metalloxide, Metallhydroxide und Metalloxidhydrate, Metallsulfide, Metallsulfate, Metallchromate und Metallmolybdate oder deren Gemische, sowie organische Farbpigmente und/oder Farbstoffe wie Carbonylfarbmittel (Chinone, Chinacridone), Cyaninfarbmittel, Azofarbmittel, Azomethine und Methine, Phthalocyanine oder Dioxazine eingesetzt werden. Insbesondere bevorzugt sind Gemische aus anorganischen Farbpigmenten und organischen Farbpigmenten oder -stoffen. Die Masse des Farbpigments oder Farbpigmentgemischs oder Farbstoffs oder Farbstoffgemischs kann je nach Art des Farbstoffs von 0,0001 bis 5 Gew.-% betragen, bezogen auf die Masse des Zellstoffs.The decorative base paper according to the invention can be dyed. For coloring inorganic color pigments such as metal oxides, metal hydroxides and metal oxide hydrates, metal sulfides, metal sulfates, metal chromates and Metallmolybdate or mixtures thereof, and organic color pigments and / or dyes such as carbonyl colorants (quinones, quinacridones), cyanine colorants, azo colorants, azomethines and methines, phthalocyanines or dioxazines used become. Particular preference is given to mixtures of inorganic color pigments and organic color pigments or substances. The mass of the color pigment or color pigment mixture or dye or dye mixture may be from 0.0001 to 5 wt .-%, based on the mass of the pulp, depending on the type of dye.

Die EinfƤrbung des erfindungsgemƤƟen Basispapiers ist konstant einstellbar. Dies ist im Falle eines mit einer gesonderten Farbaufnahmeschicht beschichteten Dekorrohpapiers komplizierter und mit hƶherem Aufwand verbunden.The coloring of the base paper according to the invention is constantly adjustable. This is more complicated and more expensive in the case of a decorative base paper coated with a separate ink receiving layer.

In einer besonderen Ausgestaltung der Erfindung kann die OberflƤchenauftragflĆ¼ssigkeit fƤrbende Additive enthalten. Das kƶnnen die gleichen Farbpigmente und/oder Farbstoffe sein, mit denen auch das Rohpapier eingefƤrbt wird.In a particular embodiment of the invention, the surface application liquid may contain coloring additives. These may be the same color pigments and / or dyes with which the raw paper is dyed.

GemƤƟ einer AusfĆ¼hrungsform betrifft die Erfindung ein Verfahren zur Herstellung eines dekorativen Beschichtungswerkstoffs oder Dekorpapiers. Dazu wir das erfindungsgemƤƟe Basispapier mit einem digitalen Druckverfahren, beispielsweise dem Ink-Jet-Druckverfahren, bedruckt. Das bedruckte Basispapiers kann dann mit einem thermisch hƤrtbaren Harz imprƤgniert und getrocknet werden. Die Trocknung kann derart erfolgen, dass das ImprƤgnierharz vollstƤndig ausgehƤrtet ist oder aber nur teilweise ausgehƤrtet ist. Teilweise ausgehƤrtet bedeutet, dass die HƤrtung des thermisch hƤrtbaren Harzes zu 70% und mehr, 80% und mehr oder 90 und mehr erfolgt ist.According to one embodiment, the invention relates to a method for producing a decorative coating material or decorative paper. For this purpose, we base paper according to the invention with a digital printing process, such as the ink-jet printing process printed. The printed base paper can then be impregnated with a thermosetting resin and dried. The drying can be carried out in such a way that the impregnating resin is completely cured or only partially cured. Partially cured means that the cure of the thermosetting resin is 70% and more, 80% and more, or 90 and more.

