EP2794211B1 - Lignocellulosematerialien mit lignocellulosefasern in den äusseren schichten und geschäumtem kunststoff partikel im kern, sowie verfahren und verwendung - Google Patents
Lignocellulosematerialien mit lignocellulosefasern in den äusseren schichten und geschäumtem kunststoff partikel im kern, sowie verfahren und verwendung Download PDFInfo
- Publication number
- EP2794211B1 EP2794211B1 EP12813353.5A EP12813353A EP2794211B1 EP 2794211 B1 EP2794211 B1 EP 2794211B1 EP 12813353 A EP12813353 A EP 12813353A EP 2794211 B1 EP2794211 B1 EP 2794211B1
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- EP
- European Patent Office
- Prior art keywords
- weight
- particles
- core
- lignocellulose
- wood
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/005—Manufacture of substantially flat articles, e.g. boards, from particles or fibres and foam
Definitions
- the present invention relates to lignocellulosic materials having a core and two outer layers, the core comprising expanded plastics particles and the outer layers comprising lignocellulosic fibers.
- the present invention furthermore relates to a process for producing a lignocellulosic material and to the use of such a material.
- CH-A-370 229 discloses compression moldings which possess both light weight and compressive strength and which consist of wood chips or wood fibers, a binder, and a porous, foamable or partly foamable, plastic that serves as filler.
- DE-U-20 2007 017 713 discloses weight-reduced chipboard panels through combination of wood chips and evenly distributed foamed polystyrene beads in the middle ply of the panel.
- WO-A-2008/046890 discloses a lignocellulosic material having a core and two outer layers in accordance with the preamble of claims 1 and 2, more especially it discloses lightweight, single-ply and multi-ply wood based materials which comprise wood particles, a filler of polystyrene and/or styrene copolymer having a bulk density of 10 to 100 kg/m 3 , and binder.
- the filler is advantageously evenly distributed within the wood based material.
- the wood based materials are produced from wood veneers, from wood chips or from wood fibers, more particularly from wood chips and and wood fibers.
- a disadvantage of these materials is that an improvement in the properties for a given panel density is achievable only with an increase in the amount of glue and/or the amount of polymer and hence with an increase in the costs.
- WO 2008/046890 discloses lightwood-based materials containing 30-92.5% by wt. of wood particles, in relation to the wood-based material.
- the wood particles have an average density between 0.4-0.85 g/cm 3 , 2.5-20% by wt. of polystyrene and/or styrene copolymer as filling material, in relation to the wood-based material.
- US 2011/217562 discloses a process for the production of a lignocellulose-containing material, in which, based in each case on the lignocellulose-containing material:
- US 2011/039090 discloses a lightwood-containing material having an average density in the range from 200 to 600 kg/m 3 , comprising, based in each case on the wood-containing material:
- a lignocellulosic material having a core and two outer layers, consisting in the core of
- the statement of the percent by weight of components A, B, C, D, E, F and G relates to the dry weight of the component in question as a proportion of the overall dry weight.
- the sum total of the percent by weight figures for components A, B, C and D is 100% by weight.
- the sum total of components E, F and G likewise makes 100% by weight.
- not only the outer layers but also the core comprise water, which is not taken into account in the weight figures.
- the water may originate from the residual moisture present in the lignocellulose particles, from the binder, from additionally added water, for dilution of the binders or for moistening of the outer layers, for example, or from the additives, such as aqueous curing agent solutions or aqueous paraffin emulsions, for example, or else from the expanded plastics particles when they are foamed, for example, using steam.
- the water content of the core and of the outer layers can be up to 20% by weight, i.e., 0% to 20% by weight, preferably 2% to 15% by weight, more preferably 4% to 10% by weight, based on 100% by weight overall dry weight.
- the ratio of the overall dry mass of the core to the overall dry mass of the outer layers is generally 100:1 and 0.25:1, preferably 10:1 to 0.5:1, more preferably 6:1 to 0.75:1, more particularly 4:1 to 1:1.
- lignocellulosic materials (lignocellulose materials) of the invention can be produced as follows:
- the components for the core and the components for the outer layers are mixed generally separately from one another.
- the lignocellulose particles A may be mixed with the components B, C and D and/or with the component constituents comprised therein (i.e., two or more constituents, such as substances or compounds, for example, from the group of one component) in any desired order.
- Components A, B, C an D may in each case be composed of one, two (A1, A2 or B1, B2, or C1, C2 or D1, D2) or a plurality of component constituents (A1, A2, A3,..., or B1, B2, B3,..., C1, C2, C3,..., or D1, D2, D3,).
- these component constituents may be added either as a mixture or separately from one another. In the case of separate addition, these component constituents may be added directly after one another or else at different points in time not following directly on from one another. In the event, for example, that component C is composed of two constituents C1 and C2, this means that C2 is added immediately after C1 or C1 is added immediately after C2, or that one or more other components or component constituents, component B for example, are added between the addition of C1 and C2. It is also possible for components and/or component constituents to be premixed with other components or component constituents before being added. For example, an additive constituent D1 may be added to the binder C or to the binder constituent C1 before this mixture is then added to the actual mixture.
- the expanded plastics particles B are added to the lignocellulose particles A, and this mixture is thereafter admixed with a binder C or with two or more binder constituents C1, C2, etc. Where two or more binder constituents are used, they are preferably added separately from one another.
- the additives D are preferably partially mixed with the binder C or with a binder constituent (i.e., a plurality of constituents, such as substances or compounds, for example, from the group of the component) and then added.
- the lignocellulose fibers E are mixed with the components F and G and/or with the component constituents present therein (i.e., a plurality of constituents, such as substances or compounds, for example, from the group of one component) in any desired order.
- the component constituents present therein i.e., a plurality of constituents, such as substances or compounds, for example, from the group of one component
- the two outer layers it is possible to use either the same mixture or two different mixtures, preferably the same mixture.
- these constituents can be added either as a mixture or separately from one another. In that case, these component constituents can be added directly after one another or else at different points in time not following directly on from one another.
- the additives G are preferably partially mixed with the binder F or a binder constituent and then added.
- the resulting mixtures A, B, C, D and E, F, G are layered one on top another and compressed by a customary process, at elevated temperature, to give a lignocellulosic molding.
- a mat is produced on a support, said mat being composed of these mixtures in the order E, F, G/A, B, C, D/E, F, G ("sandwich construction").
- This mat is compressed customarily at temperatures from 80 to 300°C, preferably 120 to 280°C, more preferably 150 to 250°C, and at pressures from 1 to 50 bar, preferably 3 to 40 bar, more preferably 5 to 30 bar, to form moldings.
