Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
  • B44C5/00—Processes for producing special ornamental bodies
  • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
  • B44C5/0469—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
  • B44C5/0476—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper with abrasion resistant properties
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/256—Heavy metal or aluminum or compound thereof
  • Y10T428/257—Iron oxide or aluminum oxide
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
  • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

• Laminate is a multi-layer, thermosetting plastic, which is produced by pressing and gluing at least two layers of the same or different materials. Combination can complement the properties of the individual materials.
• laminates are approx. 0.5 to 1.2 mm thick and are usually applied to a carrier material (eg HDF or chipboard) in further processing with a special adhesive.
• the most common type of application for such laminate coatings is the laminate floor and kitchen countertops. It is also possible to easily produce laminates with thicknesses of 2 to 20 cm. Such referred to as compact laminates products are self-supporting with increasing thickness and find z. B. in the interior but also in outdoor use as facade or balcony cladding use.
• Laminate has many positive characteristics: the surface is dense, impact and abrasion resistant. It can be provided with various structures and can withstand high temperatures for a short time without being damaged. The surface is easy to care for and clean, heat and light resistant and odorless and insensitive to alcohol or organic solvents and the effect of water vapor.
• Laminate flooring is the combination of a HPL (high pressure laminate) or CPL (continuous pressure laminate) layer, which is adhered to a carrier material (usually an HDF board).
• the resins used are melamine-formaldehyde, phenol-formaldehyde, urea-formaldehyde resins and combinations of these substances.
• the core consists of several phenol resin impregnated papers, above is the melamine resin impregnated decorative layer.
• a so-called overlay is pressed, which consists of two transparent melamine-impregnated papers, between which a corundum layer of coarse corundum (> 20 microns) may be included for reasons of stability.
• WO 02/24446 describes laminates containing metal oxide particles to improve rub resistance. These metal oxide particles, which are prepared by the sol-gel method, have a particle diameter of 5 to 70 microns and are therefore not nanoparticles.
• the invention relates to laminates, preferably a laminate overlay containing metal oxide nanoparticles with a high proportion of ⁇ -aluminum oxide.
• Preferred nanoparticles which are used according to the invention are particles having an average particle size in the range from 1 nm to 900 nm, preferably 1 to 200 nm, and consist of oxides of elements of main group 3, in particular aluminum.
• the proportion of ⁇ -alumina is preferably in Range 50-100%.
• Al 2 O 3 contain the metal oxide nanoparticles in addition to the ⁇ -Al 2 O 3 further oxides as described below. It may also be advantageous to mix these metal oxide nanoparticles with aluminum oxide whose fineness is in the ⁇ m range, preferably ⁇ 10 ⁇ m.
• the nanoparticles are prepared by deagglomeration of larger agglomerates containing or consisting of these nanoparticles in the presence of a dispersant using suitable stabilizers.
• agglomerates are known per se and can be prepared, for example, by the methods described below:
• Nanoparticles containing coating compositions are known, wherein the nanoparticles are prepared by sol-gel technique by hydrolytic (co) condensation of tetraethoxysilane (TEOS) with other metal alkoxides in the absence of organic and / or inorganic binders.
• TEOS tetraethoxysilane
• sol-gel synthesis can also be carried out in the medium. Radiation-curing formulations are preferably used.
• all materials produced by sol-gel process are characterized by low solids contents of inorganic and organic substance, by increased amounts of the condensation product (usually alcohols), by the presence of water and by limited storage stability.
• Nanoscale surface-modified particles (Degussa Aerosil ® R 7200), which are obtained by condensation of metal oxides with silanes in the absence of a binder and hence in the absence of strong shear forces, as they act in viscous media at stirring speeds of ⁇ 10 m / s. These aerosils therefore have larger particles than the raw materials used, their opacity is significantly higher and their effectiveness is less than the effect of in WO 00/22052 described particles and the varnishes produced therefrom.
• the desired molecules are obtained from chemical reactions of a Precursorgases or by rapid cooling of a supersaturated gas.
• the formation of the particles occurs either through collision or the constant equilibrium evaporation and condensation of molecular clusters.
• the newly formed particles grow by further collision with product molecules (condensation) and / or Particles (coagulation). If the coagulation rate is greater than that of the new growth or growth, agglomerates of spherical primary particles are formed.
• Flame reactors represent a production variant based on this principle. Nanoparticles are formed here by the decomposition of precursor molecules in the flame at 1500 ° C.-2500 ° C. As examples, the oxidations of TiCl 4 ; SICl 4 and Si 2 O (CH 3 ) 6 are mentioned in methane / O 2 flames leading to TiO 2 and SiO 2 particles. When using AlCl 3 so far only the corresponding clay could be produced. Flame reactors are now used industrially for the synthesis of submicroparticles such as carbon black, pigment TiO 2 , silica and alumina.
