EP1207233B1 - High opacity decorative base paper - Google Patents

High opacity decorative base paper Download PDF

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Publication number
EP1207233B1
EP1207233B1 EP01126632A EP01126632A EP1207233B1 EP 1207233 B1 EP1207233 B1 EP 1207233B1 EP 01126632 A EP01126632 A EP 01126632A EP 01126632 A EP01126632 A EP 01126632A EP 1207233 B1 EP1207233 B1 EP 1207233B1
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EP
European Patent Office
Prior art keywords
decorative
talc
paper
base paper
decorative base
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.)
Revoked
Application number
EP01126632A
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German (de)
French (fr)
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EP1207233A3 (en
EP1207233A2 (en
Inventor
Hartmut Dr. Schulz
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Technocell Dekor GmbH and Co KG
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Technocell Dekor GmbH and Co KG
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Application filed by Technocell Dekor GmbH and Co KG filed Critical Technocell Dekor GmbH and Co KG
Priority claimed from US10/006,318 external-priority patent/US6783631B2/en
Publication of EP1207233A2 publication Critical patent/EP1207233A2/en
Publication of EP1207233A3 publication Critical patent/EP1207233A3/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/73—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of inorganic material
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres
    • D21H11/22—Chemically or biochemically modified fibres cationised
    • 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
    • D21H17/68—Water-insoluble compounds, e.g. fillers, 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape

