EP1207233A2 - High opacity decorative base paper - Google Patents
High opacity decorative base paper Download PDFInfo
- Publication number
- EP1207233A2 EP1207233A2 EP01126632A EP01126632A EP1207233A2 EP 1207233 A2 EP1207233 A2 EP 1207233A2 EP 01126632 A EP01126632 A EP 01126632A EP 01126632 A EP01126632 A EP 01126632A EP 1207233 A2 EP1207233 A2 EP 1207233A2
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- EP
- European Patent Office
- Prior art keywords
- weight
- decorative
- talc
- decorative base
- base paper
- 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.)
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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, the one Contains pigment mixture of titanium dioxide and talc as well decorative coating materials obtained therefrom.
- Decorative coating materials so-called Decorative papers or decorative films are preferably used Surface coating in furniture manufacturing and in Interior fittings used.
- Decorative foil is understood a resin-impregnated or resin-impregnated and surface treated, printed or unprinted Paper web.
- Decorative films come with a backing plate glued or glued.
- Laminates high pressure Laminates
- the structure of these laminates consists in general from a highest surface resistance producing transparent overlay, one resin-soaked decorative paper and one or more phenolic resin kraft papers.
- this hardboard and chipboard for example as well as plywood used.
- Laminates Low Pressure Laminates
- synthetic resin impregnated decor paper directly with a base, for example a chipboard, using a low pressure.
- Decorative paper used is white or colored with or used without additional printing.
- DE 197 28 796 A1 relates to a base paper for the Production of decorative surfaces with a percentage of at least 80% by weight hardwood pulp on Total paper pulp, 2 to 4% by weight mineral Filler and 3.7 to 4.2% by weight of starch.
- the mineral The filler can be titanium dioxide.
- DE 199 12 149 A1 relates to a decorative base paper with improved Dry strength, its pulp one Pulp mixture of an unmodified and a contains cationically modified pulp.
- the amount the filler, for example titanium dioxide, in this Decorative base paper can be up to 55% by weight.
- Decorative base papers generally consist of bright white Sulphate pulps, mainly from hardwood pulp, up to 45% by weight of 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 lack of one when Paper with normal mass sizing or surface sizing the known sizing agents such as alkyl ketene dimers.
- Opacity is one of the most important properties of the Decorative base. This indicates the masking ability towards the document.
- a high opacity of the decorative base paper is due to the White pigments added.
- a white pigment usually used titanium dioxide. This pigment ensures high opacity and good brightness and whiteness of the decorative base paper. However, it is disadvantageous the high price of titanium dioxide.
- the object underlying the invention is an inexpensive decorative paper with a high opacity with a reduced titanium dioxide content provide.
- a decorative base paper for decorative coating materials the one Contains pigment mixture of a titanium dioxide and talc.
- the talc used according to the invention is very narrow Grain size distribution with a D50 of less than about 3 ⁇ m. This means that 50% by weight of the talc particles have a Have a diameter of less than about 3 ⁇ m. Especially talc with a particle size distribution D50 is preferred less than about 2 ⁇ m.
- the specific surface area of the talcum used according to the invention is greater than approximately 30,000 m 2 / kg, in accordance with a particularly preferred embodiment greater than approximately 40,000 m 2 / kg.
- the specific surface area of conventional types of talc 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% by weight, based on the Total pigment content.
- Titanium dioxide contained in decorative base paper can be a Titanium dioxide commonly used in decor papers his.
- Such titanium dioxides are commercially available and can be used in rutile or anatase type.
- Such Rutile-type titanium dioxides are particularly preferred.
- 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 from 30 to 300 g / m 2 and will usually be 40 to 200 g / m 2 . The basis weights are selected depending on the particular application.
- Decorative base papers can be softwood pulps (long-fiber pulps) or hardwood pulps (short fiber pulps) be used.
- the use of Cotton fibers or mixtures of the aforementioned Types of pulp can be used.
- a mixture of, for example, is preferred Softwood / hardwood pulps in a ratio of 10:90 to 90:10 or, for example, mixtures of softwood / Hardwood pulp in a ratio of 30:70 to 70:30.