- the mat is subjected to cold precompaction ahead of this hotpressing.
- Compression may take place by any of the methods known to the skilled person (see examples in “ Taschenbuch der Spanplattentechnik", H.-J. Deppe, K. Ernst, 4th edn., 2000, DRW - Verlag Weinbrenner, Leinfelden Echterdingen, pages 232 to 254 , and " MDF- Friedrich Why Faserplatten” H.-J. Deppe, K. Ernst, 1996, DRW- Verlag Weinbrenner, Leinfelden-Echterdingen, pages 93 to 104 ).
- These methods use discontinuous pressing techniques, on single-stage or multistage presses, for example, or continuous pressing techniques, on double-belt presses, for example.
- the lignocellulose materials of the invention generally have an average density of 300 to 600 kg/m 3 , preferably 350 to 590 kg/m 3 , more preferably 400 to 570 kg/m 3 , more particularly 450 to 550 kg/m 3 .
- the lignocellulose particles of component A are present in the lignocellulosic materials of the core in amounts from 30% to 98% by weight, preferably 50% to 95% by weight, more preferably 70% to 90% by weight, and their base material may be any desired wood variety or mixtures thereof, examples being spruce, beech, pine, larch, lime, poplar, eucalyptus, ash, chestnut and fir wood or mixtures thereof, preferably spruce, beech or mixtures thereof, more particularly spruce, and may comprise, for example, wood parts such as wood laths, wood strips, wood chips, wood fibers, wood dust or mixtures thereof, preferably wood chips, wood fibers, wood dust and mixtures thereof, more preferably wood chips, wood fibers or mixtures thereof - of the kind used for producing chipboard, MDF (medium-density fiberboard) and HDF (high-density fiberboard) panels.
- MDF medium-density fiberboard
- HDF high-density fiber
- the lignocellulose particles may also come from woody plants such as flax, hemp, cereals or other annual plants, preferably from flax or hemp. Particular preference is given to using wood chips of the kind used for producing chipboard. If mixtures of different lignocellulose particles are used, for example mixtures of wood chips and wood fibers, or of wood chips and wood dust, then the proportion of wood chips is preferably at least 75% by weight, i.e., 75% to 100% by weight, more preferably at least 90% by weight, i.e., 90% to 100% by weight.
- the average density of component A is generally 0.4 to 0.85 g/cm 3 , preferably 0.4 to 0.75 g/cm 3 , more particularly 0.4 to 0.6 g/cm 3 .
- Starting materials for lignocellulose particles are customarily lumber from forestry thinning, forest residuals, residual industrial lumber and used lumber, and also plants containing wood fiber. Processing to the desired lignocellulosic particles, wood particles such as wood chips or wood fibers for example, may take place in accordance with known methods (e.g., M. Dunky, P. Niemz, Holzwerkstoffe und Leime, pages 91 to 156, Springer Verlag Heidelberg, 2002 ).
- the lignocellulose fibres of component E are present in amounts of from 70% to 99% by weight, preferably 75% to 97% by weight, more preferably 80% to 95% by weight consisting of at least 75% by weight, i.e., 75% to 100% by weight, of lignocellulose fibers, preferably at least 85% by weight, i.e., 85% to 100% by weight, more preferably at least 95% by weight, i.e., 95% to 100% by weight. Most preferably, exclusively, i.e., 100% by weight of, lignocellulose fibers are used.
- Raw materials used may be woods from all of the wood varieties or woody plants listed under component A.
- the fibers can be produced by grinding operations, after a hydrothermal pretreatment, for example.
- Fiberizing processes are known from Dunky, Niemz, Holzwerkstoffe und Leime, Technologie und accountable perceptionen, Springer, 2002, pages 135 to 148 , for example.
- the average density of component E is generally 0.3 to 0.85 g/cm 3 , preferably 0.35 to 0.8 g/cm 3 , more particularly 0.4 to 0.75 g/cm 3 .
- Component A may comprise the customary small amounts of water, from 0% to 10% by weight, preferably 0.5% to 8% by weight, more preferably 1 % to 5% by weight (in a customary low range of fluctuation of 0% to 0.5% by weight, preferably 0% to 0.4% by weight, more preferably 0% to 0.3% by weight).
- This quantity figure is based on 100% by weight of absolutely dry wood substance, and describes the water content of component A after the drying (by customary methods known to the skilled person) immediately prior to mixing with the first component or with the first component constituent or with the first mixture selected from B, C and D.
- component E may comprise small amounts of water from 0% to 10% by weight, preferably 0.5% to 8% by weight, more preferably 1 % to 5% by weight (in a customary low range of fluctuation of 0% to 0.5% by weight, preferably 0% to 0.5% by weight, more preferably 0% to 0.3% by weight).
- This quantity figure is based on 100% by weight of absolutely dry wood substance, and describes the water content of component E after the drying (by customary methods known to the skilled person) immediately prior to mixing with the first component or component constituent or mixture selected from F and G.
- component E may comprise water at from 30% to 200% by weight, preferably 40% to 150% by weight, more preferably 50% to 120% by weight (in a range of fluctuation of 0% to 20% by weight, preferably 0% to 10% by weight, more preferably 0% to 5% by weight).
- This quantity figure is based on 100% by weight of absolutely dry wood substance, and describes the water content of component E immediately prior to mixing with the first component or with the first component constituent or with the first mixture selected from F and G.
- drying takes place according to methods known to the skilled person; preferably, this drying takes place after the addition of all of the components.
- Suitable expanded plastics particles include expanded plastics particles, preferably expanded thermoplastics particles, having a bulk density from 10 to 150 kg/m 3 , preferably 30 to 130 kg/m 3 , more preferably 35 to 110 kg/m 3 , more particularly 40 to 100 kg/m 3 (determined by weighing a defined volume filled with the bulk material).
- Expanded plastics particles B are used generally in the form of spheres or beads having an average diameter of 0.01 to 50 mm, preferably 0.25 to 10 mm, more preferably 0.4 to 8.5 mm, more particularly 0.4 to 7 mm.
- the spheres have a small surface area per unit volume, in the form of a spherical or elliptical particle, for example, and advantageously are closed-cell spheres.
- the open-cell proportion according to DIN ISO 4590 is generally not more than 30%, i.e., 0% to 30%, preferably 1 % to 25%, more preferably 5% to 15%.
- Suitable polymers on which the expandable or expanded plastics particles are based are generally all known polymers or mixtures thereof, preferably thermoplastic polymers or mixtures thereof, which can be foamed.
