DE19845496A1 - Radiation-curable varnish, printing ink or coatings with improved hardness, abrasion resistance and scratch resistance contains hard particles, e.g. of aluminum oxide, in the nanometer size range - Google Patents
Radiation-curable varnish, printing ink or coatings with improved hardness, abrasion resistance and scratch resistance contains hard particles, e.g. of aluminum oxide, in the nanometer size rangeInfo
- Publication number
- DE19845496A1 DE19845496A1 DE19845496A DE19845496A DE19845496A1 DE 19845496 A1 DE19845496 A1 DE 19845496A1 DE 19845496 A DE19845496 A DE 19845496A DE 19845496 A DE19845496 A DE 19845496A DE 19845496 A1 DE19845496 A1 DE 19845496A1
- Authority
- DE
- Germany
- Prior art keywords
- printing ink
- radiation
- coatings
- lacquer
- aluminum oxide
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
Abstract
Description
Die Erfindung betrifft einen Lack, eine Druckfarbe oder eine Beschichtung, die jeweils durch Strahlung härtbar sind. Derartige Systeme aus Lack, Druckfarbe oder Beschichtung als solche sind bekannt. Die Härtung erfolgt z. B. durch UV- Strahlung oder auch Elektronenstrahl. Der Begriff "Strahlung" soll hier auch Elektronenstrahlen erfassen, die ein bevorzugtes Ausführungsbeispiel darstellen.The invention relates to a lacquer, a printing ink or a Coating, each of which is curable by radiation. Such systems made of paint, printing ink or coating as such are known. The hardening takes place e.g. B. by UV Radiation or electron beam. The term "radiation" should also capture electron beams here, which is a preferred one Represent embodiment.
Die DE 43 04 491 A1 beschreibt derartige strahlenhärtbare Lac ke, Beschichtungen und Druckfarben, wobei bevorzugte Ausfüh rungsbeispiele auf Basis der in der Strahlenhärtungschemie be kannten Acrylsäureester (wie z. B. Polyurethan-, Polyester-, Polyether- oder Epoxiacrylate), aber auch auf Basis der soge nannten ungesättigten Polyester oder auf Basis kationisch här tender Bindemittel, wie Epoxiverbindungen, cycloaliphatische Epoxiverbindungen, Vinylether oder -ester aufgebaut sind. Der zitierte Stand der Technik erhöht die Abriebfestigkeit derarti ger Beschichtungen oder farbiger Dekorierungen durch Zugabe pulverförmiger harter Füllstoffe. Die Partikelgrößen liegen im Bereich von 1 bis 50 µm, also 1000-50000 nm.DE 43 04 491 A1 describes such radiation-curable lac ke, coatings and inks, preferred Ausfüh Examples based on those used in radiation curing chemistry knew acrylic acid esters (such as polyurethane, polyester, Polyether or epoxy acrylates), but also based on the so-called called unsaturated polyester or based on cationic hardness tender binders, such as epoxy compounds, cycloaliphatic Epoxy compounds, vinyl ethers or esters are constructed. The State of the art cited increases the abrasion resistance in this way coatings or colored decorations by adding powdery hard fillers. The particle sizes are in the Range from 1 to 50 µm, i.e. 1000-50000 nm.
Die US-Patentschrift 4 356 037 lehrt, einem Bindemittel harte Füllstoffe so zuzusetzen, daß jeweils zwei oder auch eventuell drei Partikelsorten mit jeweils unterschiedlicher Größe zuge setzt werden und zwar so, daß die kleineren Partikel vollstän dig in die Zwischenräume zwischen den größeren Partikeln pas sen, so daß keinerlei freies Bindemittel mehr verbleibt.U.S. Patent 4,356,037 teaches a hard binder Add fillers so that two or maybe even three particle types, each with a different size are set so that the smaller particles completely dig into the spaces between the larger particles sen so that no free binder remains.
Der vorliegenden Erfindung liegt das technische Ziel zugrunde, die Abriebfestigkeit, Schlagfestigkeit, Kratzfestigkeit und Härte einer durch Strahlung härtbaren Substanz der eingangs ge nannten Art weiter zu verbessern.The present invention is based on the technical aim of the abrasion resistance, impact resistance, scratch resistance and Hardness of a radiation-curable substance of the beginning mentioned kind to continue to improve.