Definitions

  • the invention relates to a decorative base paper, a Pigment mixture of titanium dioxide and talcum contains as well decorative coating materials obtained therefrom.
  • Decorative coating materials are preferably for Surface coating in furniture manufacturing and in the Interior fitting used.
  • Under decorative film is understood a resin impregnated or resin impregnated and surface treated, printed or unprinted Paper web.
  • Decorative foils are provided with a carrier plate glued or glued.
  • Laminates High Pressure Laminates
  • the structure of these laminates consists in general from a highest surface resistance generating transparent overlay sheet (overlay), a resin-impregnated decorative paper and one or more phenolbehechen kraft papers.
  • overlay transparent overlay sheet
  • resin-impregnated decorative paper one or more phenolbeh GmbHen kraft papers.
  • hardboard and chipboard and plywood used.
  • Laminates (Low Pressure Laminates) are treated with synthetic resin soaked decorative paper directly with a base, For example, a chipboard, using a compressed low pressure.
  • DE 197 28 796 A1 relates to a base paper for the Production of decorative surfaces with a share of at least 80% by weight of hardwood pulp on Total paper pulp, 2 to 4 wt% mineral Filler and 3.7 to 4.2 wt.% Starch.
  • the mineral Filler can be titanium dioxide.
  • DE 199 12 149 A1 concerns a decorative base paper with improved Dry strength, its pulp a Pulp mixture of a non-modified and a contains cationic-modified pulp.
  • the amount of the filler, for example titanium dioxide, in this Decorative paper can be up to 55% by weight.
  • Decorative base papers generally consist of highly white Sulphate pulps, mainly of hardwood pulp, to to 45 wt.% Pigments and fillers, based on the Weight of the base paper, as well as wet strength agent, Retention aids and fixatives.
  • decorative base paper differ from usual papers by the very much higher filler content and the absence of a Paper with standard sizing or surface sizing with the known sizing agents such as alkylketene dimers.
  • Opacity is one of the most important properties of Decorative base. This characterizes the opacity opposite the pad.
  • a high opacity of the decorative base paper is due to the Addition of white pigments achieved.
  • white pigment becomes usually used titanium dioxide. This pigment ensures high opacity and good brightness and white of the decorative base paper.
  • the disadvantage, however, is the high price of titanium dioxide.
  • the object underlying the invention is to a low-cost decorative paper with a high opacity at the same time reduced titanium dioxide content provide.
  • the talc used in the invention has a very close Grain size distribution with a D50 of less than 3 ⁇ m. This means that 50 wt.% Of talcum particles a Have diameters of less than about 3 microns. Especially talc with a particle size distribution D50 is preferred less than 2 ⁇ m.
  • the specific surface area of the talc used according to the invention is greater than about 30,000 m 2 / kg, and in a particularly preferred embodiment greater than about 40,000 m 2 / kg.
  • the specific surface area of conventional talcum types is in the range from 8,000 to 16,000 m 2 / kg.
  • the specific surface was determined according to DIN 66126.
  • the proportion of talc in the pigment mixture is preferably at 0.1 to 25 wt.%, Based on the Total pigment content.
  • the pigment mixture of the invention Decorative base paper contained titanium dioxide can be Titanium dioxide commonly used in decorative papers be. Such titanium dioxides are commercially available and can be used in rutile or anatase type. Such Rutile-type titanium dioxides are particularly preferred.
  • fillers such as zinc sulfide, Calcium carbonate, kaolin or mixtures thereof used become.
  • the proportion of the filler in the decorative base paper can be up to 55% by weight, in particular 11 to 50% by weight or 20 to 45% by weight, based on the weight of the paper.
  • the basis weight of the decorative base papers according to the invention can be in the range of 30 to 300 g / m 2 and will usually be 40 to 200 g / m 2 . The basis weights are chosen depending on the particular uses.
  • Decorative base papers can be softwood pulps (long fiber pulps) or hardwood pulps (short fiber pulps) be used.
  • Cotton fibers or mixtures of the aforementioned Pulp types can be used.
  • a mixture of is preferred Softwood / Hardwood pulps in the ratio of 10:90 to 90:10 or for example mixtures of softwood / hardwood pulps in the ratio 30:70 to 70:30.
  • the Pulp may have a freeness of 20 ° to 60 ° SR after Schopper-Riegler have.
  • the pulp mixture contains a proportion cationically modified pulp fibers of at least 5% by weight, based on the weight of the pulp mixture, contains. Particularly advantageous is a share from 10 to 50% by weight, in particular 10 to 20% by weight, of cationically modified pulp in the pulp mixture proved.
  • Cationically modified pulps are for example from THE PAPER, Issue 12 (1980) p.575-579.
  • the in the pulp cationically modified Pulp has an effective cationic charge of 20 to 300 mmol / kg pulp, determined according to the internal Method No. 4 of the TU Darmstadt.
  • an effective cationic charge is one Charge density to be understood with the charge density of un-cationized pulp.
  • the Density of pulp depends on the amount of pulp to be used cationic agent.
  • the amount of cationizing agent may be 0.005 to 200 g / 1 kg Pulp amount.
  • the cationic modification of the pulp fibers can by reaction of the fibers with epichlorohydrin resin and a tertiary amine or by reaction with quaternary ammonium chlorides, such as Chlorohydroxypropyltrimethyl-ammonium chloride or Glycidyltrimethyl ammonium chloride.
  • Pulp fibers used by a Addition reaction of quaternary, glycidylfunktionelle Group containing ammonium compounds with Hydroxyl groups of the cellulose cationically modified are.
  • the decorative base paper of the invention may be wet strength agents such as polyamide / polyamine-epichlorohydrin resin, others Polyamine derivatives or polyamide derivatives, cationic Polyacrylates, modified melamine-formaldehyde resin or cationized starches. These will be the Pulp suspension added. Likewise, the addition of Retention aids and other substances such as organic and inorganic colored pigments, dyes, optical brightener and dispersant possible.
  • the decorative base papers according to the invention can on a Fourdrinier paper machine or a Yankee paper machine getting produced. This can do that Pulp mixture at a consistency of 2 to 4 wt.% are ground to a freeness of 30 to 45 ° SR.
  • a mixing tank are fillers, such as titanium dioxide and talc, and wet strength agent and added with the Pulp mixture well mixed.
  • the thus obtained Thick material is up to a consistency of about 1 wt.% diluted and, if necessary, further excipients such as Retention aids, defoamers, aluminum sulfate and others previously added adjuvants.
  • This thin material is placed over the headbox of the paper machine on the Led wire section. It is a nonwoven fabric formed and after draining, get the decorative base paper which then dried.
  • Resin dispersions impregnated or impregnated are common synthetic resin dispersions for example, those based on polyacrylic or Polyacrylmethyl esters, polyvinyl acetate, polyvinyl chloride or synthetic resin solutions based on phenol / formaldehyde, Urea / formaldehyde or melamine / formaldehyde precondensates or their compatible mixtures.
  • the impregnation can also be done in the size press of the Paper machine done.
  • the decorative paper can be so be impregnated, that the paper is not complete is impregnated by.
  • Such decorative papers are also referred to as prepregs.
  • the proportion of in the Decorative base paper by impregnation of incorporated resin is in this case 25 to 30 wt.%, Based on the Weight of the paper.
  • the soaked papers can still be painted and printed and then on a Substrate can be applied as a wooden board.
  • the lacquered and optionally printed products generally referred to as decorative films.
  • the basic mixture was a pulp mixture of 70% by weight. Eucalyptus pulp and 30% by weight softwood pulp with 0.6% by weight of epichlorohydrin resin as wet strength agent, 0.11 % By weight of a retention aid and 0.03% by weight of a Defoamer, the latter three components in each case on the mass of the pulp mixture, added.
  • the Mixture was brought to a pH of with aluminum sulfate 6.5 set.
  • This mixture was made with a pigment mixture 55.8% by weight of titanium dioxide and 5.2% by weight of talc.
  • a decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine.
  • the titanium dioxide content was 33.5 g / m 2 (31.9 wt.%)
  • the talc content 3.1 g / m 2 (2.95 wt.%).
  • the talc had a particle size distribution D50 of 1.9 ⁇ m and a specific surface area of 44,300 m 2 / kg.
  • Example 1 To the base mixture of Example 1 was a Pigment mixture of 50.3% by weight titanium dioxide and 14.7% by weight Given talc.
  • a decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine.
  • the titanium dioxide content was 30.2 g / m 2 (28.8 wt.%)
  • the talc content 8.8 g / m 2 (8.4 wt.%).
  • the talc had a particle size distribution D50 of 1.9 ⁇ m and a specific surface area of 44,300 m 2 / kg.
  • Example 2 To the masterbatch of Example 1, a pigment mixture of 64.5 wt.% Titanium dioxide and 3.3 wt.% Talc was added. A decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine. The titanium dioxide content was 38.7 g / m 2 (36.5 wt.%) And the talc content 2.0 g / m 2 (1.9 wt.%). The talc had a particle size distribution D50 of 1.9 ⁇ m and a specific surface area of 44,300 m 2 / kg.
  • Example 2 To the base mixture from Example 1, a pigment mixture of 53.9 wt.% Titanium dioxide and 11.3 wt.% Talc was added. A decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine. The titanium dioxide content was 32.3 g / m 2 (30.8 wt.%) And the talc content 6.8 g / m 2 (6.5 wt.%). The talc had a particle size distribution D50 of 1.5 ⁇ m and a specific surface area of 47,100 m 2 / kg.
  • Example 2 As Comparative Example 1, only a 62% strength by weight titanium dioxide dispersion was added to the base mixture from Example 1.
  • Example 2 To the base mixture of Example 1, a pigment mixture of 50.8 wt.% Titanium dioxide and 14.4 wt.% Talc was added. A decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine. The titanium dioxide content was 30.5 g / m 2 (29% by weight) and the talc content 8.7 g / m 2 (8.3% by weight). The talc had a particle size distribution D50 of 3.7 ⁇ m and a specific surface area of 8,600 m 2 / kg.
  • the results of the opacity measurement show that with the The talc used according to the invention has a high opacity even with a significantly reduced titanium dioxide content can be achieved.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)

