EP1343630A1 - Multi-layered composite material with organic sandwich layers based on rubber - Google Patents
Multi-layered composite material with organic sandwich layers based on rubberInfo
- Publication number
- EP1343630A1 EP1343630A1 EP01991803A EP01991803A EP1343630A1 EP 1343630 A1 EP1343630 A1 EP 1343630A1 EP 01991803 A EP01991803 A EP 01991803A EP 01991803 A EP01991803 A EP 01991803A EP 1343630 A1 EP1343630 A1 EP 1343630A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- rubber
- laminate according
- binder
- groups
- 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- Withdrawn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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 45
- 239000005060 rubber Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000010276 construction Methods 0.000 claims abstract description 8
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 150000004291 polyenes Chemical class 0.000 claims abstract 5
- 239000010410 layer Substances 0.000 claims description 29
- 239000011230 binding agent Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 229920002857 polybutadiene Polymers 0.000 claims description 17
- 239000005062 Polybutadiene Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000004005 microsphere Substances 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 claims description 10
- 239000004604 Blowing Agent Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- -1 rheology aids Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 239000002318 adhesion promoter Substances 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000000518 rheometry Methods 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004606 Fillers/Extenders Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000003981 vehicle Substances 0.000 claims description 4
- 150000003752 zinc compounds Chemical class 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 238000005304 joining Methods 0.000 claims description 3
- 229920001083 polybutene Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 150000002832 nitroso derivatives Chemical class 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 150000003349 semicarbazides Chemical class 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- 229920002943 EPDM rubber Polymers 0.000 claims 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 244000043261 Hevea brasiliensis Species 0.000 claims 1
- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 229920000800 acrylic rubber Polymers 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 20
- 230000001070 adhesive effect Effects 0.000 abstract description 20
- 229920002994 synthetic fiber Polymers 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- WKVZMKDXJFCMMD-UVWUDEKDSA-L (5ar,8ar,9r)-5-[[(2r,4ar,6r,7r,8r,8as)-7,8-dihydroxy-2-methyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-6-yl]oxy]-9-(4-hydroxy-3,5-dimethoxyphenyl)-5a,6,8a,9-tetrahydro-5h-[2]benzofuro[6,5-f][1,3]benzodioxol-8-one;azanide;n,3-bis(2-chloroethyl)-2-ox Chemical compound [NH2-].[NH2-].Cl[Pt+2]Cl.ClCCNP1(=O)OCCCN1CCCl.COC1=C(O)C(OC)=CC([C@@H]2C3=CC=4OCOC=4C=C3C(O[C@H]3[C@@H]([C@@H](O)[C@@H]4O[C@H](C)OC[C@H]4O3)O)[C@@H]3[C@@H]2C(OC3)=O)=C1 WKVZMKDXJFCMMD-UVWUDEKDSA-L 0.000 description 8
- 235000010216 calcium carbonate Nutrition 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- URMSIZAJUFVFFU-UHFFFAOYSA-N hydroxy-(6-hydroxysulfonothioyloxyhexoxy)-oxo-sulfanylidene-lambda6-sulfane Chemical compound OS(=O)(=S)OCCCCCCOS(O)(=O)=S URMSIZAJUFVFFU-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229960004011 methenamine Drugs 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- ASRMWYDEZPXXBA-UHFFFAOYSA-N (sulfonylamino)urea Chemical class NC(=O)NN=S(=O)=O ASRMWYDEZPXXBA-UHFFFAOYSA-N 0.000 description 1
- XYLFFOSVQCBSDT-UHFFFAOYSA-N 1,2-dinitrosobenzene Chemical compound O=NC1=CC=CC=C1N=O XYLFFOSVQCBSDT-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical class CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000103 Expandable microsphere Polymers 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000004838 Heat curing adhesive Substances 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 150000004008 N-nitroso compounds Chemical class 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical class [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical class [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011185 multilayer composite material Substances 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical class [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1207—Heat-activated adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]
Definitions
- the present invention relates to a multilayer laminate composed of two outer metal sheets and an intermediate layer containing an organic binder matrix, and to a method for producing these multilayer laminates.
- Multi-layer laminates and processes for the production of multi-layer laminates are widely used wherever it is important to use specifically light structures with a high level of strength and / or rigidity.
- Specifically lightweight materials are increasingly being used in machine, vehicle or device construction, especially in automobile construction, in order to reduce the weight of the vehicles, for example.