Erfindungsgemäß wird dies durch einen Zusatz von 1 bis 15 Ge wichtsprozenten fester Partikel mit Partikelgrößen im Bereich von 2 bis 500 nm erreicht.According to the invention, this is achieved by adding 1 to 15 Ge weight percent solid particles with particle sizes in the range reached from 2 to 500 nm.
Bevorzugt ist vorgesehen, daß die Partikelgrößen im Bereich von 1 bis 100 nm, insbesondere im Bereich von 5 bis 100 nm und wei ter insbesondere im Bereich von 10 bis 100 nm liegen.It is preferably provided that the particle sizes in the range of 1 to 100 nm, in particular in the range from 5 to 100 nm and white ter are in particular in the range from 10 to 100 nm.
Eine andere bevorzugte Ausgestaltung der Erfindung sieht vor, daß der Zusatz 2 bis 8 Gewichtsprozent beträgt.Another preferred embodiment of the invention provides that the addition is 2 to 8 percent by weight.
Als Materialien für die obengenannten Nanopartikel kommen ins
besondere in Betracht:
Carbide, Nitride, Oxide, Boride, Selenide, Telluride, Sulfide,
Halogenide, Metalle.The following are particularly suitable as materials for the above-mentioned nanoparticles:
Carbides, nitrides, oxides, borides, selenides, tellurides, sulfides, halides, metals.
Da Carbide, Nitride und Boride zumeist intensiv gefärbt sind, sind sie nicht für einen Einsatz in transparenten und farblosen Beschichtungen geeignet. Für farbige Beschichtungen ist hinge gen ihre Eigenfarbe förderlichSince carbides, nitrides and borides are mostly intensely colored, they are not for use in transparent and colorless Suitable coatings. For colored coatings is hinge beneficial to their own color
Als Material für die Nanopartikel kommen auch folgende Oxide in
Betracht:
Aluminiumoxid, Antimonoxid, Ceroxid, Siliciumoxid, Titanoxid
und Zirkonoxid.The following oxides can also be used as material for the nanoparticles:
Aluminum oxide, antimony oxide, cerium oxide, silicon oxide, titanium oxide and zirconium oxide.
Dabei ist bevorzugt vorgesehen, daß die Nanopartikel hart, farblos und transparent (bzw. zumindest in der Bindemittelma trix transparent) sind.It is preferably provided that the nanoparticles are hard, colorless and transparent (or at least in the binder size trix transparent).
Eine andere bevorzugte Ausgestaltung der Erfindung sieht vor, daß die beiden widerstreitenden Maßgaben, nämlich einerseits Möglichst dichte Packung der Partikel und andererseits hinrei chende Transmission von härtender Strahlung, so miteinander vereinbart, daß die Partikel möglichst dicht gepackt sind, aber noch hinreichend Durchlässigkeit für die Strahlung gegeben ist, um die erforderliche Härtung in allen Tiefen des Systems zu er reichen.Another preferred embodiment of the invention provides that the two conflicting provisions, namely, on the one hand Pack the particles as densely as possible and on the other hand cover them appropriate transmission of curing radiation, so together agreed that the particles are packed as tightly as possible, but there is still sufficient permeability to the radiation, to achieve the required hardening in all depths of the system pass.
Die Erfindung erreicht, daß nach dem Aushärten der Lack, die Druckfarbe bzw. die Beschichtung mechanische Eigenschaften (insbesondere Abriebfestigkeit, Schlagfestigkeit, Kratzfestig keit und Härte) aufweist, die nicht denen des Lackes, der Druckfarbe bzw. der Beschichtung entsprechen, sondern denen des Partikelmaterials. Dabei läßt sich das Material vor der Strah lungshärtung wie der zugrundeliegende Lack oder die Druckfarbe verarbeiten.The invention achieves that after curing the paint, the Printing ink or the coating mechanical properties (especially abrasion resistance, impact resistance, scratch resistance speed and hardness), which is not that of the paint, the Printing ink or the coating correspond, but that of Particle material. The material can be placed in front of the beam hardening like the underlying paint or printing ink to process.