- examples of highly suitable such polymers include polyketones, polysulfones, polyoxymethylene, PVC (rigid and flexible), polycarbonates, polyisocyanurates, polycarbodiimides, polyacrylimides and polymethacrylimides, polyamides, polyurethanes, aminoplast resins and phenolic resins, styrene homopolymers (also referred to below as "polystyrene” or "styrene polymer”), styrene copolymers, C 2 -C 10 olefin homopolymers, C 2 -C 10 olefin copolymers, and polyesters.
- the 1-alkenes examples being ethylene, propylene, 1-butene, 1-hex
- the polymers may additionally be admixed with the customary additives forming a basis for the expandable or expanded plastics particles B), examples being UV stabilizers, antioxidants, coating materials, hydrophobing agents, nucleators, plasticizers, flame retardants, soluble and insoluble, organic and/or inorganic dyes, pigments, and athermanous particles, such as carbon black, graphite or aluminum powder, together or spatially separate, as adjuvants.
- the customary additives forming a basis for the expandable or expanded plastics particles B
- examples being UV stabilizers, antioxidants, coating materials, hydrophobing agents, nucleators, plasticizers, flame retardants, soluble and insoluble, organic and/or inorganic dyes, pigments, and athermanous particles, such as carbon black, graphite or aluminum powder, together or spatially separate, as adjuvants.
- Component B may customarily be obtained as follows:
- Suitable polymers using an expansion-capable medium (also called “blowing agent”) or comprising an expansion-capable medium, can be expanded by exposure to microwave energy, thermal energy, hot air, preferably steam, and/or to a change in pressure (this expansion often also being referred to as "foaming") ( Kuntstoff Handbuch 1996, volume 4 , " Polystyrol” , Hanser 1996, pages 640 to 673 or US-A-5,112,875 ).
- the blowing agent expands, the particles increase in size, and cell structures are formed.
- This expanding can be carried out in customary foaming apparatus, often referred to as "prefoamers”.
- prefoamers may be installed permanently or else may be portable.
- Expanding can be carried out in one or more stages.
- the expandable plastics particules are expanded directly to the desired final size.
- the expandable plastics particles are first expanded to an intermediate size and then, in one or more further stages, are expanded via a corresponding number of intermediate sizes to the desired final size.
- the compact plastics particles identified above, also referred to herein as "expandable plastics particles”, generally have no cell structures, in contrast to the expanded plastics particles.
- the expanded plastics particles generally have a low residual blowing agent content, of 0% to 5% by weight, preferably 0.5% to 4% by weight, more preferably 1% to 3% by weight, based on the overall mass of plastic and blowing agent.
- the expanded plastics particles obtained in this way can be placed in interim storage or used further without other intermediate steps for producing component B of the invention.
- the expandable plastics particles can be expanded using all of the blowing agents known to the skilled person, examples being aliphatic C 3 to C 10 hydrocarbons, such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane and/or hexane and isomers thereof, alcohols, ketones, esters, ethers or halogenated hydrocarbons, preferably n-pentane, isopentane, neopentane and cyclopentane, more preferably a commercial pentane isomer mixture of n-pentane and isopentane.
- the amount of blowing agent in the expandable plastics particles is generally in the range from 0.01% to 7% by weight, preferably 0.01% to 4% by weight, more preferably 0.1% to 4% by weight, based in each case on the expandable plastics particles containing blowing agent.
- styrene homopolymer also called simply “polystyrene” herein
- styrene copolymer or mixtures thereof as the sole plastic in component B.
- Polystyrene and/or styrene copolymer of this kind may be prepared by any of the polymerization techniques known to the skilled person; see, for example, Ullmann's Encyclopedia, Sixth Edition, 2000 Electronic Release or Kunststoff-Handbuch 1996, volume 4 "Polystyrol", pages 567 to 598 .
- the expandable polystyrene and/or styrene copolymer is generally prepared in a conventional way by suspension polymerization or by means of extrusion processes.
- styrene in the case of the suspension polymerization, styrene, optionally with addition of further comonomers, can be polymerized in aqueous suspension in the presence of a customary suspension stabilizer by means of radical-forming catalysts.
- the blowing agent and any other customary adjuvants may be included in the initial charge for the polymerization or else added to the batch in the course of the polymerization or after the polymerization has ended.
- the resultant beadlike, expandable styrene polymers impregnated with blowing agent, after the end of the polymerization, can be separated from the aqueous phase, washed, dried and screened.
- the blowing agent can be mixed into the polymer via an extruder, for example, conveyed through a die plate and pelletized under pressure to form particles or strands.
- the preferred or particularly preferred expandable styrene polymers or expandable styrene copolymers described above have a relatively low blowing agent content. Such polymers are also referred to as "low in blowing agent”.
- a highly suitable process for producing expandable polystyrene or expandable styrene copolymer low in blowing agent is described in US-A-5,112,875 .
- these styrene copolymers contain at least 50% by weight, i.e., 50% to 100% by weight, preferably at least 80% by weight, i.e., 80% to 100% by weight, of copolymerized styrene, based on the mass of the plastic (without blowing agent).
- comonomers contemplated include ⁇ -methylstyrene, ring-halogenated styrenes, acrylonitrile, esters of acrylic or methacrylic acid with alcohols having 1 to 8 C atoms, N-vinylcarbazole, maleic acid, maleic anhydride, (meth)acrylamides and/or vinyl acetate.
- the polystyrene and/or styrene copolymer may advantageously include a small amount of a copolymerized chain-branching agent, in other words a compound having more than one double bond, preferably two double bonds, such as divinylbenzene, butadiene and/or butanediol diacrylate.
- the branching agent is used generally in amounts from 0.0005 to 0.5 mol%, based on styrene. Mixtures of different styrene (co)polymers can be used as well.
- styrene homopolymers or styrene copolymers are crystal-clear polystyrene (GPPS), high-impact polystyrene (HIPS), anionically polymerized polystyrene or high-impact polystyrene (A-IPS), styrene- ⁇ -methylstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylic ester (ASA), methyl acrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers or mixtures thereof, or used with polyphenylene ether (PPE).
- GPPS crystal-clear polystyrene
- HIPS high-impact polystyrene
- A-IPS anionically poly
- plastics particles more preferably styrene polymers or styrene copolymers, more particularly styrene homopolymers, having a molecular weight in the range from 70 000 to 400 000 g/mol, more preferably 190 000 to 400 000 g/mol, very preferably 210 000 to 400 000 g/mol.
- expanded polystyrene particles or expanded styrene copolymer particles may be used, with or without further measures for blowing agent reduction, for producing the lignocellulosic substance.