- aluminum, fiber composite materials or high-strength body steels are used.
- the use of increasingly high strength materials with increasingly thin sheet thicknesses can meet the strength requirements in very many cases, but not the requirements for the rigidity of the components.
- Lightweight construction with increasingly thin sheet thicknesses reaches its limits especially where, due to the geometry, reduced cross-sections of the components whose rigidity no longer meets the requirements for usability.
- Examples of known multilayer composites are web plates, hump and trapezoidal composite plates in their various forms. Geometries produced by reshaping with an inner, supporting intermediate layer form the basis for the technical solutions of this type of lightweight construction.
- Intermediate layers are suitable, inter alia, foam core fillings with polymeric foams or also with metallic foams or inorganic foams based on silicate.
- Preferred technical applications today are primarily a three-layer material composite consisting of two cover sheets and an intermediate layer made of a viscoelastic material. Due to the relatively thin intermediate layer, which generally hardly contributes to increasing the rigidity, this type of composite sheet is mainly used because of its vibration-damping properties.
- DE-A-3905871 discloses a composite material for thermal insulation and / or sound absorption that has a structurally stable covering layer made of a thermally stable metal foil on at least one side.
- a thermally resistant, highly porous, inorganic material is proposed as the insulation layer, for example foamed glass with a sponge-like structure or gas concrete or foamed ceramic or clay mineral materials. Exhaust areas of an automobile are proposed as an application for this composite material in the automotive sector.
- this composite panel consists of a cover and base plate and in between a web material made of wire or a metal grid as web material, which prior to its connection to the outer Metal plates is deformed by flattening its lattice nodes. This creates enlarged connection areas between the metal grid and the metal panels, which should also enable reshaping.
- connection of the metal grid to the cover plates can in principle be done by adhesive processes, it should preferably be done by welding processes. This document does not provide any further information on suitable adhesives.
- WO 00/13890 describes glued multilayer composite panels and methods for producing multilayer composite panels which consist of two outer metal plates which serve as upper and lower base plates and which are bonded to a deformable connecting intermediate layer.
- the deformable web material lying in the intermediate layer is covered with the Lid and base plate connected by means of a foaming adhesive that fills the voids remaining in the composite.
- the web material lying between the metal plates can consist of an expanded metal mesh, a wire mesh or a web plate, and it can include a multi-layer sequence of expanded metal meshes, wire meshes, web plates with intermediate plates that are impermeable or permeable to the adhesive.
- suitable compositions of the adhesive in this document.
- the binder is composed such that it enables the production of weight-optimized, lightweight laminates with an acoustic and / or stiffening effect.
- the binder system can contain, for example, "chemical” blowing agents, or expandable hollow microspheres or expanded hollow microspheres.
- Another subject is a process for the production of the aforementioned multilayer laminate, which comprises the following essential process steps: a) application of the vulcanisable to be used according to the invention
- Roller application device on a metal sheet b) if applicable, applying the fabric to the rubber composition, c) joining the second sheet of metal, d) if necessary pressing the composite to the predetermined distance, e) curing the rubber adhesive layer by heating the composite to temperatures between 80 ° C. 250 ° C, preferably between 160 ° C and 200 ° C.
- the last-mentioned step e) can optionally also be carried out in several stages.
- the binder composition can be precured in a first curing stage.
- the multilayer laminate can then be subjected to known forming processes and punching processes, so that, for example, preformed body components can be produced from the laminate, which are joined in a later work step using conventional joining methods such as gluing and / or welding, riveting, screwing, flanging.
- the final hardening of the binder layer then takes place in a later process step e.g. in the paint oven after electro-painting the body shell of a vehicle.
- the vulcanizable rubber composition is not applied directly to a metal sheet, but in a type of "transfer method" to an intermediate carrier.
- This intermediate carrier can be an anti-adhesive cover film, but it can also be the (reinforcing) flat structure of the intermediate layer for the multilayer laminate.
- the binder layer for the intermediate storage can be provided with a cover film which, if necessary, is removed before the binder-coated fabric is applied to the metal sheets.
- the binder matrix used according to the invention essentially consists of heat-curing, reactive compositions based on natural and / or synthetic rubbers (ie elastomers containing olefinic double bonds) and vulcanizing agents which contain at least one of the following substances: one or more liquid rubbers and / or solid rubbers or elastomers,
- Suitable one-component binders are e.g. described in WO 96/23040, suitable two-component binders are e.g. in EP-A-356715.