- the Pulp can have a freeness of 20 ° to 60 ° SR Have Schopper-Riegler.
- the pulp mixture preferably contains a proportion of cationically modified cellulose fibers of at least 5% by weight, based on the weight of the pulp mixture, contains.
- a portion has proven to be particularly advantageous 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 known from DAS PAPIER, Issue 12 (1980) p.575-579.
- the cationically modified contained in the pulp Pulp an effective cationic charge of 20 to 300 mmol / kg pulp, determined according to the internal Method No. 4 of the TU Darmstadt.
- Pulp fibers with a charge density of 30 to 200 mmol / kg, in particular 30 to 100 mmol / kg.
- effective cationic charge is one To understand charge density, which corresponds to the charge density of the not cationized pulp was charged.
- the Charge density of the pulp depends on the amount of cationic agent to be used.
- the amount of cationizing agent can be 0.005 to 200 g / 1 kg Amount of pulp.
- the cationic modification of the pulp fibers can by reaction of the fibers with epichlorohydrin resin and take place with a tertiary amine or by reaction with quaternary ammonium chlorides, such as Chlorhydroxypropyltrimethyl ammonium chloride or Glycidyltrimethyl ammonium chloride.
- Pulp fibers used by a Addition reaction of quaternary, glycidyl-functional Groups containing ammonium compounds with Hydroxyl groups of cellulose modified cationically are.
- the decorative base paper according to the invention can wet strength agents such as polyamide / polyamine-epichlorohydrin resin, others Polyamine derivatives or polyamide derivatives, cationic Polyacrylate, modified melamine-formaladehyde resin or contain cationized starches. These will be the Cellulose suspension added.
- 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 be on a Fourdrinier paper machine or a Yankee paper machine getting produced. This can be done Pulp mixture with a consistency of 2 to 4% by weight be ground to a freeness of 30 to 45 ° SR. Fillers such as titanium dioxide are used in a mixing chest and talc, and wet strength additive and with the Cellulose mixture well mixed. The so obtained Thickness is up to a consistency of about 1 wt.% diluted and, if necessary, other auxiliaries such as Retention aids, defoamers, aluminum sulfate and others previously mentioned excipients admixed. This thin substance is placed on the headbox of the paper machine Screen section led. A nonwoven fabric is formed and receive the decorative base paper after drainage, which is then dried.
- Impregnated or impregnated synthetic resin dispersions are conventional synthetic resin dispersions for example those based on polyacrylic or Polyacrylic methyl 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 Paper machine done.
- the decorative base paper can be such be impregnated that the paper is not complete is impregnated by.
- Such decorative papers are also known as pre-impregnates.
- the share of that in that Decorative base paper by impregnation of the resin in this case is 25 to 30% by weight, based on the Weight of the paper.
- the soaked papers can still painted and printed and then on a Substrate can be applied like a wooden plate.
- the painted and possibly printed products generally referred to as decorative films.
- a cellulose mixture of 70% by weight was used as the basic mixture.
- the Mixture was adjusted to pH 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 with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine.
- the titanium dioxide content was 33.5 g / m 2 (31.9% by weight) and the talc content 3.1 g / m 2 (2.95% by weight).
- the talc had a grain size distribution D50 of 1.9 ⁇ m and a specific surface area of 44,300 m 2 / kg.
- Example 1 Pigment mixture of 50.3% by weight of titanium dioxide and 14.7% by weight Given talc.
- a decorative paper with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine.
- the titanium dioxide content was 30.2 g / m 2 (28.8% by weight) and the talc content 8.8 g / m 2 (8.4% by weight).
- the talc had a grain size distribution D50 of 1.9 ⁇ m and a specific surface area of 44,300 m 2 / kg.
- a pigment mixture of 64.5% by weight of titanium dioxide and 3.3% by weight of talc was added to the basic mixture from Example 1.
- a decorative paper with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine.
- the titanium dioxide content was 38.7 g / m 2 (36.5% by weight) and the talc content was 2.0 g / m 2 (1.9% by weight).