Description

Die Erfindung betrifft ein Dekorrohpapier, das ein Pigmentgemisch aus Titandioxid und Talkum enthält sowie daraus erhaltene dekorative Beschichtungswerkstoffe.The invention relates to a decorative base paper, a Pigment mixture of titanium dioxide and talcum contains as well decorative coating materials obtained therefrom.

Dekorative Beschichtungswerkstoffe, sogenannte Dekorpapiere oder Dekorfolien, werden vorzugsweise zur Oberflächenbeschichtung bei der Möbelherstellung und im Innenausbau eingesetzt. Unter Dekorfolie versteht man eine kunstharzgetränkte oder kunstharzgetränkte und oberflächenbehandelte, bedruckte oder unbedruckte Papierbahn. Dekorfolien werden mit einer Trägerplatte verleimt oder verklebt.Decorative coating materials, so-called Decorative papers or decorative films, are preferably for Surface coating in furniture manufacturing and in the Interior fitting used. Under decorative film is understood a resin impregnated or resin impregnated and surface treated, printed or unprinted Paper web. Decorative foils are provided with a carrier plate glued or glued.

Je nach Art des Imprägniervorgangs unterscheidet man zwischen Dekorfolien mit durchimprägniertem Papierkern und Dekorfolien auf Vorimprägnat-Basis, bei denen das Papier in der Papiermaschine online nur teilweise imprägniert wird. Schichtpreßstoffe (High Pressure Laminates) sind Laminate, die durch Verpressen mehrerer imprägnierter, aufeinander geschichteter Papiere entstehen. Der Aufbau dieser Schichtpreßstoffe besteht im allgemeinen aus einem höchste Oberflächenbeständigkeit erzeugenden transparenten Auflageblatt (Overlay), einem kunstharzgetränkten Dekorpapier und einem oder mehreren phenolbeharzten Kraftpapieren. Als Unterlage hierfür werden beispielsweise Hartfaser- und Holzspanplatten sowie Sperrholz eingesetzt. Depending on the type of impregnation one differentiates between decorative films with impregnated paper core and prepreg-based decorative films in which the Paper in the paper machine online only partially is impregnated. Laminates (High Pressure Laminates) are laminates made by pressing several impregnated, stacked papers arise. The structure of these laminates consists in general from a highest surface resistance generating transparent overlay sheet (overlay), a resin-impregnated decorative paper and one or more phenolbeharzten kraft papers. As a support for this For example, hardboard and chipboard and plywood used.

Bei den nach dem Kurztaktverfahren hergestellten Laminaten (Low Pressure Laminates) wird das mit Kunstharz getränkte Dekorpapier direkt mit einer Unterlage, beispielsweise einer Spanplatte, unter Anwendung eines niedrigen Drucks verpreßt.In the case of the short-cycle method Laminates (Low Pressure Laminates) are treated with synthetic resin soaked decorative paper directly with a base, For example, a chipboard, using a compressed low pressure.

Das bei den oben genannten Beschichtungswerkstoffen verwendete Dekorpapier wird weiß oder farbig mit oder ohne zusätzlichen Aufdruck eingesetzt.This with the above-mentioned coating materials Decor paper used becomes white or colored with or used without additional imprint.

An sogenannte Dekorrohpapiere als Ausgangsmaterialien zur Herstellung der oben genannten Beschichtungswerkstoffe werden besondere Anforderungen gestellt wie hohe Opazität für eine bessere Abdeckung der Unterlage, gleichmäßige Formation und Grammatur des Blatts für eine gleichmäßige Harzaufnahme, hohe Lichtbeständigkeit, hohe Reinheit und Gleichmäßigkeit der Farbe für gute Reproduzierbarkeit des aufzudruckenden Musters, hohe Naßfestigkeit für einen reibungslosen Imprägniervorgang, entsprechende Saugfähigkeit zur Erlangung des erforderlichen Harzsättigungsgrades, Trockenfestigkeit, die bei Umrollvorgängen in der Papiermaschine und beim Bedrucken in der Druckmaschine.To so-called decorative base papers as starting materials for Production of the above-mentioned coating materials special requirements are made such as high opacity for better coverage of the pad, even Formation and grammage of the sheet for a uniform Resin absorption, high light resistance, high purity and Uniformity of color for good reproducibility of the pattern to be printed, high wet strength for one smooth impregnation process, appropriate Absorbency to obtain the required Resin saturation, dry strength, at Rewinding operations in the paper machine and printing in the printing press.