• Small particles can also be formed from drops with the help of centrifugal force, compressed air, sound, ultrasound and other methods.
• the drops are then converted into powder by direct pyrolysis or by in situ reactions with other gases.
• the spray and freeze drying should be mentioned.
• precursor drops are transported through a high temperature field (flame, oven), resulting in rapid evaporation of the volatile component or initiating the decomposition reaction to the desired product.
• the desired particles are collected in filters.
• the production of BaTiO 3 from an aqueous solution of barium acetate and titanium lactate can be mentioned here.
• corundum at low temperature Another way to produce corundum at low temperature is the conversion of aluminum chlorohydrate. This is also with Seed germs, preferably of fine corundum or hematite, added. To avoid crystal growth, the samples must be calcined at temperatures of around 700 ° C to a maximum of 900 ° C. The duration of the calcination is at least four hours. Disadvantage of this method is therefore the large amount of time and the residual amounts of chlorine in the alumina. The method has been described in detail in Ber. DKG 74 (1997) no. 11/12, p. 719-722 ,
• the nanoparticles must be released. This is preferably done by grinding or by treatment with ultrasound. According to the invention, this deagglomeration is carried out in the presence of a solvent and a coating agent or stabilizer for modifying the surface, which is a silane or siloxane, during the milling process, saturating the resulting active and reactive surfaces by a chemical reaction or physical attachment and thus reagglomeration prevented.
• a solvent and a coating agent or stabilizer for modifying the surface which is a silane or siloxane
• the nano-oxide remains as a small particle. It is also possible to add the coating agent for the modification of the surface after deagglomeration.
• the starting point here is aluminum chlorohydrate, which has the formula Al 2 (OH) x Cl y , where x is a number from 2.5 to 5.5 and y is a number from 3.5 to 0.5 and the sum of x and y always 6.
• This aluminum chlorohydrate is mixed with crystallization seeds as an aqueous solution, then dried and then subjected to a thermal treatment (calcination).
• nuclei cause a lowering of the temperature for the formation of the ⁇ -modification in the subsequent thermal treatment.
• germs prefers very fine disperse corundum, diaspore or hematite.
• This starting solution may additionally contain oxide formers to produce mixed oxides containing an oxide MeO.
• oxide formers to produce mixed oxides containing an oxide MeO.
• the chlorides of the elements of the I. and II. Main group of the Periodic Table and all other metals which form alumina metal aluminates of the spinel type, such as.
• As zinc, magnesium, cobalt, copper, but also other soluble or dispersible salts such as oxides, oxychlorides, carbonates or sulfates.
• compounds can be added as oxide formers that give oxides of rare earths (lanthanides) in the calcination, such as.
• oxide formers which yield zikon or hafnium oxide or mixtures of oxide formers which give rare earth oxides together with an oxide former for MgO.
• oxide formers in addition to the corundum lattice, further crystal lattices are formed, for example garnet, spinel or magnetoplumbite lattices. In this way, the corundum mesh is reinforced and one achieves better mechanical properties.
• the amount of oxide generator is such that the finished nanoparticles preferably contain 0.01 to 50 wt .-% of the oxide Me.
• the oxides may be present as a separate phase in addition to the alumina or with this real mixed oxides such.
• spinels, etc. form.
• nanoparticles, nanocorundum and “mixed oxides” in the context of this invention should be understood to mean that both pure corundum and mixed corundum or real mixed oxides such. B. the spinels are meant.
• This suspension of aluminum chlorohydrate, germs and optionally oxide formers is then evaporated to dryness and subjected to a thermal treatment (calcination).
• This calcination takes place in this suitable devices, for example in push-through, chamber, tube, rotary kiln or microwave ovens or in a fluidized bed reactor.
• the temperature for the calcination should not exceed 1100 ° C.
• the lower temperature limit depends on the desired yield of nanocrystalline mixed oxide, the desired residual chlorine content and the content of germs.
• the formation of the nanoparticles begins at about 500 ° C, but to keep the chlorine content low and the yield of nanoparticles high, but you will work preferably at 700 to 1100 ° C, especially at 1000 to 1100 ° C.
• the nanoparticles must be released from these agglomerates containing or entirely consisting of the desired nanoparticles in the form of crystallites. This is preferably done by grinding or by treatment with ultrasound.
• the agglomerates are preferably comminuted by wet grinding in a solvent, for example in an attritor mill, bead mill or stirred mill. This gives nanoparticles which have a crystallite size of less than 1 ⁇ m, preferably less than 0.2 ⁇ m. For example, after six hours of grinding, a suspension is obtained of nanoparticles with a d90 value of approximately 90 nm.