- the teaching of these documents with regard to the rubber compositions is expressly part of the present application.
- liquid rubbers or elastomers can be selected from the following group of homo- and / or copolymers:
- Polybutadienes in particular the 1, 4- and 1, 2-polybutadienes, polybutenes, polyisobutylenes, 1, 4- and 3,4-polyisoprenes, styrene-butadiene copolymers, butadiene-acrylonitrile copolymers, these polymers being terminal and / or (statistically distributed ) may have lateral functional groups. Examples of such functional groups are hydroxyl, amino, carboxyl, carboxylic anhydride or epoxy groups.
- the molecular weight of these liquid rubbers is typically below 20,000, preferably between 900 and 10,000.
- the proportion of liquid rubber in the overall composition depends on the desired rheology of the uncured composition and the desired mechanical properties of the cured composition.
- the proportion of liquid rubber or elastomer normally varies between 5 and 50% by weight of the total formulation. It has proven to be advantageous, preferably mixtures of liquid rubbers of different molecular weights and different configuration in relation to the remaining double bonds. To achieve optimum adhesion to the various substrates, a proportion is used in the particularly preferred formulations
- Liquid rubber component with hydroxyl groups or acid anhydride groups used. At least one of the liquid rubbers should contain a high proportion of cis-1,4 double bonds, another a high proportion of vinyl double bonds.
- suitable rubbers are polybutadiene, preferably with a very high proportion of cis-1,4 double bonds (typically over 95%), styrene-butadiene rubber, Butadiene acrylonitrile rubber, synthetic or natural isoprene rubber, butyl rubber or polyurethane rubber.
- thermoplastic polymer powders brings a significant improvement in tensile shear strength while maintaining a very high elongation at break, which was previously unusual for structural adhesives. This enables tensile shear strengths of over 15 MPa to be achieved, with the elongation at break being clearly over 15%, very often over 20%.
- thermoplastic polymer powders are suitable as polymer powders, for example vinyl acetate, either as a homopolymer or as a copolymer with ethylene, such as other olefins and acrylic acid derivatives, polyvinyl chloride, vinyl chloride ⁇ / inyl acetate copolymers, styrene copolymers, as described, for example, in DE-A -4034725 are described, polymethyl methacrylate and its copolymers with other (meth) acrylic acid esters and functional comonomers, as described for example in DE-C-2454235, or polyvinyl acetals such as polyvinyl butyral.
- vinyl acetate either as a homopolymer or as a copolymer with ethylene, such as other olefins and acrylic acid derivatives
- polyvinyl chloride vinyl chloride ⁇ / inyl acetate copolymers
- styrene copolymers as described, for example,
- the average particle size should be less than 1 mm, preferably less than 350 ⁇ m, very particularly preferably between 100 and 20 ⁇ m. Most notably polyvinyl acetate or copolymers based on ethylene vinyl acetate are preferred.
- thermoplastic polymer powder The amount of thermoplastic polymer powder added depends on the desired strength range, it is between 2 and 20% by weight, based on the total composition, a particularly preferred range is 10 to 15%.
- the vulcanization system Since the crosslinking or curing reaction of the rubber composition has a decisive influence on the tensile shear strength and on the elongation at break of the cured adhesive composition, the vulcanization system must be selected and coordinated with particular care.
- a large number of vulcanization systems based on elemental sulfur as well as vulcanization systems without elemental sulfur are suitable, the latter being the vulcanization systems based on thiuram disulfides. Vulcanization systems without sulfur compounds can also be used.
- the latter include vulcanization systems based on organic peroxides, polyfunctional amines, quinones, p-benzoquinone dioxime, p-nitrosobenzene and dinitrosobenzene, or crosslinking with (blocked) diisocyanates. Vulcanization systems based on elemental sulfur and organic vulcanization accelerators and zinc compounds are particularly preferred.
- the powdered sulfur is used in amounts of 1 to 15% by weight, based on the total composition, and amounts of between 4 and 8% are particularly preferably used.
- Suitable organic accelerators are the dithiocarbamates (in the form of their ammonium or metal salts), xanthates, thiuram compounds (monosulfides and disulfides), thiazole compounds, aldehyde / amine accelerators (e.g. hexamethylene tetramine) and
- Guanidine accelerator dibenzothiazyl disulfide (MBTS) is very particularly preferred.