Das Aufbringen des dekorativen Beschichtungswerkstoffs oder Dekorpapiers auf einen permanenten TrƤger erfolgt in bekannter Weise unter Einwirkung von WƤrme und Druck sowie gegebenenfalls unter zusƤtzlicher Verwendung eines fĆ¼r diese Zwecke bekannten Klebers.
Die folgenden Beispiele dienen der weiteren ErlƤuterung der Erfindung.The application of the decorative coating material or decorative paper on a permanent support in a known manner under the action of heat and pressure and optionally with the additional use of an adhesive known for this purpose.
The following examples serve to further illustrate the invention.

BEISPIELEEXAMPLES Beispiel 1 (B1)Example 1 (B1)

Zur Herstellung der Zellstoffsuspensionen wurde ein Zellstoffgemisch aus 80 Gew.-% Eukalyptus-Zellstoff und 20 Gew.-% Kiefer-Sulfatzellstoff bei einer Stoffdichte von 5 % bis zu einem Mahlgrad von 33Ā°SR gemahlen. AnschlieƟend erfolgte die Zugabe von 1,8 Gew.-% Epichlorhydrinharz als Nassfestmittel. Diese Zellstoffsuspension wurde mit Aluminiumsulfat auf einen pH-Wert von 6,5 bis 7 eingestellt. Danach wurde der Zellstoffsuspension ein Gemisch aus 40 Gew.-% Titandioxid und 5 Gew.-% Talkum, 0,11 Gew.-% eines Retentionshilfsmittels und 0,03 Gew.-% eines EntschƤumers zugefĆ¼gt und ein Dekorrohpapier mit einem FlƤchengewicht von 90 g/m2 und einem Aschegehalt von etwa 32 Gew.-% gefertigt Die Gewichtsangaben beziehen sich auf die Masse des Zellstoffs. Im nƤchsten Schritt wurde das Dekorrohpapier mit der nachfolgend beschriebenen AuftragsflĆ¼ssigkeit in der Leimpresse behandelt und anschlieƟend getrocknet. Das Auftragsgewicht betrug 2 g/m2 (trocken).To prepare the pulp suspensions, a pulp mixture of 80% by weight of eucalyptus pulp and 20% by weight of pine sulfate pulp was milled at a stock density of 5% to a freeness of 33 Ā° SR. This was followed by the addition of 1.8 wt .-% epichlorohydrin resin as a wet strength agent. This pulp suspension was adjusted to a pH of 6.5 to 7 with aluminum sulfate. Thereafter, the pulp suspension was added to a mixture of 40% by weight of titanium dioxide and 5% by weight of talc, 0.11% by weight of a retention aid and 0.03% by weight of a defoamer, and a decorative base paper having a basis weight of 90 g / m 2 and an ash content of about 32 wt .-% made The weights are based on the mass of the pulp. In the next step was the decorative base paper treated with the application liquid described below in the size press and then dried. The coating weight was 2 g / m 2 (dry).

AuftragsflĆ¼ssigkeit fĆ¼r den OberflƤchenauftrag: Wasser 80 Gew.-% Calciumchlorid (Feststoff) 20 Gew.-% Application liquid for surface application: water 80% by weight Calcium chloride (solid) 20% by weight

Der pH-Wert der AuftragsflĆ¼ssigkeit war mit NaOH auf pH 5 eingestellt worden.The pH of the coating liquid had been adjusted to pH 5 with NaOH.

Beispiel 2 (B2)Example 2 (B2)