• a suspension is obtained of nanoparticles with a d90 value of approximately 90 nm.
• Another possibility of deagglomeration is sonication. It may also be advantageous to deagglomerate the resulting agglomerates in a dissolver or similar mixing equipment used in the coating industry.
• coating agents also called stabilizers, ie silanes or siloxanes.
• deagglomeration can be carried out in the presence of the coating agent, for example by adding the coating agent to the mill during milling.
• a second possibility consists of first destroying the agglomerates of the nanoparticles and then treating the nanoparticles, preferably in the form of a suspension in a solvent, with the coating agent.
• Suitable solvents for deagglomeration are both water and conventional solvents, preferably those which are also used in the paint industry, such as, for example, C 1 -C 4 -alcohols, in particular methanol, ethanol or isopropanol, acetone, tetrahydrofuran, butyl acetate.
• an inorganic or organic acid for example HCl, HNO 3 , formic acid or acetic acid, should be added in order to stabilize the nanoparticles formed in the aqueous suspension.
• the amount of acid may be 0.1 to 5 wt .-%, based on the nanoparticles.
• the nanoparticles in which the acidic or alkaline suspensions can also be coated with further coating agents, preferably with silane or siloxane, if a modification of the particle surface by such coating agents, also called stabilizer, is desired.
• Suitable coating agents are preferably silanes or siloxanes or mixtures thereof.
• suitable coating agents are all substances which can bind physically to the surface of the mixed oxides (adsorption) or which can bond to form a chemical bond to the surface of the mixed oxide particles. Since the surface of the mixed oxide particles is hydrophilic and free hydroxy groups are available, suitable coating agents are alcohols, compounds having amino, hydroxyl, carbonyl, carboxyl or mercapto functions, silanes or siloxanes. Examples of such coating compositions are polyvinyl alcohol, mono-, di- and tricarboxylic acids, amino acids, amines, waxes, surfactants, polymers such as. As polyacrylates, hydroxycarboxylic acids, organosilanes and organosiloxanes.
• ⁇ -OH groups are also the corresponding difunctional compounds with epoxy, isocyanato, vinyl, allyl and di (meth) acryloyl used, for.
• the coating compositions in particular the silanes or siloxanes, are preferably added in molar ratios of nanoparticles to silane of 1: 1 to 500: 1.
• the amount of solvent in the deagglomeration is generally 50 to 90 wt .-%, based on the total amount of nanoparticles and solvent.
• the deagglomeration by grinding and simultaneous modification with the coating agent is preferably carried out at temperatures of 20 to 150 ° C, more preferably at 20 to 90 ° C.
• the suspension is subsequently separated from the grinding beads.
• the suspension can be heated to complete the reaction for up to 30 hours. Finally, the solvent is distilled off and the remaining residue is dried. It may also be advantageous to use the optionally modified mixed oxide nanoparticles in the Leave solvent and use the dispersion for other applications.
• the nanoparticles thus produced, optionally modified on the surface are converted into coating compositions such as, for example, formaldehyde melamine; Urea formaldehyde; Formaldehyde-phenol and combinations of these resins incorporated as they are common in the production of laminate boards.
• This addition of the nanoparticles in the production of laminates is preferably carried out such that there is a dispersion of the nanoparticles in the aqueous phase to the impregnating resins for the production of the laminates and then the laminates finished in a conventional manner.
• nanoparticles are incorporated in the so-called overlay, especially in the final overlay of laminate plates.
• the coating compositions of the invention may also contain other additives, such as are usual in laminate boards, for example, reactive diluents, solvents and co-solvents, waxes, matting agents, lubricants, defoamers, deaerators, leveling agents, thixotropic agents, thickeners, inorganic and organic pigments, fillers, adhesion promoters, Corrosion inhibitors, anticorrosive pigments, UV stabilizers, HALS compounds, free-radical scavengers, antistatics, wetting agents and dispersants and / or the catalysts required depending on the type of curing, cocatalysts, initiators, free-radical initiators, photoinitiators, Photosensitizers, etc.
• additives such as are usual in laminate boards, for example, reactive diluents, solvents and co-solvents, waxes, matting agents, lubricants, defoamers, deaerators, leveling agents,
• additives also include polyethylene glycol and other water retention agents, PE waxes, PTFE waxes, PP waxes, amide waxes, FT paraffins, montan waxes, grafted waxes, natural waxes, macro- and microcrystalline paraffins, polar polyolefin waxes, sorbitan esters, Polyamides, polyolefins, PTFE, wetting agents or silicates in question.
• a 50% aqueous solution of aluminum chlorohydrate was added with magnesium chloride so that after calcination the ratio of alumina to magnesium oxide was 99.5: 0.5%.