- MBTS dibenzothiazyl disulfide
- These organic accelerators are used in amounts of between 2 and 8% by weight, based on the overall formulation, preferably between 3 and 6%.
- a choice can be made between the zinc salts of fatty acids, zinc dithiocarbamates, basic zinc carbonates and, in particular, finely divided zinc oxide.
- the content of zinc compounds is in the range between 1 and 10% by weight, preferably between 3 and 7% by weight.
- other typical rubber Vulcanization aids such as fatty acids (eg stearic acid) may be present in the formulation.
- compositions to be used according to the invention generally already have very good adhesion to the substrates to be bonded due to the content of liquid rubber with functional groups, if necessary, tackifiers and / or adhesion promoters can be added.
- tackifiers and / or adhesion promoters can be added.
- hydrocarbon resins, phenolic resins, terpene-phenolic resins, resorcinol resins or their derivatives, modified or unmodified resin acids or esters (abietic acid derivatives), polyamines, polyamino amides, anhydrides and anhydride-containing copolymers are suitable.
- the addition of polyepoxide resins in small amounts ( ⁇ 1% by weight) can also improve the adhesion on some substrates.
- the solid epoxy resins with a molecular weight of significantly more than 700 are preferably used in finely ground form, so that the formulations are nevertheless essentially free of epoxy resins, in particular those with a molecular weight of less than 700. If tackifiers or adhesion promoters are used, their nature depends and the amount of the polymer composition of the adhesive / sealant, the desired strength of the cured composition and the substrate to which the composition is applied.
- Typical tackifying resins such as the terpene phenolic resins or resin acid derivatives are normally used in concentrations between 5 and 20% by weight, typical adhesion promoters such as polyamines, polyaminoamides or resorcinol derivatives are used in the range between 0.1 and 10% by weight.
- blowing agents can be used to achieve foaming during the curing process, examples being organic blowing agents from the class of azo compounds, N-nitroso compounds, sulfonylhydrazides or sulfonylsemicarbazides.
- azo compounds to be used according to the invention include azobisisobutyronitrile and in particular azodicarbonamide, from the class of nitroso compounds the di-nitroso-pentamethylenetetramine is mentioned, from the class of sulfohydrazides 4,4'- Oxybis (benzenesulfonic acid hydrazide), the diphenylsulfone-3,3'-disulfohydrazide or the benzene-1,3-disulfohydrazide and from the class of the semicarbazides the p-
- microspheres are described, for example, in EP-A-559254, EP-A-
- hollow microspheres which have already been expanded can also be used or also used.
- expandable / expanded hollow microspheres can be combined in any quantity ratio with the above-mentioned "chemical" blowing agents.
- the chemical blowing agents are in foamable
- compositions in amounts between 0.1 and 3% by weight, preferably between 0.2 and 2% by weight, using hollow microspheres between 0.1 and 4% by weight, preferably between 0.2 and 2% by weight.
- compositions to be used according to the invention are preferably free from plasticizers for the thermoplastic polymer.
- they are free from phthalic acid esters.
- the rheology of the uncured composition and / or the mechanical properties of the cured composition may need to be adjusted by the addition of so-called extender oils, i.e. aliphatic, aromatic or naphthenic oils.
- extender oils i.e. aliphatic, aromatic or naphthenic oils.
- this influencing preferably takes place through the appropriate selection of the low molecular weight liquid rubbers or through the use of low molecular weight polybutenes or polyisobutylenes. If extender oils are used, amounts in the range between 2 and 15% by weight are used.
- the fillers can be selected from a large number of materials, in particular chalks, naturally ground or precipitated calcium carbonates, calcium magnesium carbonates, silicates, heavy spar, graphite and carbon black.
- Flake-like fillers such as, for example, vermiculite, mica, talc or similar sheet silicates, are also suitable as fillers. It may It should be expedient that at least some of the fillers have been surface-pretreated. In particular, a coating with stearic acid has proven to be expedient for the various calcium carbonates or chalks in order to reduce the moisture introduced and to reduce the sensitivity to moisture of the cured composition.
- the compositions according to the invention generally contain between 1 and 20% by weight, preferably between 5 and 15% by weight, calcium oxide.