Die genannten Zusatzstoffe können jeweils wahlweise für sich alleine oder in einer Mischung aus einer oder mehreren Kompo nenten eingesetzt werden.The additives mentioned can each be used individually alone or in a mixture of one or more compos nents are used.
Die Einarbeitung der Nanopartikel in die Lack-Beschichtungsma terialien kann mit bekannten Misch- und Dispergierverfahren durchgeführt werden, insbesondere also dem sog. Dissolver- Verfahren, dem Dreiwalzenstuhl, der Perlsmühle, der Kugelmühle etc. Andererseits kann die Einarbeitung der Nanopartikel in die Beschichtungs-Lacke auch direkt durch Abscheidung nach der Her stellung in einen Flüssigkeitsfilm in einer Trommel oder auf einer Walze erfolgen (sog. VERL-Verfahren [vacuum evaporation onto running liquids]).Incorporation of the nanoparticles into the coating system materials can be mixed and dispersed using known methods be carried out, in particular the so-called dissolver Process, the three-roll mill, the pearl mill, the ball mill etc. On the other hand, the incorporation of the nanoparticles into the Coating varnishes also directly by deposition after the manufacturing process position in a liquid film in a drum or on a roller (so-called VERL process [vacuum evaporation onto running liquids]).
Wegen ihrer sehr geringen Abmessungen liegen die Nanopartikel schon bei geringen Anteilen von wenigen Prozenten durchgängig durch die Schicht gleichmäßig sehr dicht gepackt vor. Außerdem besitzen Nanopartikel eine höhere elastische Verformbarkeit als ihre makroskopischen Analogen. Eine auf die Beschichtungs schicht einwirkende, "zerstörende" Kraft wird daher sehr gut in der Schicht verteilt. Infolge ihrer geringen Größe bieten Nanopartikel für makroskopische Beanspruchungen, wie Kratzen oder Abrieb, keine Angriffspunkte, was ebenfalls die beobacht bare Verbesserung dieser Eigenschaften erklärt.Because of their very small dimensions, the nanoparticles lie consistent even with a small percentage of a few percent evenly packed very densely through the layer. Moreover nanoparticles have a higher elastic deformability than their macroscopic analogues. One on the coating shifting, "destructive" force is therefore very good distributed in the shift. Offer due to their small size Nanoparticles for macroscopic stress, such as scratching or abrasion, no points of attack, which is also observed bare improvement of these properties explained.
Da die Größe der Nanopartikel im Bereich der Wellenlängen des sichtbaren Lichtes liegen, sind mit Nanopartikeln gefüllte Schichten hoch transparent und erlauben Hochglanzbeschichtun gen, die mit makroskopischen (also größeren) Füllstoffen nicht möglich sind.Since the size of the nanoparticles is in the range of the wavelengths of the visible light, are filled with nanoparticles Layers highly transparent and allow high-gloss coating conditions with macroscopic (i.e. larger) fillers possible are.
Hochabriebfeste Systeme der beschriebenen Art können zum Ein
satz komen insbesondere in folgenden Bereichen:
Highly abrasion-resistant systems of the type described can be used in particular in the following areas:
- 1. als Lack oder Beschichtung für Holz und Holzwerkstoffe, vorzugsweise bei Spanplatten, MDF (= mitteldichte Faser platten), Parkett oder Furnier;1. as a lacquer or coating for wood and wood-based materials, preferably with particle board, MDF (= medium density fiber panels), parquet or veneer;
- 2. als Lack, Beschichtung oder Druckfarbe für Kunststoffe, insbesondere Thermoplaste, vorzugsweise Polycarbonat und PVC;2. as a varnish, coating or printing ink for plastics, in particular thermoplastics, preferably polycarbonate and PVC;
- 3. als Lack, Beschichtung oder Druckfarbe für Papier und Karton.3. as a varnish, coating or printing ink for paper and Carton.
Dabei können diese Lacke und Beschichtungen als ein- oder Mehr schichtsystem aufgebracht werden. Einsatzbereiche derart be schichteter Hölzer oder Holzwerkstoffe sind vorzugsweise Möbel, Möbelfronten, Arbeitsplatten, Fußböden, Wandpaneele, Türen oder Treppen.These varnishes and coatings can be used as one or more layer system can be applied. Areas of application such Layered wood or wood-based materials are preferably furniture, Furniture fronts, worktops, floors, wall panels, doors or Stairs.