• 2% of nuclei were added to the solution to a suspension of fines. After the solution has been homogenized by stirring, the drying is carried out in a rotary evaporator. The solid aluminum chlorohydrate magnesium chloride mixture was crushed in a mortar to form a coarse powder.
• the powder was calcined in a rotary kiln at 1050 ° C.
• the contact time in the hot zone was a maximum of 5 min.
• a white powder was obtained whose grain distribution corresponded to the feed material.
• An X-ray structure analysis shows that predominantly ⁇ -alumina is present.
• the images of the SEM image taken showed crystallites in the range 10 - 80 nm (estimate from SEM image), which are present as agglomerates.
• the residual chlorine content was only a few ppm.
• this magnesium oxide-doped corundum powder were suspended in 100 g of water.
• the suspension was 1 g of ammonium acrylate polymer (Dispex N ®, Ciba) was added and a vertical stirred ball mill from. Netzsch (type PE 075).
• the grinding beads used consisted of zirconium oxide (stabilized with yttrium) and had a size of 0.3 mm. After three hours, the suspension was separated from the milling beads.
• a 50% aqueous solution of aluminum chlorohydrate was added with magnesium chloride so that after calcination the ratio of alumina to magnesium oxide was 99.5: 0.5%.
• 2% of nuclei were added to the solution to a suspension of fines. After the solution has been homogenized by stirring, the drying is carried out in a rotary evaporator. The solid aluminum chlorohydrate magnesium chloride mixture was crushed in a mortar to form a coarse powder.
• the powder was calcined in a rotary kiln at 1050 ° C.
• the contact time in the hot zone was a maximum of 5 min.
• a white powder was obtained whose grain distribution corresponded to the feed material.
• An X-ray structure analysis shows that predominantly ⁇ -alumina is present.
• the images of the SEM image taken showed crystallites in the range 10 - 80 nm (estimate from SEM image), which are present as agglomerates.
• the residual chlorine content was only a few ppm.
• this magnesium oxide-doped corundum powder were suspended in 100 g of water.
• 1 g of ammonium acrylate polymer (Dispex N, Ciba) and 0.5 g of trimethoxyaminopropylsilane (Dynasilan Ammo) were added to the suspension and fed to a vertical stirred ball mill from Netzsch (type PE 075).
• the grinding beads used consisted of zirconium oxide (stabilized with yttrium) and had a size of 0.3 mm. After three hours, the suspension was separated from the milling beads.
• a 50% aqueous solution of aluminum chlorohydrate was added with zinc chloride such that after calcination the ratio of alumina to zinc oxide is 50:50. After the solution has been homogenized by stirring, the drying is carried out in a rotary evaporator. The solid aluminum chlorohydrate zinc chloride mixture was crushed in a mortar to form a coarse powder.
• the powder was calcined in a rotary kiln at 850 ° C.
• the contact time in the hot zone was a maximum of 5 min.
• a white powder was obtained whose grain distribution corresponded to the feed material.
• the powder was calcined in a muffle furnace at 1100 ° C.
• the contact time was about 30 minutes.
• a white powder was obtained whose grain distribution corresponded to the feed material.
• the coated nanoparticles from Examples 1 to 3 were mixed with impregnating resins (dissolvers) and the mixtures were used to coat printed decorative paper.
• the melamine resin Madurit ® MW 550 (Ineos Melamines) was used for the tests. After the impregnation had been dried, the lamination of the decorative papers on support plates was carried out in a hot press at 150 ° C. and a pressure of 200 bar. The pressing time was 4 min.
• the finished pieces of laminate (40 cm * 40 cm) were checked for scratch resistance using a diamond stylus (Eriksentest).
• the scratch resistance is the better the higher the contact force of the diamond stylus.

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• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

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• 2007
  • 2007-02-19 DE DE102007008468A patent/DE102007008468A1/de not_active Withdrawn
• 2008
  • 2008-02-13 WO PCT/EP2008/001082 patent/WO2008101621A1/de active Application Filing
  • 2008-02-13 US US12/527,061 patent/US20100086770A1/en not_active Abandoned
  • 2008-02-13 ES ES08707694T patent/ES2362157T3/es active Active
  • 2008-02-13 EP EP08707694A patent/EP2129519B1/de not_active Not-in-force
  • 2008-02-13 CN CN200880003329A patent/CN101626886A/zh active Pending
  • 2008-02-13 JP JP2009549796A patent/JP2010519068A/ja not_active Withdrawn
  • 2008-02-13 AT AT08707694T patent/ATE509763T1/de active
  • 2008-02-13 PT PT08707694T patent/PT2129519E/pt unknown

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