- the expandable polystyrene or expandable styrene copolymer or the expanded polystyrene or expanded styrene copolymer customarily has an antistatic coating.
- the expanded plastics particles B are generally in an unmelted state even after compression to form the lignocellulose material, this meaning that the plastics particles B have generally not penetrated or impregnated the lignocellulose particles, but instead are distributed between the lignocellulose particles.
- the plastics particles B can customarily be separated from the lignocellulose by physical methods, as for example after the comminuting of the lignocellulose material.
- the overall amount of the expanded plastics particles B is generally in the range from 1 % to 25% by weight, preferably 3% to 20% by weight, more preferably 5% to 15% by weight. It has emerged as being advantageous to match the dimensions of the above-described expanded plastics particles B to the lignocellulose particles, preferably wood particles A), or vice versa.
- the Rosin-Rammler-Sperling-Bennet function is described in DIN 66145, for example.
- the d' values are determined by conducting sieve analyses first of all for determining the particle size distribution of the expanded plastics particles B and lignocellulose particles, preferably wood particles, A, in analogy to DIN 66165, Parts 1 and 2.
- Highly suitable lignocellulose particles A preferably wood particles, have a d' value according to Rosin-Rammler-Sperling-Bennet (definition and determination of the d' value as described above) in the range from 0.1 to 5, preferably 0.3 to 3, and more preferably 0.5 to 2.75.
- the overall amount of the binder C is in the range from 1 % to 50% by weight, preferably 2% to 15% by weight, more preferably 3% to 10% by weight.
- the overall amount of the binder F is in the range from 1 % to 30% by weight, preferably 2% to 20% by weight, more preferably 3% to 15% by weight.
- the binders of component C and of component F may be selected from the group consisting of phenoplast resin, aminoplast resin, and organic isocyanate having at least two isocyanate groups, using identical or different binders or binder mixtures of components C and F, preferably different binders, with particular preference phenoplast and aminoplast in both cases.
- the weight figure in the case of phenoplast or aminoplast resins relates to the solids content of the corresponding component (determined by evaporating the water at 120°C over the course of 2 hours in accordance with Günter Zeppenfeld, Dirk Grunwald, Klebstoffe in der Holz- und moleindustrie, 2nd edition, DRW-Verlag, page 268 ), while in relation to the isocyanate, more particularly the PMDI (polymeric diphenylmethane diisocyanate), it relates to the isocyanate component per se, in other words, for example, without solvent or emulsifying medium.
- phenoplast refers to synthetic resins or modified products obtained by condensation of phenol with aldehydes. Besides unsubstituted phenol, derivatives of phenol are used for the manufacture of phenoplast resins. These include cresols, xylenols and other alkylphenols (for example p-tert-butylphenol, p-tert-octylphenol and p-tert-nonylphenol), arylphenols (for example phenylphenol and naphthols) and divalent phenols (such as resorcinol and bisphenol A).
- cresols for example p-tert-butylphenol, p-tert-octylphenol and p-tert-nonylphenol
- arylphenols for example phenylphenol and naphthols
- divalent phenols such as resorcinol and bisphenol A
- aldehyde component is formaldehyde, which is used in variaous forms, including aqueous solution and solid paraformaldehyde, and also as compounds which give rise to formaldehyde.
- Other aldehydes for example acetaldehyde, acrolein, benzaldehyde and furfural
- Phenoplast resins can be modified by chemical reaction of the methylol or the phenolic hydroxyl groups and/or by phyisical dispersion in the modifying agent (EN ISO 10082).
- Prefered phenoplast resins are phenol aldehyde resins, most preferably phenol-formaldehyde resins.
- Phenol-formaldehyde resins also called PF resins
- PF resins are known from, for example, Kunststoff-Handbuch, 2nd edition, Hanser 1988, volume 10, "Duroplaste", pages 12 to 40 .
- aminoplast resin it is possible to use all aminoplast resins known to the skilled person, preferably those known for the production.of wood based materials. Resins of this kind and also their preparation are described in, for example, Ullmanns Enzyklopädie der ischen Chemie, 4th, revised and expanded edition, Verlag Chemie, 1973, pages 403 to 424 "Amino-plaste ", and Ullmann's Encyclopedia of Industrial Chemistry, vol. A2, VCH Verlagsgeselischaft, 1985, pages 115 to 141 "Amino Resins ", and also in M. Dunky, P.
- Preferred polycondensation products are urea-formaldehyde resins (UF resins), melamine-formaldehyde resins (MF resins) or melamine-containing urea-formaldehyde resins (MUF resins), more preferably urea-formaldehyde resins, examples being Kaurit ® glue products from BASF SE.
- UF resins urea-formaldehyde resins
- MF resins melamine-formaldehyde resins
- MAF resins melamine-containing urea-formaldehyde resins
- Kaurit ® glue products from BASF SE.
- Particularly preferred polycondensation products are those in which the molar ratio of aldehyde to the - optionally substituted partially with organic radicals - amino group and/or carbamide group is in the range from 0.3:1 to 1:1, preferably 0.3:1 to 0.6:1, more preferably 0.3:1 to 0.55:1, very preferably 0.3:1 to 0.5:1.
- the aminoplasts are used in combination with isocyanates
- the molar ratio of aldehyde to the - optionally substituted partially with organic radicals - amino group and/or carbamide group is in the range from 0.3:1 to 1:1, preferably 0.3:1 to 0.6:1, more preferably 0.3:1 to 0.45:1, very preferably 0.3:1 to 0.4:1.
- the stated aminoplast resins are used customarily in liquid form, customarily as a 25% to 90% by weight strength solution, preferably a 50% to 70% by weight strength solution, preferably in aqueous solution, but may also be used in solid form.
- the solids content of the liquid aqueous aminoplast resin can be determined in accordance with Günter Zeppenfeld, Dirk Grunwald, Klebstoffe in der Holz- und moleindustrie, 2nd edition, DRW-Verlag, page 268 .
- the constituents of the binder C and of the binder F can be used per se alone - that is, for example, aminoplast resin or organic isocyanate or PF resin as sole constituent of binder C or of binder F.
- the resin constituents of binder C and of binder F may also be used as a combination of two or more constituents of the binder C and/or of the binder F; these combinations preferably comprise an aminoplast resin and/or phenoplast resin.
- a combination of aminoplast and isocyanate can be used as binder C.
- the total amount of the aminoplast resin in the binder C is in the range from 1 % to 45% by weight, preferably 4% to 14% by weight, more preferably 6% to 9% by weight.
