EP1654322A2 - Materiaux composites contenant des materiaux plastiques et du bois - Google Patents
Materiaux composites contenant des materiaux plastiques et du boisInfo
- Publication number
- EP1654322A2 EP1654322A2 EP04763532A EP04763532A EP1654322A2 EP 1654322 A2 EP1654322 A2 EP 1654322A2 EP 04763532 A EP04763532 A EP 04763532A EP 04763532 A EP04763532 A EP 04763532A EP 1654322 A2 EP1654322 A2 EP 1654322A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- wood
- melamine resin
- mass
- melt
- composite material
- 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- Withdrawn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
- 239000002023 wood Substances 0.000 title claims abstract description 150
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 229920003023 plastic Polymers 0.000 title claims abstract description 35
- 239000004033 plastic Substances 0.000 title claims abstract description 35
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 154
- 239000004640 Melamine resin Substances 0.000 claims abstract description 136
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 58
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 55
- 150000002170 ethers Chemical class 0.000 claims abstract description 37
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 36
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 238000000265 homogenisation Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 70
- 239000002025 wood fiber Substances 0.000 claims description 35
- -1 polytetrafluoroethylene Polymers 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 27
- 239000004848 polyfunctional curative Substances 0.000 claims description 26
- 239000008187 granular material Substances 0.000 claims description 25
- 239000012803 melt mixture Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 16
- 235000013312 flour Nutrition 0.000 claims description 16
- 239000003063 flame retardant Substances 0.000 claims description 15
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 12
- 238000005187 foaming Methods 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 239000004604 Blowing Agent Substances 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical class NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000011265 semifinished product Substances 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 7
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000006266 etherification reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 229920003232 aliphatic polyester Polymers 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000004072 triols Chemical class 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical group NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract 1
- 239000000155 melt Substances 0.000 description 25
- 150000003254 radicals Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 241000218657 Picea Species 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000007872 degassing Methods 0.000 description 7
- 238000009849 vacuum degassing Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 2
- AQROEYPMNFCJCK-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-tert-butyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O AQROEYPMNFCJCK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- MHQJUHSHQGQVTM-HNENSFHCSA-N Octadecyl fumarate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C/C(O)=O MHQJUHSHQGQVTM-HNENSFHCSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002976 peresters Chemical class 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- FLQULDKEPHBJJU-UHFFFAOYSA-N (3-methoxybenzoyl) 3-methoxybenzenecarboperoxoate Chemical compound COC1=CC=CC(C(=O)OOC(=O)C=2C=C(OC)C=CC=2)=C1 FLQULDKEPHBJJU-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CEJFMOILXWJPCN-TYYBGVCCSA-N (e)-but-2-enedioic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)\C=C\C(O)=O.NC1=NC(N)=NC(N)=N1 CEJFMOILXWJPCN-TYYBGVCCSA-N 0.000 description 1
- HBQGCOWNLUOCBU-ARJAWSKDSA-N (z)-4-(ethylamino)-4-oxobut-2-enoic acid Chemical compound CCNC(=O)\C=C/C(O)=O HBQGCOWNLUOCBU-ARJAWSKDSA-N 0.000 description 1
- NWODYZCQADERLP-HNENSFHCSA-N (z)-4-(octadecylamino)-4-oxobut-2-enoic acid Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)\C=C/C(O)=O NWODYZCQADERLP-HNENSFHCSA-N 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
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- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
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- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/726—Measuring properties of mixture, e.g. temperature or density
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
- B29B7/92—Wood chips or wood fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/245—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using natural fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/32—Modified amine-aldehyde condensates
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Definitions
- the invention relates to plastics and wood-containing composite materials and a method for their production.
- Plastics and wood-containing composite materials are known.
- EP 1 172 404 A1 describes composites which consist of polypropylene, polyethylene or polystyrene with a wood fiber content of 20 to 80% by mass.
- elastomers such as ethylene-propylene-diene terpolymers
- JP 2001 121 654 A2 describes laminates made of polyolefin-wood powder blends which contain polyolefin / wood powder in a mixing ratio of 1: 2 in the inner and outer layer.
- thermoplastic and wood-containing composite materials are known.
- a disadvantage of the thermoplastic and wood-containing composite materials is the limited strength and toughness as a result of the low compatibility of the apolar polyolefins with the wood component.
- the object of the invention is achieved by plastics and wood-containing composite materials, the composite materials according to the invention having a proportion of wood which is particulate dispersed in the crosslinked plastics and the crosslinked plastics crosslinked melamine resin ethers or mixtures of 10 to 90% by mass of partially crosslinked thermoplastics and 90 are up to 10% by mass of crosslinked melamine resin ethers,
- the parameters can all be met together or individually.
- the composite materials are preferably sheets, profiles or injection molded parts.
- the particulate wood in particular in the form of wood flour, wood particles, wood fibers and / or wood chips in the composite materials, can consist of softwood and / or hardwood.
- Wood flour with a mean particle diameter of 0.01 to 0.5 mm is suitable as wood flour in the composite materials.
- Suitable wood particles are wood particles with an average diameter of 0.5 to 5 mm.
- Suitable wood granules are granules which have an average particle diameter of 1 to 5 mm.
- Suitable wood fibers in the composite materials are wood fibers which have an average length of 0.05 to 1 mm and a length / thickness ratio of 2: 1 to 20: 1.