Einsatzbereiche derart beschichteter Kunststoffe sind vorzugs weise Platten oder Folien für Fußböden, Möbel, Möbelfronten, Schilder, Verglasungen, Profile, Autokarosserieteile, wie z. B. Kotflügel oder Stoßstangen, Koffer und weitere.Areas of application for plastics coated in this way are preferred white sheets or foils for floors, furniture, furniture fronts, Signs, glazing, profiles, car body parts, such as B. Fenders or bumpers, suitcases and more.
Einsatzbereiche derart beschichteter Papiere oder Kartons sind vorzugsweise Dekorpapiere für die Holzwerkstoffindustrie, Ver packungen und weitere. Areas of application for papers or boxes coated in this way are preferably decorative papers for the wood-based panel industry, Ver packs and more.
Die erfindungsgemäß ausgestalteten Lacke und Beschichtungen können auf dem jeweiligen Substrat per Walz-, Gieß-, Spritz- oder Tauchlackierung appliziert werden. Entsprechende Druckfar ben können nach den gängigen und bekannten Druckverfahren wie Tief-, Flexo-, Offset-, Buch- oder Siebdruck aufgebracht wer den.The lacquers and coatings designed according to the invention can be rolled, cast, sprayed on the respective substrate or dip painting can be applied. Corresponding printing color ben can according to the common and known printing processes such as Gravure, flexo, offset, book or screen printing applied the.
Auf die beschriebene Weise lassen sich übliche strahlenhärtbare Systeme (Lacke, Beschichtungen und Druckfarben), die für eine Applikation im jeweiligen Einzelfall bestimmt sind, durch Zu satz der genannten Füllstoffe hinsichtlich ihrer Abriebfestig keit deutlich verbessern.In the manner described, conventional radiation-curable materials can be used Systems (paints, coatings and printing inks) that are used for a Application in the individual case are determined by Zu Set of the fillers mentioned with regard to their abrasion resistance improve significantly.
Des weiteren erfolgt zu den erfindungsgemäß ausgestalteten Sy stemen vorzugsweise eine Zugabe von Hilfsstoffen (wie z. B. Mattierungsmittel, Antiabsetzmittel oder rheologische Zusatz stoffe), Additiven (wie z. B. Wachse, Slipadditive, Entschäumer, Entlüfter, Dispergierhilfsmittel, Benetzungsmittel, Haftverbes serer und andere) oder organischen oder anorganischen farbge benden Pigmenten.Furthermore, the Sy designed according to the invention takes place preferably add additives (such as e.g. Matting agent, anti-settling agent or rheological additive substances), additives (such as waxes, slip additives, defoamers, Deaerators, dispersing agents, wetting agents, adhesive compounds serer and others) or organic or inorganic color pigment.
Die Einarbeitung der harten Füllstoffe in das jeweilige strah lenhärtbare System erfolgt mit gängigen und bekannten Rühr- und Dispergieraggregaten, wie z. B. Flügelrührer, Dissolver, Kugel- oder Perlmühlen, Dreiwalzenstühle.Incorporation of the hard fillers into the respective jet Len curable system is carried out with common and known stirring and Dispersing units, such as. B. paddle stirrer, dissolver, spherical or pearl mills, three-roll mills.
Es können auch Pulverlacke in der beschriebenen Weise durch Zu satzstoffe hinsichtlich ihrer mechanischen Eigenschaften ver bessert werden.It can also powder coatings in the manner described by Zu substitutes regarding their mechanical properties be improved.