Die DE 197 28 796 A1 betrifft ein Rohpapier für die Herstellung von dekorativen Oberflächen mit einem Anteil von mindestens 80 Gew.% Laubholzzellstoff am Gesamtpapierfaserstoff, 2 bis 4 Gew.% mineralischen Füllstoffs und 3,7 bis 4,2 Gew.% Stärke. Der mineralische Füllstoff kann Titandioxid sein. Die DE 199 12 149 A1 betrifft ein Dekorrohpapier mit verbesserter Trockenfestigkeit, dessen Papiermasse ein Zellstoffgemisch aus einem nicht-modifizierten und einem kationisch-modifizierten Zellstoff enthält. Der Anteil des Füllstoffs, beispielsweise Titandioxid, in diesem Dekorrohpapier kann bis zu 55 Gew.% betragen.DE 197 28 796 A1 relates to a base paper for the Production of decorative surfaces with a share of at least 80% by weight of hardwood pulp on Total paper pulp, 2 to 4 wt% mineral Filler and 3.7 to 4.2 wt.% Starch. The mineral Filler can be titanium dioxide. DE 199 12 149 A1 concerns a decorative base paper with improved Dry strength, its pulp a Pulp mixture of a non-modified and a contains cationic-modified pulp. The amount of the filler, for example titanium dioxide, in this Decorative paper can be up to 55% by weight.

Dekorrohpapiere bestehen im allgemeinen aus hochweißen Sulfatzellstoffen, überwiegend aus Laubholzzellstoff, bis zu 45 Gew.% Pigmenten und Füllstoffen, bezogen auf das Gewicht des Rohpapiers, sowie Naßfestmittel, Retentionsmitteln und Fixiermitteln. Dekorrohpapiere unterscheiden sich von üblichen Papieren durch den sehr viel höheren Füllstoffanteil und das Fehlen einer beim Papier üblichen Masseleimung oder Oberflächenleimung mit den bekannten Leimungsmitteln wie Alkylketendimeren.Decorative base papers generally consist of highly white Sulphate pulps, mainly of hardwood pulp, to to 45 wt.% Pigments and fillers, based on the Weight of the base paper, as well as wet strength agent, Retention aids and fixatives. decorative base paper differ from usual papers by the very much higher filler content and the absence of a Paper with standard sizing or surface sizing with the known sizing agents such as alkylketene dimers.

Die Opazität gehört zu den wichtigsten Eigenschaften des Dekorrohpapiers. Diese kennzeichnet das Abdeckvermögen gegenüber der Unterlage.Opacity is one of the most important properties of Decorative base. This characterizes the opacity opposite the pad.

Eine hohe Opazität des Dekorrohpapiers wird durch die Zugabe von Weißpigmenten erreicht. Als Weißpigment wird in der Regel Titandioxid verwendet. Dieses Pigment gewährleistet eine hohe Opazität und eine gute Helligkeit und Weiße des Dekorrohpapiers. Nachteilig ist allerdings der hohe Preis des Titandioxids.A high opacity of the decorative base paper is due to the Addition of white pigments achieved. As white pigment becomes usually used titanium dioxide. This pigment ensures high opacity and good brightness and white of the decorative base paper. The disadvantage, however, is the high price of titanium dioxide.

Bei dem teilweise oder vollständigen Austausch von Titandioxid durch andere Weißpigmente wird eine Verschlechterung dieser Eigenschaften erzielt. Eine Angleichung der Opazität ist nur durch eine Erhöhung des Pigmentanteils zu erreichen. Der Pigmentanteil läßt sich aber nicht beliebig erhöhen, da in diesem Fall mit einer Beeinträchtigung der physikalischen Eigenschaften wie Retentionsverhalten der Zellstoffsuspension, Festigkeiten, Lichtechtheit und Harzaufnahme zu rechnen ist. In the case of partial or complete exchange of Titanium dioxide by other white pigments becomes one Deterioration of these properties achieved. A Alignment of opacity is only by increasing the Reach pigment content. The pigment content can be but not increase arbitrarily, since in this case with a Impairment of physical properties such as Retention behavior of the pulp suspension, Strengths, light fastness and resin absorption to be expected is.

Die der Erfindung zugrundeliegende Aufgabe besteht darin, ein kostengünstiges Dekorpapier mit einer hohen Opazität bei gleichzeitig vermindertem Titandioxidanteil bereitzustellen.The object underlying the invention is to a low-cost decorative paper with a high opacity at the same time reduced titanium dioxide content provide.

Gelöst wird diese Aufgabe durch ein Dekorrohpapier für dekorative Beschichtungswerkstoffe, das eine Pigmentmischung aus einem Titandioxid und Talkum enthält. Das erfindungsgemäß eingesetzte Talkum hat eine sehr enge Korngrößenverteilung mit einem D50 von kleiner etwa 3 µm. Dies bedeutet, daß 50 Gew.% der Talkumteilchen einen Durchmesser von weniger als etwa 3µm aufweisen. Besonders bevorzugt ist Talkum mit einer Korngrößenverteilung D50 kleiner etwa 2 µm.This task is solved by a decorative paper for decorative coating materials, the one Pigment mixture of a titanium dioxide and talcum contains. The talc used in the invention has a very close Grain size distribution with a D50 of less than 3 μm. This means that 50 wt.% Of talcum particles a Have diameters of less than about 3 microns. Especially talc with a particle size distribution D50 is preferred less than 2 μm.

Die spezifische Oberfläche des erfindungsgemäß eingesetzten Talkums ist größer als etwa 30.000 m2/kg, gemäß einer besonders bevorzugten Ausführung größer als etwa 40.000 m2/kg. Die spezifische Oberfläche herkömmlicher Talkumtypen liegt demgegenüber im Bereich von 8.000 bis 16.000 m2/kg. Die spezifische Oberfläche wurde nach DIN 66126 bestimmt.The specific surface area of the talc used according to the invention is greater than about 30,000 m 2 / kg, and in a particularly preferred embodiment greater than about 40,000 m 2 / kg. In contrast, the specific surface area of conventional talcum types is in the range from 8,000 to 16,000 m 2 / kg. The specific surface was determined according to DIN 66126.