- Suitable wood chips are wood chips with a length of 1 to 5 mm and a thickness of 0.5 to 2 mm.
- Composite materials consisting of 65 to 80% by mass of wood in the form of mixtures of wood fibers and wood chips in a ratio of 1:10 to 10: 1 and 35 to 20% by mass of crosslinked plastics are preferred.
- the molar ratio of aldehyde component / melamine component is preferably 1.5: 1 to 4: 1.
- Preferred crosslinked melamine resin are cross-linked etherified melamine resin condensates are free from the triazine rings of the melamine resin condensate bound hydroxymethyleneamino and triazine rings linking -NH-CH 2 -O-CH 2 -NH- - groups, in which the non-crosslinked etherified melamine resin condensates by etherification Hydroxymethylamino groups of the non-crosslinked melamine resin condensates by CrC 18 alcohols and / or polyols of the type diols, triols and / or tetrols with molecular weights from 62 to 20,000 has taken place, and in which the uncrosslinked etherified melamine resin condensates have been cured thermally and / or by acid generators.
- the partially crosslinked thermoplastics are preferably partially crosslinked ethylene-vinyl acetate copolymers, partially crosslinked partially hydrolyzed ethylene-vinyl acetate copolymers, partially crosslinked thermoplastic polyurethanes, partially crosslinked high molecular weight aliphatic, aromatic aliphatic polyethers and / or partially crosslinked aliphatic and / or aromatic aliphatic polyesters, in particular partially crosslinked and / or unsaturated polycaprolactones Polyester.
- Partially crosslinked copolymers which have a vinyl acetate content of 4 to 50% by mass are suitable as partially crosslinked ethylene-vinyl acetate copolymers in the composite materials.
- Suitable partially crosslinked partially saponified ethylene-vinyl acetate copolymers in the composite materials are partially crosslinked copolymers which have a starting vinyl acetate content of 4 to 50% by mass and in which 5 to 50 mol% of the vinyl acetate groups are saponified to vinyl alcohol groups.
- Another preferred composition of the composite materials consists of 65 to 80% by mass of wood in the form of mixtures of wood fibers and wood chips in a ratio of 1:10 to 10: 1 and 35 to 20% by mass of crosslinked plastics in the form of mixtures of partially crosslinked EVA copolymers with a vinyl acetate content of 25 to 40 mass% and crosslinked melamine resin in a mixing ratio of 2: 1 to 1: 5.
- partially crosslinked polyurethanes that can be contained in the composite materials are partially crosslinked thermoplastic polyurethanes based on hexamethylene diisocyanate as the diisocyanate component and diol components such as butanediol, hexanediol, dodecanediol and / or polyalkylene glycols. If the plastics in the composite materials are in foamed form, the density of the composite materials is preferably 0.6 to 1.0 g / cm 3 .
- Suitable flame retardants which can be contained in the composite materials according to the invention are ammonium polyphosphate, melamine cyanurate, boron trioxide, boric acid, ammonium borate and zinc borate.
- suitable pigments which can be contained in the composite materials according to the invention are iron oxide, ester group-containing isoindoline pigments, anthracene fluorescent dyes, carbazole dioxazine and delta indanthrone blue pigment.
- the stabilizers contained in the composite materials are preferably UV absorbers and / or radical scavengers.
- UV absorbers examples include 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) benzotriazole, 2,4-dihydroxybenzophenone and sodium 3- (2H -benzo-triazol-2-yl) -5-sec.butyl-4-hydroxybenzenesulfate.
- Suitable radical scavengers which can be contained in the composite materials according to the invention are bis- [2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl] ester, bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, N, N'- (2-hydroxyphenyl) ethanediamide and N, N'-diformyl-N, N'-di- (1-oxyl radical-2,2,6,6-tetramethyl -4-piperidinyl) -1, 6-hexanediamine.
- the auxiliaries contained in the composite materials are preferably lubricants of the zinc stearate, calcium stearate and / or magnesium stearate type, and / or talc, aluminum oxide, sodium carbonate, calcium carbonate, silica and / or polytetrafluoroethylene powder non-stick agents.
- a plastic and wood-containing composite material is produced according to a variant with an extruder process, in which in a first process step a melt mixture of melamine resin ether, wood or thermoplastics is produced in a first extruder segment, the melt mixture is degassed after homogenization, and in a second extruder segment in the melt mixture Hardeners, thermally decomposing radical formers and / or blowing agents are metered and homogenized in the melt mixture, and flame retardants, pigments, stabilizers and / or auxiliaries can be metered in the first and / or second extruder segment, and in a second process step the wood-containing melt mixture either in heated in a third extruder segment, discharged with crosslinking and optionally foaming through a molding tool and removed as a semi-finished product or discharged from the extruder, granulated and the granules in a third process step is processed in presses, extruders or injection molding machines with crosslinking and, if necessary, foaming to give semi-
- Composites according to claim 1 are produced in the extruder process, the crosslinked melamine resin ethers and the partially crosslinked thermoplastics being able to be present in the composite materials in foamed form and the composite materials 3 to 10 mass% flame retardants, 0J to 2 mass% pigments, 0J to 5 mass% Stabilizers and / or 0J to 5% by mass, each based on the sum of wood and plastics, can contain auxiliaries, in which in the a) first stage of the process in extruders with a length of 30 to 60 D, with side-flow metering devices for solid and liquid media and vacuum degassing are equipped, in a first extruder segment, melt mixtures of melamine resin ether with molecular weight from 1500 to 200000 and a molar ratio of melamine / formaldehyde of 1: 1, 5 to 1: 4, wood in the form of wood flour, wood particles, wood granules, wood fibers and / or wood chips with a residual moisture of up to 10%
- thermoplastic and melamine resin ether can be used as a masterbatch containing 60 to 90% by mass of thermoplastic, and wherein 3 to 10% by mass of flame retardants, 0J to 2% by mass Pigments, 0.1 to 5 mass% stabilizers and / or 0J to 5 mass% each based on the sum of melamine resin ether, wood and thermoplastic, auxiliaries in the first and / or second extruder segment can be metered into the extruder, and in which b) second stage of the process, the wood in the form of wood flour, wood particles, wood granules, wood fiber
- Twin-screw extruders or extruders with a plunger screw are preferably used as extruders in the extruder process.