- the talc had a grain size distribution D50 of 1.9 ⁇ m and a specific surface area of 44,300 m 2 / kg.
- a pigment mixture of 53.9% by weight of titanium dioxide and 11.3% by weight of talc was added to the basic mixture from Example 1.
- a decorative paper with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine.
- the titanium dioxide content was 32.3 g / m 2 (30.8% by weight) and the talc content 6.8 g / m 2 (6.5% by weight).
- the talc had a grain size distribution D50 of 1.5 ⁇ m and a specific surface area of 47,100 m 2 / kg.
- a pigment mixture of 50.8% by weight of titanium dioxide and 14.4% by weight of talc was added to the basic mixture from Example 1.
- a decorative paper with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine.
- the titanium dioxide content was 30.5 g / m 2 (29% by weight) and the talc content was 8.7 g / m 2 (8.3% by weight).
- the talc had a grain size distribution D50 of 3.7 ⁇ m and a specific surface area of 8,600 m 2 / kg.
- the opacity was determined on paper samples from Examples B1 to B4 and Comparative Examples V1 and V2 using an ACE color measuring device from Data Color in accordance with DIN 53146.
- the titanium dioxide content in the decorative base paper was determined in accordance with DIN 54370.
- the results obtained are shown in the table. sample Opacity (%) Talc 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
- the results of the opacity measurement show that with the Talc used according to the invention has a high opacity even with a significantly reduced proportion of titanium dioxide can be achieved.
Abstract
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, the one Contains pigment mixture of titanium dioxide and talc 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 used Surface coating in furniture manufacturing and in Interior fittings used. Decorative foil is understood a resin-impregnated or resin-impregnated and surface treated, printed or unprinted Paper web. Decorative films come with a backing 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. A distinction is made depending on the type of impregnation process between decorative foils with impregnated paper core and pre-impregnated decorative foils, where 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 producing transparent overlay, one resin-soaked decorative paper and one or more phenolic resin kraft papers. As a document for this hardboard and chipboard, for example as well as 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.For those manufactured using the short cycle process Laminates (Low Pressure Laminates) with synthetic resin impregnated decor paper directly with a base, for example a chipboard, using a low pressure.
Das bei den oben genannten Beschichtungswerkstoffen verwendete Dekorpapier wird weiß oder farbig mit oder ohne zusätzlichen Aufdruck eingesetzt.That with the coating materials mentioned above Decorative paper used is white or colored with or used without additional printing.
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.On so-called decorative base papers as starting materials for Manufacture of the above coating materials there are special requirements such as high opacity for better coverage of the underlay, even Formation and grammage of the sheet for an even 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, corresponding Absorbency to get the necessary Resin saturation levels, dry strength, which at Rewinding processes in the paper machine and during 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 percentage of at least 80% by weight hardwood pulp on Total paper pulp, 2 to 4% by weight mineral Filler and 3.7 to 4.2% by weight of starch. The mineral The filler can be titanium dioxide. DE 199 12 149 A1 relates to a decorative base paper with improved Dry strength, its pulp one Pulp mixture of an unmodified and a contains cationically modified pulp. The amount the filler, for example titanium dioxide, in this Decorative base 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 bright white Sulphate pulps, mainly from hardwood pulp, up to 45% by weight of 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 lack of one when Paper with normal mass sizing or surface sizing the known sizing agents such as alkyl ketene 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 the Decorative base. This indicates the masking ability towards the document.