Der Anteil an Talkum im Pigmentgemisch liegt vorzugsweise bei 0,1 bis 25 Gew.%, bezogen auf den Gesamtpigmentgehalt.The proportion of talc in the pigment mixture is preferably at 0.1 to 25 wt.%, Based on the Total pigment content.

Das im Pigmentgemisch des erfindungsgemäßen Dekorrohpapiers enthaltene Titandioxid kann ein üblicherweise in Dekorpapieren verwendetes Titandioxid sein. Solche Titandioxide sind im Handel erhältlich und können in Rutil- oder Anatas-Typ verwendet werden. Solche Titandioxide vom Rutil-Typ sind besonders bevorzugt. The pigment mixture of the invention Decorative base paper contained titanium dioxide can be Titanium dioxide commonly used in decorative papers be. Such titanium dioxides are commercially available and can be used in rutile or anatase type. Such Rutile-type titanium dioxides are particularly preferred.

Es können weitere Füllstoffe wie Zinksulfid, Calciumcarbonat, Kaolin oder deren Gemische verwendet werden.There may be other fillers such as zinc sulfide, Calcium carbonate, kaolin or mixtures thereof used become.

Der Anteil des Füllstoffs im Dekorrohpapier kann bis zu 55 Gew.%, insbesondere 11 bis 50 Gew.% oder 20 bis 45 Gew.%, bezogen auf das Papiergewicht, betragen. Das Flächengewicht der erfindungsgemäßen Dekorrohpapiere kann im Bereich von 30 bis 300 g/m2 liegen und wird üblicherweise 40 bis 200 g/m2 betragen. Die Flächengewichte werden in Abhängigkeit vom besonderen Verwendungszwecke gewählt.The proportion of the filler in the decorative base paper can be up to 55% by weight, in particular 11 to 50% by weight or 20 to 45% by weight, based on the weight of the paper. The basis weight of the decorative base papers according to the invention can be in the range of 30 to 300 g / m 2 and will usually be 40 to 200 g / m 2 . The basis weights are chosen depending on the particular uses.

Als Zellstoffe zur Herstellung der erfindungsgemäßen Dekorrohpapiere können Nadelholz-Zellstoffe (Langfaser-Zellstoffe) oder Laubholz-Zellstoffe (Kurzfaser-Zellstoffe) verwendet werden. Auch der Einsatz von Baumwollfasern oder Gemische der zuvor genannten Zellstoffsorten können verwendet werden. Besonders bevorzugt wird beispielsweise eine Mischung aus Nadelholz-/Laubholz-Zellstoffen im Verhältnis 10:90 bis 90:10 oder beispielsweise Gemischen aus Nadelholz-/Laubholz-Zellstoffen im Verhältnis 30:70 bis 70:30. Der Zellstoff kann einen Mahlgrad von 20° bis 60°SR nach Schopper-Riegler haben.As pulps for the production of the inventive Decorative base papers can be softwood pulps (long fiber pulps) or hardwood pulps (short fiber pulps) be used. Also the use of Cotton fibers or mixtures of the aforementioned Pulp types can be used. Especially For example, a mixture of is preferred Softwood / Hardwood pulps in the ratio of 10:90 to 90:10 or for example mixtures of softwood / hardwood pulps in the ratio 30:70 to 70:30. Of the Pulp may have a freeness of 20 ° to 60 ° SR after Schopper-Riegler have.

Vorzugsweise enthält das Zellstoffgemisch einen Anteil an kationisch modifizierten Zellstoffasern von mindestens 5 Gew.%, bezogen auf das Gewicht des Zellstoffgemischs, enthält. Als besonders vorteilhaft hat sich ein Anteil von 10 bis 50 Gew.%, insbesondere 10 bis 20 Gew.%, des kationisch modifizierten Zellstoffs im Zellstoffgemisch erwiesen. Preferably, the pulp mixture contains a proportion cationically modified pulp fibers of at least 5% by weight, based on the weight of the pulp mixture, contains. Particularly advantageous is a share from 10 to 50% by weight, in particular 10 to 20% by weight, of cationically modified pulp in the pulp mixture proved.

Kationisch modifizierte Zellstoffe sind beispielsweise aus DAS PAPIER, Heft 12 (1980) S.575-579 bekannt.Cationically modified pulps are for example from THE PAPER, Issue 12 (1980) p.575-579.

In einer besonderen Ausgestaltung der Erfindung weist der in der Papiermasse enthaltene kationisch modifizierte Zellstoff eine wirksame kationische Ladung von 20 bis 300 mmol/kg Zellstoff auf, bestimmt nach der internen Methode Nr. 4 der TU Darmstadt. Bevorzugt werden Zellstoffasern mit einer Ladungsdichte von 30 bis 200 mmol/kg, insbesondere 30 bis 100 mmol/kg. Unter dem Begriff "wirksame kationische Ladung" ist eine Ladungsdichte zu verstehen, die mit der Ladungsdichte des nicht kationisierten Zellstoffs verrechnet wurde. Die Ladungsdichte des Zellstoffs hängt von der Menge des einzusetzenden kationischen Mittels ab. Die Menge des kationisierenden Mittels kann 0,005 bis 200 g/1 kg Zellstoff betragen.In a particular embodiment of the invention, the in the pulp cationically modified Pulp has an effective cationic charge of 20 to 300 mmol / kg pulp, determined according to the internal Method No. 4 of the TU Darmstadt. To be favoured Pulp fibers with a charge density of 30 to 200 mmol / kg, in particular 30 to 100 mmol / kg. Under the The term "effective cationic charge" is one Charge density to be understood with the charge density of un-cationized pulp. The Density of pulp depends on the amount of pulp to be used cationic agent. The amount of cationizing agent may be 0.005 to 200 g / 1 kg Pulp amount.