Eine Zellstoffsuspension aus 100 Gew.-% Eukalyptus-Zellstoff wurde bei einer Stoffdichte von 5 % bis zu einem Mahlgrad von 33Ā°SR gemahlen. AnschlieƟend erfolgte die Zugabe von 1,8 Gew.-% Epichlorhydrinharz als Nassfestmittel. Diese Zellstoffsuspension wurde mit Aluminiumsulfat auf einen pH-Wert von 6,5 bis 7 eingestellt. Danach wurde der Zellstoffsuspension ein Gemisch aus 36 Gew.-% Titandioxid und 5 Gew.-% Talkum, 0,11 Gew.-% eines Retentionshilfsmittels und 0,03 Gew.-% eines EntschƤumers zugefĆ¼gt und daraus ein Dekorrohpapier mit einem FlƤchengewicht von etwa 80 g/m2 und einem Aschegehalt von etwa 30 Gew.-% gefertigt. Die Gewichtsangaben beziehen sich auf die Masse des Zellstoffs. Im nƤchsten Schritt wurde das Dekorrohpapier mit der folgenden AuftragsflĆ¼ssigkeit in der Leimpresse behandelt und anschlieƟend getrocknet. Das Auftragsgewicht betrug 6 g/m2 (trocken).A pulp suspension of 100% by weight eucalyptus pulp was milled at a stock consistency of 5% to a freeness of 33 Ā° SR. This was followed by the addition of 1.8 wt .-% epichlorohydrin resin as a wet strength agent. This pulp suspension was adjusted to a pH of 6.5 to 7 with aluminum sulfate. Thereafter, a mixture of 36 wt .-% titanium dioxide and 5 wt .-% talcum, 0.11 wt .-% of a retention aid and 0.03 wt .-% of a defoamer was added to the pulp suspension and from a decorative base paper with a basis weight of about Made 80 g / m 2 and an ash content of about 30 wt .-%. The weights are based on the mass of the pulp. In the next step, the decorative base paper was treated with the following application liquid in the size press and then dried. The coating weight was 6 g / m 2 (dry).

AuftragsflĆ¼ssigkeit fĆ¼r den OberflƤchenauftrag: Wasser 80 Gew.-% Calciumchlorid (Feststoff) 10 Gew.-% Pyrogene KieselsƤure (Feststoff) 10 Gew.-% (AerosilĀ® 300, Evonik) Application liquid for surface application: water 80% by weight Calcium chloride (solid) 10% by weight Pyrogenic silica (solid) 10% by weight (AerosilĀ® 300, Evonik)

Der pH-Wert der AuftragsflĆ¼ssigkeit war zuvor mit NaOH auf 5 eingestellt worden.The pH of the coating liquid had previously been adjusted to 5 with NaOH.

Beispiel 3 (B3)Example 3 (B3)

Eine Dispersion von kationisierte pyrogener KieselsƤure wurde folgendermaƟen hergestellt:

  • Zu 1 kg Wasser von 20Ā°C wurden 35 g der kationischen Silanzubereitung DYNASILAN HYDROSILĀ® 2999 (Fa. Evonik Industries AG) und 8 g MethansulfonsƤure zugegeben. Zu dieser Lƶsung wurden 300 g AerosilĀ® 300 (Evonik Industries AG) unter starken RĆ¼hren zugegeben und die Mischung danach mit einem Rotor-Stator-Dispergiersystem ULTRA-TURRAXĀ® Modell T25 20 Minuten lang bei 9600 Umdrehungen pro Minute (U/min) dispergiert. Der Feststoffgehalt der so hergestellten Dispersion von kationisieter pyrogener KieselsƤure betrug 22 Gew.%.
A dispersion of cationized fumed silica was prepared as follows:
  • To 1 kg of water at 20 Ā° C., 35 g of the cationic silane preparation DYNASILAN HYDROSILĀ® 2999 (from Evonik Industries AG) and 8 g of methanesulfonic acid were added. To this solution was added 300 g of AerosilĀ® 300 (Evonik Industries AG) with vigorous stirring, and the mixture was then dispersed with a ULTRA-TURRAX Model T25 Rotor-Stator Dispersing System at 9600 rpm (rpm) for 20 minutes. The solids content of the dispersion of cationic fumed silica thus prepared was 22% by weight.

Ein gemƤƟ Beispiel 1 hergestelltes Dekorrohpapier wurde mit der folgenden AuftragsflĆ¼ssigkeit in der Leimpresse imprƤgniert und anschlieƟend getrocknet. Das Auftragsgewicht betrug 8 g/m2 (trocken).A decorative base paper prepared according to Example 1 was impregnated with the following application liquid in the size press and then dried. The coating weight was 8 g / m 2 (dry).