- the composite material is produced by a pre-impregnation process, with wood in mixers containing solutions or dispersions of melamine resin condensates in water or mixtures of water and % impregnated and dried, the melamine resin condensates etherified melamine resin condensates and / or partially etherified with CC ⁇ alcohols melamine resin condensates with weight-average molar masses of 150 to 50,000 and a molar ratio of melamine / formaldehyde being 1: 1, 5 to 1: 4 and the melamine resin condensates optionally to 3% by mass hardener, based on the melamine resin condensates, and then the melt mixture in the first stage of the process is made from wood pre-impregnated with melamine resins and - melamine resin ether or - thermoplastics or mixtures of melamine resin ether and thermoplastics.
- the melamine resin condensates etherified melamine resin condensates and / or partially etherified with C 1 -C 4 alcohols melamine resin condensates with molar mass weight means of 150 to 50,000 and a molar ratio of melamine / formaldehyde 1: 1.5 to 1: 4, - in the partially etherified melamine resin condensates the proportion of the hydroxy groups not etherified
- the melamine resin ether can be metered via a side-flow metering device to the pre-impregnated wood-containing thermoplastic melt, the melt mixture is degassed after homogenization, and in the second extruder segment at melt temperatures of 100 to 150 ° C in the melt mixture 0J to 2 mass%, based on the melamine resin ether , Hardener, 0.1 to 2% by mass, based on the thermoplastics, thermally decomposing radical formers, and optionally 0.2 to 4% by mass, based on the sum of thermoplastic and melamine resin ether, blowing agent, metered and in the melt mixture are homogenized, blowing agents, hardeners and / or thermally decomposing radical formers can be used as masterbatch containing 60 to 90% by mass of thermoplastic,
- auxiliaries in first and / or second extruder segment can be metered into the extruder, and in the third process stage the wood mixture in the form of wood flour, wood particles, wood granules, wood fibers and / or wood chips and melt mixture
- - Or discharged from the extruder, granulated, and the molding compound granulate is processed in a third process stage at temperatures of 150 to 240 ° C in presses, extruders or injection molding machines with curing and optionally foaming to give semi-finished products or molding materials.
- suitable mixers that can be used in the pre-impregnation process for impregnating wood in the form of wood flour, wood particles, wood granules, wood fibers and / or wood chips with aqueous solutions or dispersions of melamine resin condensates are paddle mixers, ploughshare mixers, centrifugal mixers and mixing devices with a mixing screw.
- a third method for producing composite materials according to the invention is that they are produced by a sintering process, in a) first process stage mixtures of wood and plastics, which consist of melamine resin ether or mixtures of melamine resin ether and thermoplastics or thermoplastics, are sintered in high-speed mixers, which Sinter mixture is cooled and, after cooling, the sinter mixture, hardener, thermally decomposing radical formers and / or blowing agents, flame retardants, pigments, stabilizers and / or auxiliaries are tumbled, and in a b) second process step the sinter mixture containing wood, melamine resin ether and optionally thermoplastics in presses , Extruders or injection molding machines with crosslinking and possibly foaming to semi-finished or molded materials.
- the heat input in the internal mixer takes place both through the friction heating and through the jacket heating.
- Wood can be used in the process variants in the form of wood flour, wood particles, wood granules, wood fibers and / or wood chips with a residual moisture of up to 10% by mass.
- the residual moisture refers to the amount of water that is released within 24 hours when the wood dries at 103 ° C.
- wood is preferably used in the form of wood flour, wood particles, wood granules, wood fibers or wood chips which contains 3 to 10% by mass of sodium borate or sodium borate / boric acid mixtures in a mass ratio of 1: 9 to 9: 1.
- the content of sodium borate or sodium borate / boric acid mixtures in the wood can be achieved by impregnation from aqueous solution and subsequent drying or by powdering.
- melamine resin ethers used in the process variants for the production of composite materials, etherified melamine resin condensates, which are free of -NH-CH 2 -O-CH 2 -NH- groups linking hydroxymethylamino groups and triazine rings which are bonded to the triazine rings of the melamine resin condensate, and in which the etherification of the hydroxymethylamino groups by CC 18 alcohols and / or diols of the HO-R-OH type with molecular weights from 62 to 20,000.