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 White pigments added. As a white pigment usually used titanium dioxide. This pigment ensures high opacity and good brightness and whiteness of the decorative base paper. However, it is disadvantageous 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. With the partial or complete exchange of Titanium dioxide from other white pigments becomes one Worsening of these properties is achieved. A Adjustment of the opacity is only possible by increasing the Achieve pigment content. The pigment content can be but don't increase it arbitrarily, because in this case with a Impairment of physical properties such as Retention behavior of the pulp suspension, Strengths, lightfastness and resin absorption are 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 an inexpensive decorative paper with a high opacity with a 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 base paper for decorative coating materials, the one Contains pigment mixture of a titanium dioxide and talc. The talc used according to the invention is very narrow Grain size distribution with a D50 of less than about 3 µm. This means that 50% by weight of the talc particles have a Have a diameter of less than about 3 µm. Especially talc with a particle size distribution D50 is preferred less than about 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 talcum used according to the invention is greater than approximately 30,000 m 2 / kg, in accordance with a particularly preferred embodiment greater than approximately 40,000 m 2 / kg. In contrast, the specific surface area of conventional types of talc 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% by weight, 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. That in the pigment mixture of the invention Titanium dioxide contained in decorative base paper can be a Titanium dioxide commonly used in decor papers his. 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.Other fillers such as zinc sulfide, Calcium carbonate, kaolin or mixtures thereof are 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 from 30 to 300 g / m 2 and will usually be 40 to 200 g / m 2 . The basis weights are selected depending on the particular application.
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 cellulose for the production of the invention Decorative base papers can be softwood pulps (long-fiber pulps) or hardwood pulps (short fiber pulps) be used. The use of Cotton fibers or mixtures of the aforementioned Types of pulp can be used. Especially a mixture of, for example, is preferred Softwood / hardwood pulps in a ratio of 10:90 to 90:10 or, for example, mixtures of softwood / Hardwood pulp in a ratio of 30:70 to 70:30. The Pulp can have a freeness of 20 ° to 60 ° SR Have Schopper-Riegler.
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. The pulp mixture preferably contains a proportion of cationically modified cellulose fibers of at least 5% by weight, based on the weight of the pulp mixture, contains. A portion has proven to be particularly advantageous 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 known from DAS PAPIER, 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 special embodiment of the invention, the cationically modified contained in the pulp Pulp 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 To understand charge density, which corresponds to the charge density of the not cationized pulp was charged. The Charge density of the pulp depends on the amount of cationic agent to be used. The amount of cationizing agent can be 0.005 to 200 g / 1 kg Amount of pulp.
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 take place with a tertiary amine or by reaction with quaternary ammonium chlorides, such as Chlorhydroxypropyltrimethyl 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, glycidyl-functional Groups containing ammonium compounds with Hydroxyl groups of cellulose modified cationically 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 according to the invention can wet strength agents such as polyamide / polyamine-epichlorohydrin resin, others Polyamine derivatives or polyamide derivatives, cationic Polyacrylate, modified melamine-formaladehyde resin or contain cationized starches. These will be the Cellulose suspension added. 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 be on a Fourdrinier paper machine or a Yankee paper machine getting produced. This can be done Pulp mixture with a consistency of 2 to 4% by weight be ground to a freeness of 30 to 45 ° SR. Fillers such as titanium dioxide are used in a mixing chest and talc, and wet strength additive and with the Cellulose mixture well mixed. The so obtained Thickness is up to a consistency of about 1 wt.% diluted and, if necessary, other auxiliaries such as Retention aids, defoamers, aluminum sulfate and others previously mentioned excipients admixed. This thin substance is placed on the headbox of the paper machine Screen section led. A nonwoven fabric is formed and receive the decorative base paper after drainage, which is 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 decor papers, the Decorative base papers with the usual for this purpose Impregnated or impregnated synthetic resin dispersions. For this purpose are conventional synthetic resin dispersions for example those based on polyacrylic or Polyacrylic methyl 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 Paper machine done. The decorative base paper can be such be impregnated that the paper is not complete is impregnated by. Such decorative papers are also known as pre-impregnates. The share of that in that Decorative base paper by impregnation of the resin in this case is 25 to 30% by weight, 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 painted and printed and then on a Substrate can be applied like a wooden plate. The painted and possibly 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 are provided for further explanation the invention. Figures in percent by weight refer on the weight of the pulp, unless otherwise is specified.