Die kationische Modifizierung der Zellstoffasern kann durch Reaktion der Fasern mit Epichlorhydrin-Harz und einem tertiären Amin erfolgen oder durch Reaktion mit quaternären Ammoniumchloriden, wie Chlorhydroxypropyltrimethyl-Ammoniumchlorid oder Glycidyltrimethyl-Ammoniumchlorid.The cationic modification of the pulp fibers can by reaction of the fibers with epichlorohydrin resin and a tertiary amine or by reaction with quaternary ammonium chlorides, such as Chlorohydroxypropyltrimethyl-ammonium chloride or Glycidyltrimethyl ammonium chloride.

In einer bevorzugten Ausgestaltung der Erfindung werden Zellstoffasern eingesetzt, die durch eine Additionsreaktion von quaternären, glycidylfunktionelle Gruppen aufweisenden Ammoniumverbindungen mit Hydroxylgruppen der Cellulose kationisch modifiziert sind.In a preferred embodiment of the invention Pulp fibers used by a Addition reaction of quaternary, glycidylfunktionelle Group containing ammonium compounds with Hydroxyl groups of the cellulose cationically modified are.

Das erfindungsgemäße Dekorrohpapier kann Naßfestmittel wie Polyamid/Polyamin-Epichlorhydrin-Harz, andere Polyaminderivate oder Polyamidderivate, kationische Polyacrylate, modifiziertes Melamin-Formaladehyd-Harz oder kationisierte Stärken enthalten. Diese werden der Zellstoffsuspension zugegeben. Ebenso ist die Zugabe von Retentionshilfsmitteln und weiteren Stoffen wie organischen und anorganischen Buntpigmenten, Farbstoffen, optischem Aufheller und Dispergiermittel möglich.The decorative base paper of the invention may be wet strength agents such as polyamide / polyamine-epichlorohydrin resin, others Polyamine derivatives or polyamide derivatives, cationic Polyacrylates, modified melamine-formaldehyde resin or cationized starches. These will be the Pulp suspension added. Likewise, the addition of Retention aids and other substances such as organic and inorganic colored pigments, dyes, optical brightener and dispersant possible.

Die erfindungsgemäßen Dekorrohpapiere können auf einer Fourdrinier-Papiermaschine oder einer Yankee-Papiermaschine hergestellt werden. Dazu kann das Zellstoffgemisch bei einer Stoffdichte von 2 bis 4 Gew.% bis zu einem Mahlgrad von 30 bis 45°SR gemahlen werden. In einer Mischbütte werden Füllstoffe, wie Titandioxid und Talkum, und Naßfestmittel zugesetzt und mit dem Zellstoffgemisch gut vermischt. Der so erhaltene Dickstoff wird bis zu einer Stoffdichte von etwa 1 Gew.% verdünnt und soweit erforderlich weitere Hilfsstoffe wie Retentionsmittel, Entschäumer, Aluminiumsulfat und andere zuvor genannte Hilfsstoffe zugemischt. Dieser Dünnstoff wird über den Stoffauflauf der Papiermaschine auf die Siebpartie geführt. Es wird ein Faservlies gebildet und nach Entwässerung das Dekorrohpapier erhalten, welches anschließend noch getrocknet wird.The decorative base papers according to the invention can on a Fourdrinier paper machine or a Yankee paper machine getting produced. This can do that Pulp mixture at a consistency of 2 to 4 wt.% are ground to a freeness of 30 to 45 ° SR. In a mixing tank are fillers, such as titanium dioxide and talc, and wet strength agent and added with the Pulp mixture well mixed. The thus obtained Thick material is up to a consistency of about 1 wt.% diluted and, if necessary, further excipients such as Retention aids, defoamers, aluminum sulfate and others previously added adjuvants. This thin material is placed over the headbox of the paper machine on the Led wire section. It is a nonwoven fabric formed and after draining, get the decorative base paper which then dried.

Zur Herstellung von Dekorpapieren werden die Dekorrohpapiere mit für diesen Zweck üblichen Kunstharzdispersionen imprägniert oder getränkt. Für diesen Zweck übliche Kunstharzdispersionen sind beispielsweise solche auf der Basis von Polyacryl- oder Polyacrylmethylestern, Polyvinylacetat, Polyvinylchlorid oder Kunstharzlösungen auf Basis von Phenol/Formaldehyd-, Harnstoff/Formaldehyd- oder Melamin/Formaldehyd-Vorkondensaten oder deren verträgliche Gemische. For the production of decorative papers, the Decorative base papers with customary for this purpose Resin dispersions impregnated or impregnated. For this purpose are common synthetic resin dispersions for example, those based on polyacrylic or Polyacrylmethyl esters, polyvinyl acetate, polyvinyl chloride or synthetic resin solutions based on phenol / formaldehyde, Urea / formaldehyde or melamine / formaldehyde precondensates or their compatible mixtures.

Die Imprägnierung kann auch in der Leimpresse der Papiermaschine erfolgen. Das Dekorrohpapier kann derart imprägniert werden, daß das Papier nicht vollständig durch imprägniert wird. Derartige Dekorpapiere werden auch als Vorimprägnate bezeichnet. Der Anteil des in das Dekorrohpapier durch Imprägnierung eingebrachten Harzes beträgt in diesem Fall 25 bis 30 Gew.%, bezogen auf das Gewicht des Papiers.The impregnation can also be done in the size press of the Paper machine done. The decorative paper can be so be impregnated, that the paper is not complete is impregnated by. Such decorative papers are also referred to as prepregs. The proportion of in the Decorative base paper by impregnation of incorporated resin is in this case 25 to 30 wt.%, Based on the Weight of the paper.