- the overall amount of the organic isocyanate, preferably of the oligomeric isocyanate having 2 to 10, preferably 2 to 8 monomer units and on average at least one isocyanate group per monomer unit, more preferably PMDI, in the binder C, based on the overall dry mass of the core, is in the range from 0.05% to 5% by weight, preferably 0.1 % to 3.5% by weight, more preferably 0.5% to 1.5% by weight.
- Components D and G may each independently of one another comprise different or identical, preferably identical curing agents that are known to the skilled person, or mixtures thereof. These components are customarily used if the binder C and/or F comprises aminoplasts or phenoplast resins. These curing agents are preferably added to the binder C and/or F, in the range, for example, from 0.01 % to 10% by weight, preferably 0.05% to 5% by weight, more preferably 0.1 % to 3% by weight, based on the overall amount of aminoplast resin or phenoplast resin.
- Curing agents for the aminoplast resin component or for the phenoplast resin component are understood herein to encompass all chemical compounds of any molecular weight that accelerate or bring about the polycondensation of aminoplast resin or phenoplast resin.
- One highly suitable group of curing agents for aminoplast resin or phenol-formaldehyde resin are organic acids, inorganic acids, acidic salts of organic acids, and acidic salts of inorganic acids, or acid-forming salts such as ammonium salts or acidic salts of organic amines.
- the components of this group can of course also be used in mixtures.
- ammonium sulfate or ammonium nitrate or organic or inorganic acids as for example sulfuric acid, formic acid or acid-regenerating substances, such as aluminum chloride, aluminum sulfate or mixtures thereof.
- One preferred group of curing agents for aminoplast resin or phenoplast resin are organic or inorganic acids such as nitric acid, sulfuric acid, formic acid, acetic acid, and polymers with acid groups, such as homopolymers or copolymers of acrylic acid or methacrylic acid or maleic acid.
- Phenoplast resins, preferably phenol-formaldehyde resins can also be cured alkylenically. It is preferred to use carbonates or hydroxides such as potassium carbonate and sodium hydroxide.
- curing agents for aminoplast resins are known from M. Dunky, P. Niemz, Holzwerkstoffe und Leime, Springer 2002, pages 265 to 269
- curing agents for phenoplast resins, preferably phenol-formaldehyde resins are known from M. Dunky, P. Niemz, Holzwerkstoffe und Leime, Springer 2002, pages 341 to 352 .
- the lignocellulose materials of the invention may comprise further, commercially customary additives and additives known to the skilled person, as component D and as component G, independently of one another identical or different, preferably identical additives, in amounts from 0% to 10% by weight, preferably 0.5% to 5% by weight, more preferably 1% to 3% by weight, examples being hydrophobizing agents such as paraffin emulsions, antifungal agents, formaldehyde scavengers, such as urea or polyamines, for example, and flame retardants.
- hydrophobizing agents such as paraffin emulsions, antifungal agents, formaldehyde scavengers, such as urea or polyamines, for example, and flame retardants.
- the thickness of the lignocellulose materials of the invention with expanded plastics particles in the core and with lignocellulosic fibers in the outer layers varies with the field of application and is situated in general in the range from 0.5 to 100 mm, preferably in the range from 10 to 40 mm, more particularly 15 to 20 mm.
- the expandable plastics particles B are present In nonuniform distribution in the core. This means that the weight ratio X of expanded plastics particles B to lignocellulose particles A in the outer regions of the core (“exterior”) is different from the weight ratio Y of expanded plastic particles B to lignocellulose particles A in the inner region of the core (“interior”), in other words is greater or lesser in the outer regions of the core ("exterior") than in the inner region of the core (“interior”).
- the inner region of the core is generally separated from the two outer regions of the core by faces extending parallel to the panel plane.
- the inner region of the core is understood to be the region which comprises 20% to 80% by weight, preferably 30% to 70% by weight, more preferably 40% to 60% by weight, more particularly 45% to 55% by weight, very preferably 50% by weight of the overall dry mass of the core and is situated between the two outer regions.
- the two outer regions may have the same mass, in other words in each case 25% by weight, or approximately the same mass, i.e., 25.01:24.99% to 25.99:24.01% by weight, preferably 25.01:24.99% to 25.8:24.2%, more preferably 25.01:24.99% to 25.6:24.4%, more particularly 25.01:24.99% to 25.4:24.6%, or a different mass, based on the overall dry mass of the core, i.e., 26:24% to 40:10% by weight, preferably 26:24% to 30:20% by weight, more preferably 26:24% to 27:23% by weight, more particularly 26:24% to 26.5:23.5% by weight.
- the sum total of the inner region and of the two outer regions of the core makes up 100% by weight.
- the weight ratio X of expanded plastics particles B to lignocellulose particles A in the outer regions of the core all expanded plastics particles B and all lignocellulose particles A which are comprised in the two outer regions are used.
- the ratio X' which describes the ratio of plastics particles B to lignocellulose particles A in one of the two outer regions, can be different from or the same as the ratio X" which describes the ratio in the other of the two outer regions.
- the ratio Z between the weight ratio X of expanded plastics particles to lignocellulose particles in the outer regions of the core (“exterior”) and the weight ratio Y of expanded plastics particles to lignocellulose particles in the inner region of the core (“interior”) is 1.05:1 to 1000:1, preferably 1.1:1 to 500:1, more preferably 1.2:1 to 200:1.
- this ratio Z is 0.001:1 to 0.95:1, preferably 0.002:1 to 0.9:1, more preferably 0.005:1 to 0.8:1.
- the nonuniform distribution of the plastics particles B in the core may be generated as follows:
- a plurality of mixtures of components A, B, C and D can be produced, containing different mass ratios of components A and B. These mixtures can be scattered in succession. In this case, there ought generally to be only slight mixing, or none, of the mixtures with different mass ratios of components A and B. As a result, a nonuniform distribution of the expanded plastics particles in the core of the lignocellulose material can be achieved.
- both the wood particles A and the plastics particles B can be separated beforehand into different fractions, by screening, for example. Each of the mixtures may comprise different fractions of the wood particles A and/or of the plastics particles B.
- the nonuniform distribution of the plastics particles B in the core may be accomplished by separative scattering.
- scattering takes place using a means which ensures that the spheres accumulate either in the outer regions or in the inner regions of the core, depending on the size and/or on the weight. This can be accomplished, for example, by scattering the mixture A, B, C, D using a screening system. In one preferred embodiment, this system is equipped with screens of different hole sizes which are arranged mirror-symmetrically.
- a support bearing the material for the lower outer layer is conveyed beneath a scattering means in which a screen system is disposed in such a way that at the beginning of the scattering means (in production direction) there are screens with a small hole size, with the hole size of the screens increasing inwardly toward the middle of the scattering station, and decreasing again at the end of the station.