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.A cellulose mixture of 70% by weight was used as the basic mixture. Eucalyptus pulp and 30% by weight softwood sulfate pulp with 0.6% by weight 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 each related to the mass of the pulp mixture. The Mixture was adjusted to pH 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 with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine. The titanium dioxide content was 33.5 g / m 2 (31.9% by weight) and the talc content 3.1 g / m 2 (2.95% by weight). The talc had a grain size distribution D50 of 1.9 µm and a specific surface area of 44,300 m 2 / kg.
Zu der Grundmischung aus Beispiel 1 wurde ein Pigmentgemisch aus 50,3 Gew.% Titandioxids und 14,7 Gew.% Talkum gegeben.A was added to the basic mixture from Example 1 Pigment mixture of 50.3% by weight of 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 with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine. The titanium dioxide content was 30.2 g / m 2 (28.8% by weight) and the talc content 8.8 g / m 2 (8.4% by weight). The talc had a grain size distribution D50 of 1.9 µm and a specific surface area of 44,300 m 2 / kg.
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. A pigment mixture of 64.5% by weight of titanium dioxide and 3.3% by weight of talc was added to the basic mixture from Example 1. A decorative paper with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine. The titanium dioxide content was 38.7 g / m 2 (36.5% by weight) and the talc content was 2.0 g / m 2 (1.9% by weight). The talc had a grain size distribution D50 of 1.9 µm and a specific surface area of 44,300 m 2 / kg.
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.A pigment mixture of 53.9% by weight of titanium dioxide and 11.3% by weight of talc was added to the basic mixture from Example 1. A decorative paper with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine. The titanium dioxide content was 32.3 g / m 2 (30.8% by weight) and the talc content 6.8 g / m 2 (6.5% by weight). The talc had a grain size distribution D50 of 1.5 µm and a specific surface area of 47,100 m 2 / kg.
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 a comparative example 1, only a 62% by weight titanium dioxide dispersion was added to the base mixture from example 1. A decorative paper with a basis weight of 120 g / m 2 and a titanium dioxide content of 37.2 g / m 2 (31% by weight) was produced using a Fourdrinier paper machine.
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.A pigment mixture of 50.8% by weight of titanium dioxide and 14.4% by weight of talc was added to the basic mixture from Example 1. A decorative paper with a weight per unit area of 105 g / m 2 was produced using a Fourdrinier paper machine. The titanium dioxide content was 30.5 g / m 2 (29% by weight) and the talc content was 8.7 g / m 2 (8.3% by weight). The talc had a grain 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.
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 Talc used according to the invention has a high opacity even with a significantly reduced proportion of titanium dioxide can be achieved.
Claims (6)
Applications Claiming Priority (3)
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DE10057294 | 2000-11-17 | ||
DE10057294A DE10057294C5 (en) | 2000-11-17 | 2000-11-17 | Decorative paper with high opacity, as well as decorative paper or decorative foil |
US10/006,318 US6783631B2 (en) | 2000-11-17 | 2001-11-13 | Decorative paper with a high opacity |
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EP1207233A2 true EP1207233A2 (en) | 2002-05-22 |
EP1207233A3 EP1207233A3 (en) | 2003-12-03 |
EP1207233B1 EP1207233B1 (en) | 2005-01-05 |
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EP01126632A Revoked EP1207233B1 (en) | 2000-11-17 | 2001-11-08 | High opacity decorative base paper |
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EP (1) | EP1207233B1 (en) |
CN (1) | CN1237226C (en) |
BR (1) | BR0105275B1 (en) |
CA (1) | CA2363357C (en) |
DE (1) | DE10057294C5 (en) |
PL (1) | PL201227B1 (en) |