Nach Trocknung können die getränkten Papiere noch lackiert und bedruckt werden und anschließend auf ein Substrat wie eine Holzplatte aufgebracht werden. Die lackierten und gegebenenfalls bedruckten Produkte werden im allgemeinen als Dekorfolien bezeichnet.After drying, the soaked papers can still be painted and printed and then on a Substrate can be applied as a wooden board. The lacquered and optionally printed products generally referred to as decorative films.

Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung. Angaben in Gewichtsprozent beziehen sich auf das Gewicht des Zellstoffs, sofern nichts anderes angegeben ist.The following examples serve for further explanation the invention. Data in percent by weight relate on the weight of the pulp, unless otherwise is specified.

Beispiel 1example 1

Als Grundmischung wurde ein Zellstoffgemisch aus 70 Gew.% Eukalyptuszellstoff und 30 Gew.% Nadelholzsulfatzellstoff mit 0,6 Gew.% Epichlorhydrin-Harz als Naßfestmittel, 0,11 Gew.% eines Retentionshilfsmittels und 0,03 Gew.% eines Entschäumers, letztere drei Komponenten jeweils bezogen auf die Masse des Zellstoffgemischs, versetzt. Die Mischung wurde mit Aluminiumsulfat auf einen pH-Wert von 6,5 eingestellt.The basic mixture was a pulp mixture of 70% by weight. Eucalyptus pulp and 30% by weight softwood pulp with 0.6% by weight of epichlorohydrin resin as wet strength agent, 0.11 % By weight of a retention aid and 0.03% by weight of a Defoamer, the latter three components in each case on the mass of the pulp mixture, added. The Mixture was brought to a pH of with aluminum sulfate 6.5 set.

Diese Mischung wurde mit einem Pigmentgemisch aus 55,8 Gew.% Titandioxid und 5,2 Gew.% Talkum versetzt. This mixture was made with a pigment mixture 55.8% by weight of titanium dioxide and 5.2% by weight of talc.

Mit einer Fourdrinier-Papiermaschine wurde ein Dekorpapier mit einem Flächengewicht von 105 g/m2 hergestellt. Der Titandioxidgehalt betrug 33,5 g/m2 (31,9 Gew.%) und der Talkumgehalt 3,1 g/m2 (2,95 Gew.%). Das Talkum hatte eine Korngrößenverteilung D50 von 1,9 µm und eine spezifische Oberfläche von 44.300 m2/kg.A decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine. The titanium dioxide content was 33.5 g / m 2 (31.9 wt.%) And the talc content 3.1 g / m 2 (2.95 wt.%). The talc had a particle size distribution D50 of 1.9 μm and a specific surface area of 44,300 m 2 / kg.

Beispiel 2Example 2

Zu der Grundmischung aus Beispiel 1 wurde ein Pigmentgemisch aus 50,3 Gew.% Titandioxids und 14,7 Gew.% Talkum gegeben.To the base mixture of Example 1 was a Pigment mixture of 50.3% by weight titanium dioxide and 14.7% by weight Given talc.

Mit einer Fourdrinier-Papiermaschine wurde ein Dekorpapier mit einem Flächengewicht von 105 g/m2 hergestellt. Der Titandioxidgehalt betrug 30,2 g/m2 (28,8 Gew.%) und der Talkumgehalt 8,8 g/m2 (8,4 Gew.%). Das Talkum hatte eine Korngrößenverteilung D50 von 1,9 µm und eine spezifische Oberfläche von 44.300 m2/kg.A decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine. The titanium dioxide content was 30.2 g / m 2 (28.8 wt.%) And the talc content 8.8 g / m 2 (8.4 wt.%). The talc had a particle size distribution D50 of 1.9 μm and a specific surface area of 44,300 m 2 / kg.

Beispiel 3Example 3

Zu der Grundmischung aus Beispiel 1 wurde ein Pigmentgemisch aus 64,5 Gew.% Titandioxids und 3,3 Gew.% Talkum gegeben. Mit einer Fourdrinier-Papiermaschine wurde ein Dekorpapier mit einem Flächengewicht von 105 g/m2 hergestellt. Der Titandioxidgehalt betrug 38,7 g/m2 (36,5 Gew.%) und der Talkumgehalt 2,0 g/m2 (1,9 Gew.%). Das Talkum hatte eine Korngrößenverteilung D50 von 1,9 µm und eine spezifische Oberfläche von 44.300 m2/kg. To the masterbatch of Example 1, a pigment mixture of 64.5 wt.% Titanium dioxide and 3.3 wt.% Talc was added. A decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine. The titanium dioxide content was 38.7 g / m 2 (36.5 wt.%) And the talc content 2.0 g / m 2 (1.9 wt.%). The talc had a particle size distribution D50 of 1.9 μm and a specific surface area of 44,300 m 2 / kg.