- the melamine resin ethers used for the production of the composite materials are preferred by etherification of melamine resin precondensates with CC 4 alcohols, optionally with subsequent partial etherification with C 4 -C 18 alcohols, C 2 -C 8 diols, polyhydric alcohols of the glycerol type or Pentaerythritol, C 5 -C 18 amino alcohols, polyalkylene glycols, hydroxyl-terminated polyesters, siloxane polyesters, siloxane polyethers, melamine-alkylene oxide adducts and / or bipolar phenol-alkylene oxide adducts and subsequent thermal condensation of the melamine resin ethers in the melt in the continuous melt Temperatures of 140 to 220 ° C produced.
- Weak inorganic acids such as boric acid and / or organic acids or acid formers can be used as hardeners for the melamine resin ethers in the process variants for producing the composite materials.
- Preferred hardeners for the melamine resin ethers in the processes for the production of composite materials are aliphatic C 4 -C 18 carboxylic acids, aromatic C 7 -C 18 carboxylic acids, acid formers of the type blocked sulfonic acids, alkali metal salts or ammonium salts of phosphoric acid, C r C 12 alkyl esters or C 2 -C 8 - hydroxyalkyl esters of C 7 -C 1 aromatic carboxylic acids or inorganic acids, salts of melamine or guanamines with C 1 -C 18 aliphatic carboxylic acids, anhydrides, half esters or half amides of C -C 20 dicarboxylic acids, half esters or Half-amides of copolymers of ethylenically unsaturated C 4 -C 20 dicarboxylic acid anhydrides and ethylenically unsaturated monomers of the type C 2 -C 20 olefins and / or C 8
- aromatic C 7 -C 18 carboxylic acids as hardeners for the melamine resin ethers are benzoic acid, phthalic acid or naphthalenedicarboxylic acid.
- blocked sulfonic acids as hardeners for the melamine resin ethers are benzilmonoxime tosylate, benzilmonoxime-p-dodecylbenzenesulfonate, 4-chloro- ⁇ -tri-fluoroacetophenonoxime-benzenesulfonate, and 2-pentafluorophenylsulfonyloxyimino-4-phenyl-but-3-uterol.
- alkali metal salts or ammonium salts of phosphoric acid as hardeners for the melamine resin ethers are ammonium hydrogen phosphate, sodium polyphosphate and potassium hydrogen phosphate.
- Examples of CC 12 alkyl esters or C 2 -C 8 hydroxyalkyl esters of C 7 -C 14 aromatic carboxylic acids as hardeners for the melamine resin ethers are dibutyl phthalate, phthalic acid diglycol ester and / or trimellitic acid glycol ester.
- salts of melamine or guanamines with dC t ⁇ -aliphatic carboxylic acids as hardeners for the melamine resin ethers are melamine formate, melamine citrate, melamine maleate, melamine fumarate and / or acetoguanamine butyrate.
- Examples of anhydrides, half esters or half amides of C 4 -C 20 dicarboxylic acids as hardeners for the melamine resin ethers are maleic anhydride, succinic anhydride, phthalic anhydride, mono-CrCt ⁇ -alkyl maleates, maleic acid monoamide or maleic acid mono-C 18 alkylamides.
- Examples of mono-C Ci 8 -alkyl maleates as hardeners for the melamine resin ethers are maleic acid monobutyl ester, maleic acid monoethylhexyl ester or monostearyl maleate.
- maleic acid mono -CC 18 alkyl amides as hardeners for the melamine resin ethers are maleic acid monoethylamide, maleic acid monooctylamide or maleic acid monostearylamide.
- half esters or half amides of copolymers of ethylenically unsaturated C 4 -C 20 dicarboxylic acid anhydrides and ethylenically unsaturated monomers of the type C 2 -C 20 olefins and / or C 8 -C 20 vinyl aromatics as hardeners for the melamine resin ethers are half esters or half amides of Copolymers of maleic anhydride and C 3 -C 8 - ⁇ -olefins of the isobutene, diisobutene and / or 4-methylpentene and / or styrene type with a molar ratio of maleic anhydride / C 3 - C 8 - ⁇ -olefin or styrene or corresponding monomer mixtures of 1: 1 to 1: 5.
- salts of C 1 -C 12 -alkylamines or alkanolamines with CrC 8 - aliphatic, C 7 -C 12 -aromatic or alkylaromatic carboxylic acids or inorganic acids of the hydrochloric acid, sulfuric acid or phosphoric acid type as hardeners for the melamine resin ethers are ethanolammmonium chloride, triethy- lammonium maleate, diethanolammonium phosphate and / or isopropylammonium p-toluenesulfonate.
- thermoplastics Preferred in the process variants for producing the composite materials as thermoplastics are ethylene-vinyl acetate copolymers, partially saponified ethylene-vinyl acetate copolymers, thermoplastic polyurethanes, high-molecular aliphatic and / or aromatic aliphatic polyethers and / or aliphatic and / or aromatic aliphatic polyesters, preferably polycaprolactones and / or unsaturated polyester.
- Copolymers which have a vinyl acetate content of 4 to 50% by mass and melt indices in the range from 0.5 to 400 g / 10 min at 190 ° C./2.16 kp are suitable as ethylene-vinyl acetate copolymers in the production of the composite materials.