- the disposition of the screens means that small lignocellulose particles enter into the outer regions of the core, those close to the outer layer, and large lignocellulose particles enter the inner region of the core.
- small plastics particles enter the outer regions of the core, those close to the outer layer, and large plastics particles enter the inner region of the core.
- the lignocellulose particle scattering station may comprise two metering silos each housing a plurality of back-scraping rakes.
- the bulk material composed of different large particles A and of components B, C and D ("core mixture"), can be supplied to the metering silos (e.g., from above).
- Disposed on the underside of each of the metering silos may be a bottom belt which runs over two deflecting rollers and which, in each case together with a discharge roll, forms a discharge unit for the core mixture.
- the screen devices form fractionating means by which the lignocellulosic particles A and the plastics particles B of the core mixture can be fractionated according to their sizes.
- the sections of the screen devices may be disposed in such a way that the fine lignocellulose particles A and/or plastics particles B are each scattered, in those regions of the scattering station that lie externally in the transport direction of the web, onto the lower outer layer, while the coarse lignocellulose particles A and/or plastics particles B are scattered, via the internal regions of the fractionating means, onto the outer layer (see in detail EP-B-1140447 ).
- At least a part of the apportioning sections in each case comprises an abrasive element which bears against the surface of the screen means and, when the apportioning sections are moved, is guided abradingly over the surface of the screen means.
- An abrasive element bearing under gentle pressure against the surface of the screen means for each apportioning section or at least some of the apportioning sections further strengthens the cleaning effect which comes about when the apportioning sections are moved over the surface of the screen means.
- the abrasive elements reinforce the force component that acts on the particles in a direction perpendicular to the screen surface, thereby producing an increase in the throughput.
- the transport means is preferably designed as a scraper belt, more particularly as a continuous scraper belt.
- the scraper belt is formed previously for the particles at least over a subregion in a direction perpendicular to the surface of the screen means, thereby allowing the particles to be tipped from the metering silo via its feed unit through the scraper belt and onto the screen means. This does away with the need for any complicated configuration of the feed unit.
- the scraper belt comprises drivers, more particularly platelike drivers, which are provided preferably at regular intervals on a continuous support element in chain or belt form. In this case, the support element may be mounted in each case centrally on the drivers.
- the drivers are fastened detachably on the support element or support elements, and/or are of air-impervious design. This ensures that, on the one hand, the drivers used can be optimally tailored to the screen means employed, and on the other hand that worn drivers can be replaced by new ones.
- the abrasive elements are formed in each case by a section of the drivers.
- the design of the means of the invention can be particularly cost-effective, since no separate components are needed for the abrasive elements.
- the drivers are of flexible design, being made from hard rubber, for example. This allows the abrasive elements to conform to the surface of the screen means, thereby ensuring, even in the event of a certain irregularity in the screen surface, that the abrasive elements bear on the surface of the screen means with a certain pressure over their entire width and also over their entire range of movement.
- the drivers are of abrasion-resistant design, at least in their sections forming the abrasive elements, and more particularly possess an abrasion-resistant coating, such as a Teflon coating, for example.
- the sections of the drivers that form the abrasive elements may be designed either in one piece with the drivers or else as separate components. Where the abrasive elements are designed as separate components, they are preferably mounted detachably on the drivers, so that they can be replaced in the event of wear.
- the drivers, at least in their sections forming the abrasive elements are formed from water-repellent nonadhering material.
- the screen means comprises screen zones, more particularly two screen zones, with different screen openings.
- the screen zones are arranged one after another along the direction of movement of the apportioning sections that are movable over the surface of the screen means, and preferably the screen openings of the screen zone/zones situated in the direction of movement of the apportioning sections are larger than the screen openings of the screen zone/screen zones situated counter to the direction of movement.
- fractionated particles may either be tipped, in accordance with the screen zones, into different collecting means for the different particle sizes, or, for example, may be tipped onto a moving conveyor belt which is disposed beneath the screen means and on which, in this way, a web with different distributions of particle sizes over its thickness can be produced.
- the continuous scraper belt is guided via two deflection rolls, and so a lower belt section runs directly on the surface of the screen means, and an upper belt section runs at a particular distance from the surface of the screen means, more particularly in each case substantially parallel to the surface of the screen means.
- a particularly compact design is possible for a means of the invention.
- these particles may be alien bodies present in the bulk material, such as screws or nails, for example; alternatively, they may be aggregations or particles which exceed a maximum permissible size, and which are expelled and taken away in order that even the largest screen openings of the screen means cannot become clogged.
- an intermediate base is provided, and the drivers bear, with their ends opposed to the sections forming the abrasive elements, against the intermediate base, meaning that, when the apportioning sections are moved, these ends are guided abradingly over the intermediate base.
- the intermediate base may extend from one deflection roller in the direction of movement of the upper belt section toward the opposite, other deflection roller; between this other deflection roller and the end of the intermediate base that faces this other deflection roller, a region is formed which is pervious for the particles in a direction perpendicular to the surface of the screen means. Particularly when this region is formed from further screen means possessing relatively large screen openings, it is possible here for there to be a preliminary deposition of alien bodies or particles having a size which is above the size of these screen openings.
- a distribution means is positioned downstream of the feed unit of the metering silo, and can be used to supply the particles taken from the metering silo through the feed unit to the two scraper belts, more particularly in alternation.
- the two scraper belts can be driven in opposing directions, and so the two upper belt sections can be moved in a mutually divergent way, and, between the upper and the lower belt sections, in a manner already described, an intermediate base is provided, it is possible for the particles applied via the distribution means to the respective intermediate bases to be transported to the ends of the scraper belts that are situated in opposite directions, where they are applied in each case to the screen means disposed beneath the scraper belts.
- the material for the core can be formed on a moving conveyor belt disposed beneath the screen means, and on which the lower outer layer has already been scattered, the formation of the core material being such that the fine lignocellulose particles A and/or plastics particles B are accumulated in the outer layers of the core, and the coarse lignocellulose particles A and/or plastics particles B are accumulated in the inner layer of the core.
- a distribution means it is also possible, for example, for there to be two metering silos by which the two scraper belts are charged with particles.
- the screen means and/or the further screen means is preferably designed as an oscillating screen or as a vibrating shaker screen.
- the bulk material fed to the screen means is loosened further, meaning that fine particles and, subsequently, medium-sized particles at a distance from the screen pass more quickly toward the screen openings and through them (see in detail DE-C-197 16 130 ).
- Another preferred embodiment is the use of a roller scattering system with specially profiled rolls (roll screen).