Die beiliegende Figur erläutert die dichte Packung der Partikel im Lack, der Druckfarbe oder Beschichtung. Gemäß der Figur ist auf einem Gegenstand 10 aus z. B. Holz oder einem Holzwerkstoff eine Lackschicht 12 aus mit Elektronenstrahl härtbarem Lack aufgetragen. In der Lackschicht 12 sind Partikel 14 aus z. B. Titannitrid in der gezeigten Weise so zugesetzt, daß jedes Par tikel 14 seine benachbarten Partikel 14 im wesentlichen jeweils berührt oder fast berührt, zumindest sind die Abstände zwischen jedem Partikel und seinen benachbarten Partikel im Durchschnitt und im wesentlichen nicht größer als der durchschnittliche Par tikel-Durchmesser. Dies ist so zu verstehen, daß die beiden wi derstreitenden Maßgaben, nämlich einerseits möglichst dichte Packung der Partikel und andererseits hinreichende Transmission von härtender Strahlung, so miteinander vereinbart, daß die Partikel möglichst dicht gepackt sind, aber noch hinreichend Durchlässigkeit für die Strahlung gegeben ist, um die erforder liche Härtung in allen Tiefen des Systems zu erreichen.The attached figure explains the dense packing of the particles in the lacquer, the printing ink or coating. According to the figure is on an object 10 from z. B. wood or a wood material, a lacquer layer 12 is applied from electron beam curable lacquer. In the paint layer 12 particles 14 from z. As titanium nitride in the manner shown added so that each par Tikel 14 its neighboring particles 14 substantially touching each or almost touches, at least the distances between each particle and its neighboring particles are not greater on average and substantially as the average par Tikel -Diameter. This is to be understood in such a way that the two contradicting stipulations, namely packing the particles as densely as possible and adequately transmitting hardening radiation on the one hand, are agreed with one another in such a way that the particles are packed as tightly as possible, but there is still sufficient transparency for the radiation to achieve the required hardening in all depths of the system.
Dies bedeutet, daß der Lack oder das andere strahlenhärtbare Material 16 in der Schicht 12 nur in sehr kleinen Zwischenräu men zwischen den Partikeln verbleibt, so daß die mechanischen Eigenschaften des Systems im wesentlichen durch die mechani schen Eigenschaften der hoch kratzfesten, hoch abriebfesten, hoch schlagfesten und extrem harten Nanopartikel bestimmt ist.This means that the paint or other radiation-curable material 16 remains in the layer 12 only in very small spaces between the particles, so that the mechanical properties of the system are essentially due to the mechanical properties of the highly scratch-resistant, highly abrasion-resistant, highly impact-resistant and extremely hard nanoparticles.
Die so erzeugten Beschichtungen aus insbesondere Lack oder Druckfarbe weisen gegenüber dem Stand der Technik eine Verbes serung hinsichtlich der genannten mechanischen Eigenschaften auf, die im Bereich einer Größenordnung oder sogar noch mehr liegt.The coatings produced in particular from paint or Printing inks have a verb compared to the prior art the mechanical properties mentioned on that are in the order of magnitude or even more lies.
Claims (6)
Carbide, Nitride, Oxide, Boride, Selenide, Telluride, Sul fide, Halogenide und Metalle. 5. Lacquer, printing ink or coating according to one of the preceding claims, characterized in that one or more of the following materials is provided as the material for the solid particles (nanoparticles):
Carbides, nitrides, oxides, borides, selenides, tellurides, sul fides, halides and metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19845496A DE19845496A1 (en) | 1998-10-02 | 1998-10-02 | Radiation-curable varnish, printing ink or coatings with improved hardness, abrasion resistance and scratch resistance contains hard particles, e.g. of aluminum oxide, in the nanometer size range |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19845496A DE19845496A1 (en) | 1998-10-02 | 1998-10-02 | Radiation-curable varnish, printing ink or coatings with improved hardness, abrasion resistance and scratch resistance contains hard particles, e.g. of aluminum oxide, in the nanometer size range |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19845496A1 true DE19845496A1 (en) | 2000-04-06 |
Family