- Suitable partially saponified ethylene-vinyl acetate copolymers in the production of the composite materials are copolymers which have a starting vinyl acetate content of 4 to 50% by mass and melt indices in the range from 0.5 to 400 g / 10 min at 190 ° C./2J6 kp, and in which 5 to 50 mol% of the vinyl acetate groups are saponified to vinyl alcohol groups.
- ethylene copolymers with a high vinyl acetate content can be used as talc powdered granules.
- thermoplastic polyurethanes that can be used in the process variants for producing the composite materials are polyurethanes based on tolylene diisocyanate, diphenylmethane diisocyanate, butane diisocyanate and / or hexane diisocyanate as diisocyanate components and butane diol, hexane diol and / or polyalkylene glycols as diol components with molar masses from 2000 to 30000.
- polyethers which can be used in the process variants for producing the composite materials are preferably polyalkylene glycols with molecular weights from 20,000 to 70,000.
- polycaprolactones examples include polycaprolactones with densities of 1.05 to 1.15 g / cm 3 at 60 ° C., viscosities in the range from 500 to 5000 Pas at 100 ° C. and melt indices in the range of 2 to 80 g / 10 min at 160 ° C / 2.16 kp.
- the polycaprolactones can also be ethylene oxide adducts with polycaprolactone.
- Radical formers the thermal decomposition of which is below 210 ° C.
- the thermal decomposition of which is below 210 ° C. of the acyl peroxide, alkyl peroxide, hydroperoxide, peroxycarbonate and / or perester type are preferably used as thermally decomposing radical formers for crosslinking the thermoplastic component in the process for producing composite materials.
- acyl peroxides which can be used as thermally decomposing radical formers in the production of composite materials are benzoyl peroxide, 4-chlorobenzoyl peroxide, 3-methoxybenzoyl peroxide and methylbenzoyl peroxide.
- alkyl peroxides which can be used as thermally decomposing radical formers in the production of composite materials are allyl tert-butyl peroxide, 1 J-bis (tert-butyl peroxy) -3,3,5-trimethyl-cyclohexane, di- (tert.-butylperoxyisopropyl) benzene, diethylaminomethyl-tert.butylperoxide, tert.butylcumylperoxide and tert.butylperoxide.
- peresters and peroxycarbonates which can be used as thermally decomposing radical formers in the production of composite materials are butyl peracetate, cumyl peracetate, cumyl perpropionate, cyclohexyl peracetate, di-tert.butylperadipat, tert.butylcyclobutane percarboxylate, tert.-butyl-2-butyl-2-propyl -2-oat, tert-butyl-1-methylcypropyl percarboxylate and tert-butyl perpropionate.
- ethylene-vinyl acetate copolymers and / or partially saponified ethylene-vinyl acetate copolymers are used as thermoplastics in the production process for composite materials, the necessary crosslinking can also be achieved by adding alkali metal alkoxylates such as sodium methylate, potassium methylate or sodium tert-butoxide.
- gas-releasing propellants in particular sodium hy- bicarbonate, azodicarbonamide, citric acid / bicarbonate propellant systems and / or acid hydrazides such as cyanuric acid hydrazide, toluenesulfonic acid hydrazide or oxo-bis-sulfonic acid hydrazide.
- the foaming can also take place with the metering in of C 3 -C 6 -hydrocarbons such as isobutane or pentane or with metering in of inert gases as physical blowing agents. These blowing agents can also be used if the semi-finished products or molded materials are produced from the molding compound by extrusion.
- the composite materials according to the invention are preferably used in the construction industry, in particular for the production of windows, doors, cladding elements and roof elements in the outdoor area, and in the sports and leisure sector for garden furniture, outdoor seating and for playground design.
- the viscosity measurements were carried out on a high-pressure capillary rheometer, type Rheograph 2002, manufacturer Göttfert Maschinenstoff-Prüfmaschinen GmbH, Buchen, Germany, in accordance with DIN 53014 or ISO 11443.
- the measurements were carried out with a slot nozzle with a gap height H of 2.5 mm and a gap width B of 10 mm.
- the diameter of the feed cylinder was 15 mm.
- a cross-sectional view of the test chamber of the high-pressure capillary rheometer with the slot nozzle used is shown in Fig. 1.
- the pressure was measured at 4 measuring points along the flow channel
- the temperature was measured at 3 measuring points along the flow channel in
- the wall shear stress ⁇ w is calculated from the nozzle geometry and the pressure difference between two pressure transducers.
- the pressure difference ⁇ p is formed from the pressures P 2 and P 4 in order to rule out any interfering effects caused by the nozzle inlet and the nozzle end.
- the wall shear stress taking into account the lateral wall surfaces, results from Eq. (2) _ ⁇ p - (B - H) ⁇ w _ 2 - L - (B + H) (2) with B - gap width, H - gap height, L - measuring gap length.
- the volume throughput V is calculated from the stamp speed v Ko , ben .
- Width of the slot channel is associated with an increase in the shear rate.
- the viscosity is determined with the corrected volume throughput.