AuftragsflĆ¼ssigkeit fĆ¼r den OberflƤchenauftrag: Wasser 80 Gew.-% Magnesiumnitrat (Feststoff) 10 Gew.-% Kationisierte pyrogene KieselsƤure (als Feststoff) 10 Gew.-% Application liquid for surface application: water 80% by weight Magnesium nitrate (solid) 10% by weight Cationized pyrogens Silica (as a solid) 10% by weight

Der pH-Wert der AuftragsflĆ¼ssigkeit war zuvor mit NaOH auf pH 5 eingestellt worden.The pH of the coating liquid had previously been adjusted to pH 5 with NaOH.

VERGLEICHSBEISPIELECOMPARATIVE EXAMPLES Vergleichsbeispiel 1 (V1)Comparative Example 1 (V1)

Ein gemƤƟ Beispiel 1 hergestelltes Dekorrohpapier wurde ohne weiteren Leimflottenauftrag als Basispapier verwendet.A decorative base paper produced according to Example 1 was used as base paper without further application of glue liquor.

Vergleichsbeispiel 2 (V2)Comparative Example 2 (V2)

Ein gemƤƟ Beispiel 1 hergestelltes Dekorrohpapier wurde mit der folgenden AuftragsflĆ¼ssigkeit in der Leimpresse behandelt und anschlieƟend getrocknet. Das Auftragsgewicht betrug 8 g/m2 (trocken). Die Herstellung der kationisierten pyrogenen KieselsƤure ausgehend von AerosilĀ® 300 (Evonik Industries AG) erfolgte gemƤƟ Beispiel 3.A decorative base paper prepared according to Example 1 was treated with the following application liquid in the size press and then dried. The coating weight was 8 g / m 2 (dry). The preparation of the cationized fumed silica starting from AerosilĀ® 300 (Evonik Industries AG) was carried out according to Example 3.

AuftragsflĆ¼ssigkeit fĆ¼r den OberflƤchenauftrag: Wasser 50 Gew.-% StƤrke C-Film 7311 (Cerestar) 30 Gew.-% Calciumchlorid (Feststoff) 10 Gew.-% Kationisierte pyrogene KieselsƤure 10 Gew.-% (AerosilĀ® 300, Evonik) Application liquid for surface application: water 50% by weight Thickness C-Film 7311 (Cerestar) 30% by weight Calcium chloride (solid) 10% by weight Cationized fumed silica 10% by weight (AerosilĀ® 300, Evonik)

Vergleichsbeispiel 3 (V3)Comparative Example 3 (V3)

Ein gemƤƟ Beispiel 1 hergestelltes Dekorrohpapier wurde gemƤƟ den Beispielen der EP 1 044 822 B1 mit einer Tintenaufnahmeschicht beschichtet. Das Auftragsgewicht betrug 5 g/m2. Hierbei handelte es sich um folgende Zusammensetzung der Tintenaufnahmeschicht: Polyvinylalkohol 20%-ige Lƶsung 33 Gew.-% (MOWIOL 26-88, Kuraray Europe GmbH) Polyamin 20%-ige Lƶsung 9 Gew.-% (Magnaflox 1597, BASF SE) AcrylsƤureester-Styrol-Polymer 20%-ige Dispersion (Basoplast 265D, BASF SE) 10 Gew.-% Amorphe KieselsƤure 20%-ige Dispersion 48 Gew.-% (Gasil 200DF, PQ Corporation) A decorative base paper prepared according to Example 1 was prepared according to the examples of EP 1 044 822 B1 coated with an ink receiving layer. The application weight was 5 g / m 2 . This was the following composition of the ink receiving layer: Polyvinyl alcohol 20% solution 33% by weight (MOWIOL 26-88, Kuraray Europe GmbH) Polyamine 20% solution 9% by weight (Magnaflox 1597, BASF SE) Acrylate-styrene polymer 20% dispersion (Basoplast 265D, BASF SE) 10% by weight Amorphous silica 20% dispersion 48% by weight (Gasil 200DF, PQ Corporation)

ANGEWENDETE PRƜFMETHODENAPPLIED TESTING METHODS

Die gemƤƟ den Beispielen und Vergleichsbeispielen hergestellten Basispapiere wurden in einem Tintenstrahldrucker (EPSON 4800 mit pigmentierten Tinten) bedruckt.The base papers prepared according to the Examples and Comparative Examples were printed in an ink jet printer (EPSON 4800 with pigmented inks).