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EP3026175A1 (en) * | 2014-11-27 | 2016-06-01 | Schoeller Technocell GmbH & Co. KG | Paper with high opacity |
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DE112006001459B4 (en) | 2005-06-07 | 2019-05-29 | The Chemours Company Fc, Llc | PAPER AND LAMB PAPERS CONTAINING MODIFIED TITANIUM DIOXIDE |
DE102008030955B3 (en) * | 2008-07-02 | 2009-11-19 | Hülsta-Werke Hüls Gmbh & Co. Kg | Use of printing paper printed with a decor for flat components |
DE102013100353A1 (en) | 2012-01-12 | 2013-08-22 | Bene_Fit Systems Gmbh & Co. Kg | Reactive composite, useful as filler in paper, comprises carrier and titanium dioxide that are connected to form stable aggregates, and organic reaction product as binder adapted to form chemical and/or physical bond by a reaction |
AU2013210055B2 (en) * | 2012-01-16 | 2017-06-01 | E. I. Du Pont De Nemours And Company | Paper laminates made from decor paper having improved optical performance comprising treated inorganic particles |
EP2804980B1 (en) * | 2012-01-16 | 2016-03-16 | E. I. du Pont de Nemours and Company | Dispersions made from treated inorganic particles for making decor paper having improved optical performance |
CA2867795A1 (en) * | 2012-03-20 | 2013-09-26 | Coldenhove Know How B.V. | Decorative paper |
DE102013009635A1 (en) | 2012-06-28 | 2014-05-22 | Kronos International, Inc. | Titanium dioxide-containing and carbonate-containing composite pigments and process for their preparation |
FR2997421B1 (en) * | 2012-10-30 | 2015-04-17 | Munksjo Arches | DECORATIVE PAPER FOR LAMINATES. |
CA2895946C (en) * | 2013-01-09 | 2020-10-20 | E. I. Du Pont De Nemours And Company | Decor paper having improved optical performance comprising treated inorganic particles |
EP2999818A4 (en) | 2013-05-22 | 2017-01-11 | Dow Global Technologies LLC | Paper composition and process for making the same |
DE202013009496U1 (en) | 2013-10-24 | 2013-11-14 | Samtastic Products GmbH | Multilayer decorative plastic sheet or plate |
EP2883917A1 (en) | 2013-12-13 | 2015-06-17 | Kronos International, Inc. | Composite pigments containing calcium phosphate and method for their preparation |
ES2629518T3 (en) | 2014-05-15 | 2017-08-10 | Omya International Ag | Vulcanized fiber product comprising a material containing calcium carbonate |
CN104313936B (en) * | 2014-08-26 | 2016-08-24 | 淄博欧木特种纸业有限公司 | Composite decoration paper of wood-based plate and preparation method thereof |
EP3081602A1 (en) | 2015-04-17 | 2016-10-19 | Kronos International, Inc. | Composite pigments containing aluminium hydroxide and method for their preparation |
KR20170126998A (en) | 2015-03-10 | 2017-11-20 | 크로노스 인터내셔널, 인코포레이티드 | Composite pigments comprising aluminum hydroxide and a process for their preparation |
DE102015002946A1 (en) | 2015-03-10 | 2016-09-15 | Kronos International, Inc. | Aluminum hydroxide-containing composite pigments and process for their preparation |
US20180223104A1 (en) * | 2015-06-09 | 2018-08-09 | Imerys Usa, Inc. | Compositions and methods for reducing or extending titanium dioxide in paper |
CN106436451B (en) * | 2016-08-18 | 2018-01-16 | 西藏亚吐克工贸有限公司 | The application of talcum powder and titanium white compound powder on papermaking filler |
CN106480776B (en) * | 2016-08-18 | 2018-01-19 | 西藏亚吐克工贸有限公司 | The application of silicon powder and titanium white compound powder in papermaking |
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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US9976257B2 (en) | 2014-11-27 | 2018-05-22 | Schoeller Technocell Gmbh & Co. Kg | Paper with high covering power |
Also Published As
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CA2363357A1 (en) | 2002-05-17 |
PL350718A1 (en) | 2002-05-20 |
EP1207233A3 (en) | 2003-12-03 |
CN1354304A (en) | 2002-06-19 |
BR0105275A (en) | 2002-06-25 |
DE10057294C5 (en) | 2005-06-30 |
CN1237226C (en) | 2006-01-18 |
DE10057294C1 (en) | 2002-06-27 |
EP1207233B1 (en) | 2005-01-05 |
CA2363357C (en) | 2004-05-25 |
PL201227B1 (en) | 2009-03-31 |
BR0105275B1 (en) | 2012-03-20 |
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