- the apparent shear rate ⁇ s in the rectangular gap results from Eq. (5)
- the Arrhenius temperature shift factor a ⁇ is used for semi-crystalline thermoplastics and is defined as
- a melamine dispersion is prepared in a 30 l stirred autoclave by introducing 4.0 kg melamine in 14.2 kg methanol at 95 ° C., and after setting a pH value of 5.9 with 10% HCl in the stirred autoclave, 7.7 kg a 37% formaldehyde solution, which has been preheated to 60 ° C., is metered in under pressure, and the reaction mixture is reacted at a reaction temperature of 95 ° C. and a reaction time of 20 min.
- a pH of 9 is set by adding 10% sodium hydroxide solution, and the etherified melamine resin condensate dissolved in the water-methanol mixture is transferred to a first vacuum evaporator after adding 2.5 kg of butanol which the solution of the etherified melamine resin condensate is concentrated at 82 ° C. to a highly concentrated melamine resin solution which has a solids content of 76% by mass and a butanol content of 8% by mass.
- the highly concentrated solution of the etherified melamine resin is then transferred to a second vacuum evaporator and concentrated at 90 ° C. to a syrupy melt which has a solids content of 96% by mass and a butanol content of 2% by mass.
- the syrupy melt is mixed in a mixing section with 2.27 kg of polyethylene glycol (molecular weight 1,000), into the feed hopper of a laboratory extruder GL 27 D44 (temperature profile 150/200/200/230/230/230/230/230/230/130/130 ° C, extruder speed 150 min '1 ) with vacuum degassing zones after the feed zone and after the reaction zone before the product is discharged, the reaction mixture is degassed at 800 mbar, and after a residence time in the reaction zone of 3J min, the volatile components are degassed at 900 mbar, and the emerging strand is cut in a granulator. To improve the meterability, the granules are powdered with 0.3% by mass of talc.
- the etherified melamine resin condensate has a weight-average molecular weight (GPC) of 24,000 and a proportion of butoxy groups of 0.3% by mass.
- GPC weight-average molecular weight
- thermoplastic melamine resin ethers listed in Table 2 were synthesized in an analogous manner according to the above working procedure.
- Table 2 shows an overview of batch sizes and molar mass weight average of the melamine resin ethers obtained.
- the etherified melamine resin condensate 1 according to 1.1 is fed into the feed hopper at 1.86 kg / h , with 0.8 kg / h an ethylene-vinyl acetate copolymer (vinyl acetate content 28% by mass, melt index 25 g / 10 min at 190 ° C / 2J6 kg), which as a crosslinking agent 0.5% by mass di- ( contains tert-butylperoxyisopropyl) benzene, and metered in at 0.54 kg / h borax and melted at 130 ° C.
- Punched out test specimens from the wood fiber composite panel have a density of 1, 22 g / cm 3 and a tensile modulus of elasticity of 3.1 GPa.
- a melamine dispersion is prepared in a 30 l stirred autoclave by introducing 4.0 kg of melamine in 14.2 kg of methanol at 95 ° C., and after setting a pH of 5.9 with p-toluenesulfonic acid in the stirred autoclave, 7.7 kg a 37% formaldehyde solution, which is preheated to 60 ° C, metered in under pressure, and the reaction mixture is reacted at a reaction temperature of 95 ° C and a reaction time of 20 min.
- a pH of 9 is set by adding 10% sodium hydroxide solution.
- 1.2 kg of polyethylene glycol (molar mass 1000) are then added to the etherified melamine resin condensate dissolved in the water-methanol mixture.
- the aqueous methanolic solution is transferred to a first vacuum evaporator, in which the etherified melamine resin condensate solution is concentrated at 82 ° C. to a highly concentrated melamine resin solution which has a solids content of 78% by mass.
- the highly concentrated solution of the etherified melamine resin is subsequently transferred to a second vacuum evaporator and concentrated at 90 ° C. to a syrupy melt which has a solids content of 97% by mass.
- the syrupy melt of the melamine resin mixed with polyethylene glycol is fed into the feed hopper of a laboratory extruder GL 27 D44 (temperature profile 195/195/195/195/250/250/250/250/135/130/130 ° C, extruder speed 250) at 11 kg / h min "1 ) with vacuum degassing zones after the feed zone and after the reaction zone, metered and degassed at 800 mbar.
- a masterbatch based on an ethylene-vinyl acetate is added to the melamine resin melt by means of a side stream metering at 4.7 kg / h.
- Copolymer (vinyl acetate content 28% by mass, melt index 25 g / 10 min at 190 ° C / 2.16 kg), which as a crosslinking agent benzene 0.5% by mass di- (tert-butylperoxyisopropyl) and 5% by mass Nat - rium-3- (2H-benzotriazol-2-yl) -5-sec-butyl-4-hydroxybenzenesulfate contains, metered, and the resulting melt of the melamine resin ether / ethylene-vinyl acetate copolymer - blends at a melt temperature of 130 ° C homogenized and the emerging strand is cut in a granulator.
- the etherified melamine resin cond ensat has a weight average molecular weight (GPC) of 22,000. Hydroxymethylene amino groups bound to the triazine rings of the melamine resin condensate and -NH-CH 2 -0-CH 2 - NH- groups linking triazine rings cannot be detected in the IR spectrum.
- the thermoplastic melamine resin ethers listed in Table 5 were homogenized with ethylene-vinyl acetate copolymers or partially saponified ethylene-vinyl acetate copolymers to give thermoplastically processable plastic mixtures in accordance with the above procedure.