- a symmetrical construction is selected, meaning that small lignocellulose particles A and/or small plastics particles B enter the outer regions of the core, those close to the outer layer, and large lignocellulose particles A and/or large plastics particles B enter the inner region of the core.
- One particularly preferred embodiment is the use of one or more ClassiFormerTM devices. Suitability is possessed, for example, by the Classiformer CC from Dieffenbacher, which has a symmetrical construction. Alternatively it is possible to use two Classiformers C, arranged opposite and one after the other.
- Lignocellulose materials as for example wood based materials, are an inexpensive and resource-protecting alternative to solid wood, and have become very important particularly in furniture construction, for laminate floors and as construction materials.
- Customarily serving as starting materials are wood particles of different thicknesses, examples being wood chips or wood fibers from a variety of woods. Such wood particles are customarily compressed with natural and/or synthetic binders and optionally with addition of further additives to form wood based materials in panel or strand forms.
- Lightweight wood based materials are very important for the following reasons: Lightweight wood based materials lead to greater ease of handling of the products by the end customers, as for example when packing, transporting, unpacking or constructing the furniture. Lightweight wood based materials result in lower costs for transport and packaging, and it is also possible to save on materials costs when producing lightweight wood based materials. Lightweight wood based materials may, as when used in means of transport, for example, result in a lower energy consumption by those means of transport. Furthermore, using lightweight wood based materials, it is possible to carry out more cost-effective production of, for example, materials-intensive decorative parts, relatively thick worktops and side panels in kitchens.
- the expandable polystyrene Polystyrol Kaurit® Light 200 from BASF SE served as starting material.
- the polystyrene particles were treated with steam and foamed to a bulk density of 50 g/l in a batch prefoamer.
- the expanded polymer particles obtained in this way (component B) were stored at room temperature in an air-permeable cloth sack for 7 days before further use.
- Component B is omitted for comparative example 1, i.e. the mixtures 2 and 3 then comprise only the components A, C and D.
- mixtures 2 and 3 are identical.
- mixture 1 comprises wood shavings as component E, in all other examples wood fibers.
- the mixtures were each produced in a laboratory mixer, with the solid constituents being introduced first and mixed.
- the liquid constituents were premixed in a vessel and then sprayed on.
- middle layer shavings composed of shavings having a moisture content of 3.2% were used (component A).
- Kaurit® glue 347 having a solids content of 67% from BASF SE was used as binder (components C and F).
- binder components C and F.
- 40 parts by weight of water and 1 part by weight of 52% strength ammonium nitrate solution (in each case based on 100 parts by weight of Kaurit glue 347) were added to the glue before application to the solid constituents of the mixture.
- mixtures 2 and 3 4 parts by weight of 52% strength ammonium nitrate solution (based on 100 parts by weight of Kaurit glue 347) were added to the glue before application to the solid constituents of the mixtures.
- the amount of glue mix is set so that a glue addition of 10% is obtained, i.e. 10 parts by weight of glue (based on solids) per 100 parts by weight of E (based on solids).
- the amount of glue mix is set so that a glue addition of 8.0% is obtained, i.e. 8.0 parts by weight of glue (based on solids) per 100 parts by weight of the mixture of A and B (based on solids).
- the mixtures were subsequently placed on top of one another in layers in a 30 ⁇ 30 cm mold so as to obtain a wood material mat having a symmetrical structure made up of 5 layers (sequence: mixture 1, mixture 2, mixture 3, mixture 2, mixture 1).
- the amounts were selected so that the weight ratio of the layers (based on dry matter) was in each case 15.5:20.5:28:20.5:15.5.
- the mass ratio of the total amount of component B comprised in the inner three layers to the total amount of component A comprised in the inner three layers is the same (based on solids).
- the total weight of the wood material mat was selected so that the desired density is obtained at a prescribed thickness of 18.5 mm at the end of the pressing process.
- the wood material mat was then precompacted cold and pressed in a hot press. A thickness of 16 mm was set here.
- the pressing temperature was in each case 210°C and the pressing time was 210 s.
- the determination of the density was carried out 24 hours after production in accordance with EN 1058.
- Examples 1 and 2 Comparative examples using shavings in the covering layer (with and without expanded polymer particles in the core)
- Examples 3 to 7 Examples according to the invention
- Example Component E Ratio X (“exterior”) Ratio Y (“interior”) Ratio Z ( X:Y) Density Transverse tensile strength Flexural strength Screw pullout res.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Claims (7)
- Lignocellulosehaltige Werkstoffe mit einem Kern und zwei Deckschichten, die im KernA) 30 bis 98 Gew.-% Lignocellulosepartikel;B) 1 bis 25 Gew.-% expandierte Kunststoffteilchen mit der Schüttdichte im Bereich von 10 bis 150 kg/m3,C) 1 bis 50 Gew.-% eines oder mehrerer Bindemittel ausgewählt aus der Gruppe bestehend aus Phenoplastharz, Aminoplastharz und organischem Isocyanat mit mindestens zwei Isocyanatgruppen undD) 0 bis 10 Gew.-% Additive
und in den DeckschichtenE) 70 bis 99 Gew.-% lignocellulosehaltige Fasern,F) 1 bis 30 Gew.-% eines oder mehrerer Bindemittel ausgewählt aus der Gruppe bestehend aus Phenoplastharz, Aminoplastharz und organischem Isocyanat mit mindestens zwei Isocyanatgruppen undG) 0 bis 30 Gew.-% Additiveenthalten, dadurch gekennzeichnet, dass die expandierten Kunststoffteilchen B im Kern inhomogen verteilt vorliegen, was bedeutet, dass sich das Gewichtsverhältnis X von expandierten Kunststoffteilchen B zu Lignocellulosepartikeln A in den äußeren Bereichen des Kerns vom Gewichtsverhältnis Y von expandierten Kunststoffteilchen B zu Lignocellulosepartikeln A im inneren Bereich des Kerns unterscheidet. - Lignocellulosehaltige Werkstoffe mit einem Kern und zwei Deckschichten, die im Kern ausA) 30 bis 98 Gew.-% Lignocellulosepartikeln;B) 1 bis 25 Gew.-% expandierten Kunststoffteilchen mit der Schüttdichte im Bereich von 10 bis 150 kg/m3,C) 1 bis 50 Gew.-% eines oder mehrerer Bindemittel ausgewählt aus der Gruppe bestehend aus Phenoplastharz, Aminoplastharz, und organischem Isocyanat mit mindestens zwei Isocyanatgruppen undD) 0 bis 30 Gew.-% Additiven
und in den Deckschichten ausE) 70 bis 99 Gew.-% lignocellulosehaltigen Fasern,F) 1 bis 30 Gew.-% eines oder mehrerer Bindemittel ausgewählt aus der Gruppe bestehend aus Phenoplastharz, Aminoplastharz, und organischem Isocyanat mit mindestens zwei Isocyanatgruppen undG) 0 bis 30 Gew.-% Additivenbestehen, dadurch gekennzeichnet, dass die expandierten Kunststoffteilchen B im Kern inhomogen verteilt vorliegen, was bedeutet, dass sich das Gewichtsverhältnis X von expandierten Kunststoffteilchen B zu Lignocellulosepartikeln A in den äußeren Bereichen des Kerns vom Gewichtsverhältnis Y von expandierten Kunststoffteilchen B zu Lignocellulosepartikeln A im inneren Bereich des Kerns unterscheidet. - Verfahren zur Herstellung von lignocellulosehaltigen Werkstoffen nach einem der Ansprüche 1 bis 2, indem man die Komponenten E, F und G für die Deckschichten und Komponenten A, B, C und D für den Kern mischt, dadurch gekennzeichnet, dass man das Material für den Kern so streut, dass eine inhomogene Mischung der Komponenten A und B entsteht.