ID=7883239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19845496A Withdrawn DE19845496A1 (en) | 1998-10-02 | 1998-10-02 | Radiation-curable varnish, printing ink or coatings with improved hardness, abrasion resistance and scratch resistance contains hard particles, e.g. of aluminum oxide, in the nanometer size range |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19845496A1 (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001047726A1 (en) * | 1999-12-23 | 2001-07-05 | Perstorp Flooring Ab | A process for achieving a wear resistant translucent surface on surface elements |
| US6291078B1 (en) | 1997-10-22 | 2001-09-18 | Mannington Mills, Inc. | Surface coverings containing aluminum oxide |
| WO2002028665A1 (en) * | 2000-10-03 | 2002-04-11 | Pergo Ab | A process for the manufacture of surface elements |
| WO2002081579A2 (en) * | 2000-12-08 | 2002-10-17 | Ppg Industries Ohio, Inc. | Coating compositions providing improved mar and scratch resistance and methods of using the same |
| US6467897B1 (en) | 2001-01-08 | 2002-10-22 | 3M Innovative Properties Company | Energy curable inks and other compositions incorporating surface modified, nanometer-sized particles |
| US6555216B2 (en) | 1997-02-20 | 2003-04-29 | Mannington Mill, Inc. | Contrasting gloss surface coverings optionally containing dispersed wear-resistant particles and methods of making the same |
| WO2003070840A1 (en) * | 2002-02-20 | 2003-08-28 | Ppg Industries Ohio, Inc. | Curable film-forming composition exhibiting improved impact strength and chip resistance |
| WO2004040627A3 (en) * | 2002-10-30 | 2005-02-10 | Hewlett Packard Co | Electronic components |
| US7101616B2 (en) | 2001-09-11 | 2006-09-05 | 3M Innovative Properties Company | Smudge resistant nanocomposite hardcoats and methods for making same |
| US7255040B2 (en) | 2003-12-11 | 2007-08-14 | Pergo (Europe) Ab | Process for the manufacturing of panels having a decorative surface |
| WO2009152872A1 (en) | 2008-06-20 | 2009-12-23 | Dieter Ostermann | Sheathing element |
| US7816434B2 (en) | 2001-09-11 | 2010-10-19 | Henkel Kommanditgesellschaft Auf Aktien | UV-curing anti-fingerprinting coatings |
| US7829176B2 (en) | 2001-12-07 | 2010-11-09 | Pergo AG | Structured boards with matched surface |
| US8258225B2 (en) | 2000-12-08 | 2012-09-04 | Ppg Industries Ohio, Inc | Coating compositions providing improved mar and scratch resistance and methods of using the same |
| CN103522719A (en) * | 2013-10-25 | 2014-01-22 | 黑龙江华信家具有限公司 | Manufacturing method of high-strength scratch-resistant veneer |
-
1998
- 1998-10-02 DE DE19845496A patent/DE19845496A1/en not_active Withdrawn
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7384697B2 (en) | 1997-02-20 | 2008-06-10 | Mannington Mills, Inc. | Surface coverings containing aluminum oxide |
| US6555216B2 (en) | 1997-02-20 | 2003-04-29 | Mannington Mill, Inc. | Contrasting gloss surface coverings optionally containing dispersed wear-resistant particles and methods of making the same |
| US6291078B1 (en) | 1997-10-22 | 2001-09-18 | Mannington Mills, Inc. | Surface coverings containing aluminum oxide |
| US6685993B1 (en) | 1999-12-23 | 2004-02-03 | Pergo (Europe) Ab | Process for achieving a wear resistant translucent surface on surface elements |
| US6991830B1 (en) | 1999-12-23 | 2006-01-31 | Pergo (Europe) Ab | Process for the manufacturing of surface elements with a structured upper surface |
| US10464339B2 (en) | 1999-12-23 | 2019-11-05 | Pergo (Europe) Ab | Process for the manufacturing of surface elements |
| US9656476B2 (en) | 1999-12-23 | 2017-05-23 | Pergo (Europe) Ab | Process for the manufacturing of surface elements |
| WO2001047725A1 (en) * | 1999-12-23 | 2001-07-05 | Perstorp Flooring Ab | A process for the manufacturing of surface elements with a structured upper surface |
| WO2001047726A1 (en) * | 1999-12-23 | 2001-07-05 | Perstorp Flooring Ab | A process for achieving a wear resistant translucent surface on surface elements |
| US9636922B2 (en) | 1999-12-23 | 2017-05-02 | Pergo (Europe) Ab | Process for the manufacturing of surface elements |
| US8944543B2 (en) | 1999-12-23 | 2015-02-03 | Pergo (Europe) Ab | Process for the manufacturing of surface elements |
| US9636923B2 (en) | 1999-12-23 | 2017-05-02 | Pergo (Europe) Ab | Process for the manufacturing of surface elements |
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