- Punched out test specimens from the wood fiber composite board have a density of 1, 22 g / cm 3 and a tensile modulus of elasticity of 3.2 GPa.
- a melamine resin dispersion is prepared in a 30 I stirred autoclave by introducing 1.0 kg of melamine in 13.9 kg of methanol at 95 ° C., and after setting a pH of 6.0 with 10% HCl in the stirred autoclave, 2.25 kg 37% formaldehyde solution, which is preheated to 60 ° C, metered in under pressure, and the reaction mixture is reacted at a reaction temperature of 90 ° C and a reaction time of 15 min.
- a pH of 9 is adjusted by adding 10% NaOH.
- thermoplastically processable melamine resin ether 1 In the feed hopper of a Werner & Pfleiderer twin screw extruder ZSK 30, UD 48, a 7: 3 mixture of the thermoplastically processable melamine resin ether 1 according to 1.1 and a granulate based on an ethylene-vinyl acetate copolymer (vinyl acetate content 28% by mass, melt index 150 g / 10 min at 190 ° C / 2J6 kg) dosed at 4.5 kg / h and melted at a melt temperature of 130 ° C.
- ethylene-vinyl acetate copolymer (vinyl acetate content 28% by mass, melt index 150 g / 10 min at 190 ° C / 2J6 kg) dosed at 4.5 kg / h and melted at a melt temperature of 130 ° C.
- the spruce wood chips impregnated with the melamine resin solution and 0.5 kg / h of polyethylene glycol (molecular weight 35,000) are metered into the melt via a side-stream metering at 10 kg / h, homogeneously distributed in the melt at 130 ° C., and the mixture is vacuum degassed at 850 mbar subjected. After degassing, an EVA masterbatch containing 5% by mass of phthalic anhydride, 20% by mass of azodicarbonamide and 2.5% by mass is introduced into the melt at a melt temperature of 125 ° C.
- the molding compound containing wood chips is melted in an extruder with a U-profile tool at 140 ° C, discharged through the U-profile tool at 180 ° C and removed as a cross-linked profile.
- Punched out test specimens from the wood fiber composite panel have a density of 0.95 g / cm 3 and a tensile modulus of elasticity of 2.9 GPa.
- LD 44 extruder with side-flow metering for solid and liquid media, vacuum degassing and plate tool (4.0 x 100.0 mm), an ethylene-vinyl acetate copolymer is loaded into the feed hopper at 3.0 kg / h (Vinyl acetate content 20% by mass, melt index 25 g / 10 min at 190 ° C / 2J6 kp) melted at 130 ° C.
- Punched out test specimens from the wood fiber composite panel have a density of 1.2 g / cm 3 and a tensile modulus of elasticity of 5.0 GPa.
- Test specimens made from the plate showed fire behavior B1 (flame retardant) in accordance with DIN 4102.
- the sintered mixture containing oak wood particles is melted in a plate tool with a movable die at 155 ° C / 80 bar and foamed after the pressure has been reduced to 2 bar.
- the foamed cross-linked composite plate has a density of 0.82 g / cm 3 .
- Test specimens made from the plate showed fire behavior B1 (flame retardant) in accordance with DIN 4102.
- thermoplastic melamine resin 1 When a melt temperature of 145 ° C is reached, the speed is reduced to 1200 min '1 , and then Cooling to a melt temperature of 110 ° C., 0.3 kg of the thermoplastic melamine resin 1 according to 1.1 are metered onto the whirled sinter mixture.
- the speed is reduced to 1200 min "1 , and after cooling to a melt temperature of 120 ° C, 250 g of the melamine resin 4 according to 1.1 are metered onto the whirled sintered mixture.
- the standard test rods have a density of 0.90 g / cm 3 and a tensile modulus of elasticity of 2.8 GPa and, in accordance with DIN 4102, show fire behavior B1 (flame-retardant).
- Table 1 Flow correction factor - F D with different ratios of nozzle widths to nozzle heights.
- Table 2 batch size (in kg) and temperature profile (in ° C) for the production of thermoplastic melamine resins and the molar mass weight average (GPC) of the products obtained
- Table 3 Viscosity values of the uncrosslinked compound shown in 1.2 (Compound I, see Tab. 4) at three melt temperatures and a nozzle gap of 2.5 mm
- Table 4 Composition (in kg / h), homogenization temperature (T h0 mo in ° C), take-off temperature (T ab in ° C) and mechanical properties of the composite materials produced according to Example 1.2 (density in g / cm 3 , tensile E- Module in GPa) and the viscosity of the uncrosslinked compounds ( ⁇ c o mp at 130 ° C in Pa * s).
- Table 5 Composition and homogenization temperature (Th 0mo in ° C) of the thermoplastically processable plastics produced according to Example 2 ⁇ (resin type and batch sizes see Table 2),
- Table 6 Composition (in kg / h), homogenization temperature (T hom o in ° C), take-off temperature (T ab in ° C) and mechanical properties of the composite materials (density in g / cm 3 , tensile modulus in GPa) , and the viscosity of the uncrosslinked compound ( ⁇ c omp at 130 ° C in Pa * s).