An den unbedruckten Basispapieren wurde die ImprƤgnierfƤhigkeit geprĆ¼ft. Bei den bedruckten Basispapieren wurden die BildqualitƤt und das Durchschlagen der Tinte auf die RĆ¼ckseite des Papiers bewertet.The impregnation ability was tested on the unprinted base papers. The printed base papers were evaluated for image quality and ink penetration on the back of the paper.

Die zur PrĆ¼fung der Papiere herangezogenen Methoden sind nachfolgend beschrieben.The methods used to test the papers are described below.

Luftwiderstand nach GurleyAir resistance to Gurley

Zweck der PrĆ¼fung ist die Charakterisierung der PorositƤt des PapiergefĆ¼ges und damit fĆ¼r die ImprƤgnierfƤhigkeit. Es wird die Zeit gemessen, die eine bestimmte Menge Luft benƶtigt, um bei einem konstanten Druck durch eine PapierflƤche zu strƶmen. Die Messung erfolgt in Anlehnung an die ISO 5636-5 mit Hilfe des Densometers 121D der Fa. Lorenzen & Wettre. Die Messwerte sind in Gurley Sekunden/100 ml angegeben. Werte kleiner 25 s/hml zeigen Papiere mit sehr guter LuftdurchlƤssigkeit. Werte hƶher als 60 s/hml weisen auf eine verdichtete Struktur und somit schlechte DurchlƤssigkeit hin.The purpose of the test is the characterization of the porosity of the paper structure and thus for the impregnation ability. It measures the time taken for a given amount of air to flow through a paper surface at a constant pressure. The measurement is carried out on the basis of ISO 5636-5 with the help of the densometer 121D from Lorenzen & Wettre. The readings are given in Gurley seconds / 100 ml. Values less than 25 s / hml show papers with very good air permeability. Values higher than 60 s / hml indicate a compacted structure and thus poor permeability.

Farbdichtecolor density

Die BildqualitƤt wird durch Messung der Farbdichte fĆ¼r die Grundfarben Cyan, Magenta, Gelb und Schwarz bewertet. Die Farbdichten werden mit dem Densitometer SpectroEye der Firma x-rite im Auflicht gemessen.The image quality is evaluated by measuring the color density for the primary colors cyan, magenta, yellow and black. The color densities are measured with the densitometer SpectroEye from x-rite.

Durchschlagen der TintePenetration of the ink

Beim Durchschlagen der Tinte handelt es sich um ein punktuelles oder auch partielles Durchdringen der Druckfarbe zur RĆ¼ckseite des Papiers hin. Gerade bei Dekorpapieren mit hoher DurchlƤssigkeit besteht die Gefahr des Penetrierens der Druckfarbe ins Papierinnere und damit des Durchschlagens zur RĆ¼ckseite des Papierblatts.Penetration of the ink is a punctiform or even partial penetration of the ink towards the back of the paper. Especially with decorative papers with high permeability there is a risk of penetration of the Printing ink inside the paper and thus breaking through to the back of the paper sheet.

Die visuelle Bewertung des Durchschlag-Verhaltens stellt ein MaƟ fĆ¼r die Fixierung der Tinte auf der OberflƤche des Basispapiers dar.