- the total proportion of fillers in the formulation can vary between 10 and 70% by weight, the preferred range is between 25 and 60% by weight.
- compositions according to the invention Against the thermal, thermooxidative or ozone depletion of the compositions according to the invention, conventional stabilizers such as sterically hindered phenols or amine derivatives are used, typical quantity ranges for these stabilizers are 0.1 to 5% by weight.
- the rheology of the compositions according to the invention can normally be brought into the desired range by the selection of the fillers and the quantitative ratio of the low-molecular liquid rubbers
- conventional rheological aids such as e.g. pyrogenic silicas, bentones or fibrillated or pulp short fibers in the range between 0.1 and 7% can be added.
- other conventional auxiliaries and additives can be used in the compositions according to the invention.
- these flat structures can consist of an expanded metal grid, a wire grid, a web plate or a perforated plate.
- Such metallic fabrics are for example from WO 00/13890 or known from DE-A-3935120. The ones mentioned there
- the two outer metal sheets have a thickness between 0.1 and 0.5 mm, preferably between 0.2 and 0.3 mm.
- These sheets can be normal steel sheets, but also steel sheets that have been refined by the various galvanizing processes, here are the electrolytically galvanized, hot-dip galvanized sheets and the corresponding thermally post-treated or galvanized or subsequently phosphated steel sheets as well as aluminum sheets or magnesium sheets.
- the laminate has a total layer thickness between 1 mm and 2 mm, preferably between 1.2 and 1.8 mm.
- the above-mentioned 1- or 2-component heat-curing adhesive / sealant compositions are used for the production of multilayer laminates, which are preferably used for the body-in-white in the automotive industry.
- the curing of the compositions should be in a temperature range between 80 and 240 ° C in about 10 to 35 minutes. , possibly in two stages. Temperatures between 160 and 200 ° C are preferably used in the shell.
- a decisive advantage of the compositions used according to the invention is that here too all advantages of the rubber-based adhesives / sealants known per se can be used, i.e.
- compositions used according to the invention have the following preferred compositions: % By weight Chemical name
- Examples 1 to 3 below list the compositions of 3 rubber adhesives used in the manufacture of multilayer laminates.
- Example 2 Relining adhesive based on rubber
- Loss factor d as a function of the excitation frequency kHz structural adhesive according to example 1
- the good acoustic properties of the laminates are documented by the loss factor d compared to normal single-layer solid steel.
Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Adhesive compositions based on vulcanisable rubber materials, containing liquid polyenes, optionally solid rubbers and/or thermoplastic polymer powders and vulcanising agents are suitable for the production of multi-layered laminates, comprising two external metal sheets and an adhesive sandwich layer. Said sandwich layer can optionally comprise additional flat materials made from synthetic fibres and/or metallic expanded mesh, wire mesh or similar. Said multi-layered laminates are suitable for the inclusion of intrinsically light materials in machine, vehicle or instrument construction, in particular in automobile construction.
Description
mehrschichtige Verbundmaterialien mit organischen Zwischenschichten auf autschukbasismultilayer composite materials with organic intermediate layers based on rubber
Die vorliegende Erfindung betrifft ein mehrschichtiges Laminat aus zwei äußeren Metallblechen und einer Zwischenschicht enthaltend eine organische Bindemittelmatrix sowie ein Verfahren zur Herstellung dieser mehrschichtigen Laminate.The present invention relates to a multilayer laminate composed of two outer metal sheets and an intermediate layer containing an organic binder matrix, and to a method for producing these multilayer laminates.
Mehrschichtige Laminate und Verfahren zur Herstellung von mehrschichtigen Laminaten finden überall dort breite Anwendung, wo es darauf ankommt spezifisch leichte Strukturen bei hohem Festigkeits- und / oder Steifigkeitsniveau einzusetzen.Multi-layer laminates and processes for the production of multi-layer laminates are widely used wherever it is important to use specifically light structures with a high level of strength and / or rigidity.