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Abstract
L'invention concerne des matériaux composites qui contiennent des matériaux plastiques et du bois et qui sont constitués de 55 à 90 % en masse de bois sous forme de farine de bois, particules de bois, fibres de bois et/ou copeaux de bois, et de 45 à 10 % en masse d'éthers de résine mélamine partiellement réticulés ou de mélanges constitués de thermoplastes partiellement réticulés et d'éthers de résine mélamine réticulés. Selon l'invention, les matériaux plastiques contenus dans les matériaux composites se présentent sous la forme d'une mousse. Les matériaux composites selon l'invention sont produits par homogénéisation des composants dans l'extrudeuse, par imprégnation préalable du bois avec les résines mélamine dans le mélangeur à vis puis homogénéisation des composants dans l'extrudeuse, ou au moyen d'un procédé de frittage, chacune de ces possibilités de production étant suivie d'une étape de formage. Lesdits matériaux composites sont conçus pour être utilisés dans l'industrie du bâtiment, ainsi que dans le secteur des sports et des loisirs.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10333893A DE10333893A1 (de) | 2003-07-22 | 2003-07-22 | Kunststoffe und Holz enthaltende Verbundwerkstoffe |
| PCT/EP2004/008399 WO2005009701A2 (fr) | 2003-07-22 | 2004-07-21 | Materiaux composites contenant des materiaux plastiques et du bois |
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| EP1654322A2 true EP1654322A2 (fr) | 2006-05-10 |
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| EP04763532A Withdrawn EP1654322A2 (fr) | 2003-07-22 | 2004-07-21 | Materiaux composites contenant des materiaux plastiques et du bois |
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| Country | Link |
|---|---|
| US (1) | US20070267609A1 (fr) |
| EP (1) | EP1654322A2 (fr) |
| JP (1) | JP2006528089A (fr) |
| KR (1) | KR20060037386A (fr) |
| CN (1) | CN1906247A (fr) |
| CA (1) | CA2532955A1 (fr) |
| DE (1) | DE10333893A1 (fr) |
| WO (1) | WO2005009701A2 (fr) |
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| DE10361878A1 (de) * | 2003-12-19 | 2005-07-14 | Ami-Agrolinz Melamine International Gmbh | Flammschutzmischung für lignocellulosische Verbundstoffe |
| FR2867160B1 (fr) * | 2004-03-05 | 2006-07-14 | Oreal | Emballage revetu d'un vernis de protection vis-a-vis de la lumiere |
| NZ530339A (en) | 2004-06-23 | 2007-01-26 | Nz Forest Research Inst Ltd | Method for producing wood fibre pellets |
| DE102005029685A1 (de) * | 2005-06-20 | 2006-12-21 | Ami-Agrolinz Melamine International Gmbh | Verbundwerkstoff |
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| NZ544493A (en) | 2005-12-22 | 2008-07-31 | Nz Forest Research Inst Ltd | Method for producing wood fibre composite products |
| US20080006960A1 (en) * | 2006-07-06 | 2008-01-10 | Sara Rose International Inc. | Melamine utensil and manufacturing method thereof |
| DE102006034608A1 (de) * | 2006-07-21 | 2008-02-14 | Ami-Agrolinz Melamine International Gmbh | Thermoplastisch verarbeitbare Duroplastformmassen mit verbessertem Eigenschaftsspektrum |
| US20080277833A1 (en) * | 2007-05-09 | 2008-11-13 | Sara Rose International Inc. | Melamine utensil and manufacturing method thereof |
| WO2008144333A1 (fr) * | 2007-05-16 | 2008-11-27 | Nova Chemicals Inc. | Articles composites de plastique cellulosique |
| DE102007041438A1 (de) * | 2007-08-28 | 2009-03-05 | Ami Agrolinz Melamine International Gmbh | Verbundwerkstoff, Verwendung eines Verbundwerkstoffes und Verfahren zur Herstellung eines Verbundwerkstoffes |
| AT507040B1 (de) * | 2008-06-19 | 2013-11-15 | Lackinger Gerald Mag | Verbundkörper |
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| JPS5790050A (en) * | 1980-11-26 | 1982-06-04 | Toyota Central Res & Dev Lab Inc | Preparation of composite material consisting of clay mineral and organic polymer |
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-
2003
- 2003-07-22 DE DE10333893A patent/DE10333893A1/de not_active Withdrawn
-
2004
- 2004-07-21 KR KR1020067001419A patent/KR20060037386A/ko not_active Withdrawn
- 2004-07-21 US US10/565,463 patent/US20070267609A1/en not_active Abandoned
- 2004-07-21 WO PCT/EP2004/008399 patent/WO2005009701A2/fr not_active Ceased
- 2004-07-21 JP JP2006520817A patent/JP2006528089A/ja not_active Withdrawn
- 2004-07-21 EP EP04763532A patent/EP1654322A2/fr not_active Withdrawn
- 2004-07-21 CN CNA2004800212777A patent/CN1906247A/zh active Pending
- 2004-07-21 CA CA002532955A patent/CA2532955A1/fr not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2005009701A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070267609A1 (en) | 2007-11-22 |
| JP2006528089A (ja) | 2006-12-14 |
| WO2005009701A3 (fr) | 2005-06-30 |
| KR20060037386A (ko) | 2006-05-03 |
| CN1906247A (zh) | 2007-01-31 |
| WO2005009701A2 (fr) | 2005-02-03 |
| DE10333893A1 (de) | 2005-02-10 |
| CA2532955A1 (fr) | 2005-02-03 |
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