Beispiel 4Example 4

Zu der Grundmischung aus Beispiel 1 wurde ein Pigmentgemisch aus 53,9 Gew.% Titandioxids und 11,3 Gew.% Talkum gegeben. Mit einer Fourdrinier-Papiermaschine wurde ein Dekorpapier mit einem Flächengewicht von 105 g/m2 hergestellt. Der Titandioxidgehalt betrug 32,3 g/m2 (30,8 Gew.%) und der Talkumgehalt 6,8 g/m2 (6,5 Gew.%). Das Talkum hatte eine Korngrößenverteilung D50 von 1,5 µm und eine spezifische Oberfläche von 47.100 m2/kg.To the base mixture from Example 1, a pigment mixture of 53.9 wt.% Titanium dioxide and 11.3 wt.% Talc was added. A decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine. The titanium dioxide content was 32.3 g / m 2 (30.8 wt.%) And the talc content 6.8 g / m 2 (6.5 wt.%). The talc had a particle size distribution D50 of 1.5 μm and a specific surface area of 47,100 m 2 / kg.

Vergleichsbeispiel 1Comparative Example 1

Als Vergleichsbeispiel 1 wurde zu der Grundmischung aus Beispiel 1 ausschließlich eine 62 Gew.%ige Titandioxid-Dispersion zugegeben. Mit einer Fourdrinier-Papiermaschine wurde ein Dekorpapier mit einem Flächengewicht von 120 g/m2 und einem Titandioxidgehalt von 37,2 g/m2 (31 Gew.%) hergestellt.As Comparative Example 1, only a 62% strength by weight titanium dioxide dispersion was added to the base mixture from Example 1. A decorative paper having a basis weight of 120 g / m 2 and a titanium dioxide content of 37.2 g / m 2 (31% by weight) was produced on a Fourdrinier paper machine.

Vergleichsbeispiel 2Comparative Example 2

Zu der Grundmischung aus Beispiel 1 wurde ein Pigmentgemisch aus 50,8 Gew.% Titandioxids und 14,4 Gew.% Talkum gegeben. Mit einer Fourdrinier-Papiermaschine wurde ein Dekorpapier mit einem Flächengewicht von 105 g/m2 hergestellt. Der Titandioxidgehalt betrug 30,5 g/m2 (29 Gew.%) und der Talkumgehalt 8,7 g/m2 (8,3 Gew.%). Das Talkum hatte eine Korngrößenverteilung D50 von 3,7 µm und eine spezifische Oberfläche von 8.600 m2/kg.To the base mixture of Example 1, a pigment mixture of 50.8 wt.% Titanium dioxide and 14.4 wt.% Talc was added. A decorative paper having a basis weight of 105 g / m 2 was produced on a Fourdrinier paper machine. The titanium dioxide content was 30.5 g / m 2 (29% by weight) and the talc content 8.7 g / m 2 (8.3% by weight). The talc had a particle size distribution D50 of 3.7 μm and a specific surface area of 8,600 m 2 / kg.

An Papierproben der Beispiele B1 bis B4 und der Vergleichsbeispiele V1 und V2 wurde die Opazität mit einem ACE Farbmeßgerät von Data Color nach DIN 53146 bestimmt. Der Titandioxidgehalt im Dekorrohpapier wurde nach DIN 54370 ermittelt. Die erhaltenen Ergebnisse sind in der Tabelle dargestellt. Probe Opazität (%) Talkumgehalt, bezogen auf Gesamtpigment (%) Talkumgehalt (g/m2) B1 92,68 8,5 3,1 B2 92,55 22,6 8,8 B3 92,61 4,9 2,0 B4 92,62 17,3 6,8 V1 92,71 0,0 0,0 V2 90,28 22,2 8,7 On paper samples of Examples B1 to B4 and Comparative Examples V1 and V2, the opacity was determined with an ACE colorimeter from Data Color according to DIN 53146. The titanium dioxide content in the decorative base paper was determined according to DIN 54370. The results obtained are shown in the table. sample Opacity (%) Talcum content, based on total pigment (%) Talc content (g / m 2 ) B1 92.68 8.5 3.1 B2 92.55 22.6 8.8 B3 92.61 4.9 2.0 B4 92.62 17.3 6.8 V1 92.71 0.0 0.0 V2 90.28 22.2 8.7

Die Ergebnisse der Opazitätsmessung zeigen, daß mit dem erfindungsgemäß eingesetzten Talkum eine hohe Opazität auch bei einem wesentlich verringerten Titandioxidanteil erreicht werden kann.The results of the opacity measurement show that with the The talc used according to the invention has a high opacity even with a significantly reduced titanium dioxide content can be achieved.

Claims (6)

  1. A decorative base paper for decorative coating materials, characterized in that a pigment mixture of titanium dioxide and talc, and the talc has a particle size distribution D50 of less than approximately 3.0 µm.
  2. A decorative base paper according to claim 1, characterized in that the talc has a specific surface area of more than approximately 30,000 m2/kg.
  3. A decorative base paper according to claim 1 or 2, characterized in that the talc content is 0.1 to 25 wt%, based on the total pigment content.
  4. A decorative base paper according to one of the claims 1 to 3, characterized in that the paper contains cationically modified cellulose fibers.
  5. A decorative base paper according to claim 4, characterized in that the cellulose fibers are modified with quaternary ammonium compounds with glycidyl function.
  6. A decorative paper or decorative sheet containing a decorative base paper according to one of the claims 1 to 5.
EP01126632A 2000-11-17 2001-11-08 High opacity decorative base paper Revoked EP1207233B1 (en)

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US10/006,318 US6783631B2 (en) 2000-11-17 2001-11-13 Decorative paper with a high opacity

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EP4202117A1 (en) 2021-12-23 2023-06-28 Schoeller Technocell GmbH & Co. KG Two-layer decorative paper for improving print quality

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EP4202117A1 (en) 2021-12-23 2023-06-28 Schoeller Technocell GmbH & Co. KG Two-layer decorative paper for improving print quality

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