- Verfahren zur Herstellung von lignocellulosehaltigen Werkstoffen nach Anspruch 3, dadurch gekennzeichnet, dass man die inhomogene Mischung der Komponenten A und B erhält, indem man unterschiedliche Mischungen mit unterschiedlichen Verhältnissen A zu B nacheinander streut.
- Verfahren zur Herstellung von lignocellulosehaltigen Werkstoffen nach einem der Ansprüche 3 bis 4, dadurch gekennzeichnet, dass man die inhomogene Mischung der Komponenten A und B durch separierendes Streuen der Mischung enthaltend A, B, C und D erhält.
- Verwendung der lignocellulosehaltigen Werkstoffe nach einem der Ansprüche 1 bis 2 im Möbelbau, für Laminatfußböden und für Baumaterialien.
- Verwendung der lignocellulosehaltigen Werkstoffe nach einem der Ansprüche 1 bis 2 zur Herstellung von Platten für den Möbelbau, für Laminatfußböden und für Baumaterialien.
Priority Applications (4)
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SI201230627A SI2794211T1 (sl) | 2011-12-23 | 2012-12-21 | Lignocelulozni materiali z lignoceluloznimi vlakni v zunanjih plasteh in ekspandiranimi delci plastike, prisotni v jedru ter procesi in njihova uporaba |
EP12813353.5A EP2794211B1 (de) | 2011-12-23 | 2012-12-21 | Lignocellulosematerialien mit lignocellulosefasern in den äusseren schichten und geschäumtem kunststoff partikel im kern, sowie verfahren und verwendung |
RS20160493A RS54924B1 (sr) | 2011-12-23 | 2012-12-21 | Lignocelulozni materijali sa lignoceluloznim vlaknima u spoljašnjim slojevima i ekspandiranim plastičnim česticama u jezgru, kao i postupci i njihova primena |
HRP20160779TT HRP20160779T1 (hr) | 2011-12-23 | 2016-07-01 | Lignocelulozni materijali s lignoceluloznim vlaknima u vanjskim slojevima i ekspandiranim plastičnim česticama u jezgri, kao i postupci i njihova primjena |
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EP11195611 | 2011-12-23 | ||
EP12813353.5A EP2794211B1 (de) | 2011-12-23 | 2012-12-21 | Lignocellulosematerialien mit lignocellulosefasern in den äusseren schichten und geschäumtem kunststoff partikel im kern, sowie verfahren und verwendung |
PCT/EP2012/076568 WO2013092963A2 (en) | 2011-12-23 | 2012-12-21 | Lignocellulosic materials with lignocellulosic fibers in the outer layers and expanded plastics particles present in the core |
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JP (1) | JP6223355B2 (de) |
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EP2942208A1 (de) * | 2014-05-09 | 2015-11-11 | Akzenta Paneele + Profile GmbH | Verfahren zur Herstellung eines dekorierten Wand- oder Bodenpaneels |
RU2696283C2 (ru) | 2014-08-08 | 2019-08-01 | Басф Се | Непрерывный способ получения однородной плиты |
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EP2464691A1 (de) | 2009-08-13 | 2012-06-20 | Basf Se | Leichte lignocellulosewerkstoffe mit guten mechanischen eigenschaften |
WO2011107365A1 (de) * | 2010-03-04 | 2011-09-09 | Basf Se | Lignocellulosewerkstoffe mit guten mechanischen eigenschaften |
US8920923B2 (en) * | 2010-03-04 | 2014-12-30 | Basf Se | Lignocellulose materials having good mechanical properties |
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Also Published As
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BR112014015299B1 (pt) | 2021-04-13 |
WO2013092963A3 (en) | 2013-08-15 |
ZA201405333B (en) | 2017-11-29 |
EA027974B1 (ru) | 2017-09-29 |
CL2014001694A1 (es) | 2014-11-28 |
MY168545A (en) | 2018-11-12 |
DK2794211T3 (en) | 2016-08-01 |
MX352162B (es) | 2017-11-13 |
CA2860245C (en) | 2021-03-02 |
KR102030206B1 (ko) | 2019-10-08 |
PT2794211E (pt) | 2016-06-20 |
EP2794211A2 (de) | 2014-10-29 |
SI2794211T1 (sl) | 2016-09-30 |
WO2013092963A2 (en) | 2013-06-27 |
UA113421C2 (xx) | 2017-01-25 |
PL2794211T3 (pl) | 2016-12-30 |
EA201491143A1 (ru) | 2016-01-29 |
KR20140107606A (ko) | 2014-09-04 |
CA2860245A1 (en) | 2013-06-27 |
HRP20160779T1 (hr) | 2016-08-26 |
ES2576481T3 (es) | 2016-07-07 |
AR089420A1 (es) | 2014-08-20 |
AU2012356874A1 (en) | 2014-08-07 |
JP2015506284A (ja) | 2015-03-02 |
CN104136179A (zh) | 2014-11-05 |
AU2012356874B2 (en) | 2017-01-19 |
NZ625930A (en) | 2015-08-28 |
HUE028569T2 (en) | 2016-12-28 |
CN104136179B (zh) | 2016-10-12 |
JP6223355B2 (ja) | 2017-11-01 |
RS54924B1 (sr) | 2016-10-31 |
MX2014007513A (es) | 2014-10-17 |
LT2794211T (lt) | 2016-09-26 |
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