  • + kein Durchschlagen, gute Tintenfixierung
  • o leichtes Durchschlagen, mittlere Tintenfixierung
  • - Durchdringen der Tinte auf die RĆ¼ckseite, schlechte Tintenfixierung
The visual evaluation of the breakdown behavior provides a measure of the fixation of the ink on the surface of the base paper.
  • + no penetration, good ink fixation
  • o easy penetration, medium ink fixation
  • - Penetration of the ink on the back, poor ink fixation

Die PrĆ¼fergebnisse sind in folgender Tabelle zusammengestellt: Farbdichte Luftwiderstand s/hml Durchschlag Cyan Magenta Gelb Schwarz B1 0,40 0,55 0,63 0,99 18 ā—‹ B2 0,41 0,57 0,64 1,02 22 + B3 0,41 0,57 0,62 1,00 22 + V1 0,38 0,34 0,50 0,52 14 - V2 0,40 0,58 0,63 1,07 28 + V3 0,40 0,71 0,68 1,30 50 + The test results are summarized in the following table: color density Air resistance s / hml punch cyan magenta yellow black B1 0.40 0.55 0.63 0.99 18 ā—‹ B2 0.41 0.57 0.64 1.02 22 + B3 0.41 0.57 0.62 1.00 22 + V1 0.38 0.34 0.50 0.52 14 - V2 0.40 0.58 0.63 1.07 28 + V3 0.40 0.71 0.68 1.30 50 +

Claims (12)

  1. Base paper for decorative coating materials comprising a paper which is not internally sized, characterized in that the base paper comprises a surface application which contains an alkaline earth salt and an inorganic pigment having a specific BET surface area of from 100 to 400 cm2/g, whereby the surface application does not contain a polymeric binding agent.
  2. Base paper according to claim 1, characterized in that the alkaline earth salt is a water-soluble calcium salt.
  3. Base paper according to claim 1, characterized in that the alkaline earth salt is calcium chloride or calcium nitrate.
  4. Base paper according to claim 3, characterized in that the specific BET surface area of the inorganic pigment is from 200 to 330 cm2/g.
  5. Base paper according to claim 3 or 4, characterized in that the inorganic pigment is an aluminium oxide, an aluminium hydroxide, a boehmite and/or a silica.
  6. Base paper according to claim 3 or 4, characterized in that the inorganic pigment is a cationised pyrogenic silica.
  7. Base paper according to at least one of claims 3 to 6, characterized in that the alkaline earth salt/inorganic pigment ratio, based on the mass, is from 60:40 to 40:60.
  8. Base paper according to at least one of claims 1 to 7, characterized in that the surface application is applied in an amount of from 1 to 10 g/m2, based on the mass of the dry substance.
  9. Base paper according to at least one of claims 1 to 8, characterized in that the surface of the base paper has a pH value of from 4.5 to 8.
  10. Use of the base paper according to at least one of claim 1 to 9 for the production of laminated materials and laminates of all types
  11. Method for producing a decorative coating material characterized in that a base paper which is not internally sized is provided with a surface application which contains an alkaline earth salt according to claim 1, is printed by a digital printing method, impregnated with a thermoplastic resin and dried.
  12. Method for producing a decorative coating material according to claim 11, characterized in that the paper is impregnated with a thermoplastic resin and is dried in such a way that the thermoplastic resin is only up to approximately 80 % cured.
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US9920486B2 (en) * 2013-01-09 2018-03-20 The Chemours Company Fc, Llc DĆ©cor paper having improved optical performance comprising treated inorganic particles
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EP3231596B1 (en) * 2016-04-12 2018-10-10 SWISS KRONO Tec AG Support carrier material with a modified resin layer, and the production thereof.
WO2018017089A1 (en) 2016-07-21 2018-01-25 Hewlett-Packard Development Company, L.P. Ink fixative solution
FR3062660B1 (en) 2017-02-03 2019-06-07 Ahlstrom-Munksjƶ Oyj DECORATION PAPER FOR LAMINATES
EP3754109B1 (en) 2019-06-18 2022-09-28 Schoeller Technocell GmbH & Co. KG Pre-impregnate with improved flatness
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