Spezifisch leichte Werkstoffe werden in steigendem Maße im Maschinen-, Fahrzeug- oder Gerätebau, insbesondere im Automobilbau eingesetzt, um das Gewicht z.B. der Fahrzeuge zu reduzieren. Beispielsweise werden Aluminium, Faserverbundwerkstoffe oder auch hochfeste Karosseriestähle eingesetzt. Der Einsatz von immer höher festen Werkstoffen mit immer dünneren Blechstärken kann zwar in sehr vielen Fällen die Festigkeitsanforderungen erfüllen, nicht jedoch die Anforderungen an die Steifigkeit der Bauteile. Der Leichtbau mit immer dünneren Blechstärken stößt vor allem dort an Grenzen wo, geometrisch bedingt, durch reduzierte Querschnitte der Bauteile deren Steifigkeit den Anforderungen an die Gebrauchstüchtigkeit nicht mehr genügt. Beispiele für bekannte Mehrschichtverbunde sind Stegbleche, Höcker- und Trapez-Verbundbleche in ihren vielfältigen Ausführungsformen. Durch Umformung hergestellte Geometrien mit einer innen liegenden, stützenden Zwischenlage bilden dabei die Grundlage für die technischen Lösungen dieser Art von Leichtbauweisen. Als Zwischenlagen eignen sich dabei unter anderem Schaumkernfüllungen mit polymeren Schäumen oder auch mit metallischen Schäumen oder anorganischen Schäumen auf silikatischer Basis.
Bevorzugte technische Anwendungen findet heute vor allem ein dreischichtiger Werkstoffverbund aus zwei Deckblechen und einer Zwischenschicht aus einem viskoelastischen Material. Diese Art von Verbundblechen werden auf Grund der relativ dünnen Zwischenschicht, die in der Regel kaum zur Steifigkeitserhöhung beiträgt, hauptsächlich wegen ihrer schwingungsdämpfenden Eigenschaften verwendet.Specifically lightweight materials are increasingly being used in machine, vehicle or device construction, especially in automobile construction, in order to reduce the weight of the vehicles, for example. For example, aluminum, fiber composite materials or high-strength body steels are used. The use of increasingly high strength materials with increasingly thin sheet thicknesses can meet the strength requirements in very many cases, but not the requirements for the rigidity of the components. Lightweight construction with increasingly thin sheet thicknesses reaches its limits especially where, due to the geometry, reduced cross-sections of the components whose rigidity no longer meets the requirements for usability. Examples of known multilayer composites are web plates, hump and trapezoidal composite plates in their various forms. Geometries produced by reshaping with an inner, supporting intermediate layer form the basis for the technical solutions of this type of lightweight construction. Intermediate layers are suitable, inter alia, foam core fillings with polymeric foams or also with metallic foams or inorganic foams based on silicate. Preferred technical applications today are primarily a three-layer material composite consisting of two cover sheets and an intermediate layer made of a viscoelastic material. Due to the relatively thin intermediate layer, which generally hardly contributes to increasing the rigidity, this type of composite sheet is mainly used because of its vibration-damping properties.
Aus der DE-A-3905871 ist ein Verbundmaterial zur Wärmeisolierung und / oder Schalldämpfung bekannt, das auf mindestens einer Seite eine strukturfeste Hüllschicht aus einer thermisch stabilen Metallfolie aufweist. Als Isolationsschicht wird ein thermisch beständiges, hochporöses, anorganisches Material vorgeschlagen, beispielsweise aufgeschäumtes Glas mit schwammartiger Struktur oder Gasbeton oder aufgeschäumte keramische oder tonmineralische Materialien. Als Anwendung für dieses Verbundmaterial im Automobilbereich werden Auspuffbereiche eines Automobils vorgeschlagen.DE-A-3905871 discloses a composite material for thermal insulation and / or sound absorption that has a structurally stable covering layer made of a thermally stable metal foil on at least one side. A thermally resistant, highly porous, inorganic material is proposed as the insulation layer, for example foamed glass with a sponge-like structure or gas concrete or foamed ceramic or clay mineral materials. Exhaust areas of an automobile are proposed as an application for this composite material in the automotive sector.
Aus der DE-A-3935120 ist ein Verfahren zur Herstellung von Mehrschicht- Verbundplatten bekannt, bei dem diese Verbundplatte aus einer Deckel- und Bodenplatte besteht und dazwischen liegend ein Stegmaterial aus Draht oder ein Metallgitter als Stegmaterial aufweist, welches vor seiner Verbindung mit den äußeren Metalltafeln unter Abflachung seiner Gitterknotenpunkte verformt wird. Dadurch werden vergrößerte Verbindungsflächen zwischen dem Metallgitter und dem Metalltafeln geschaffen die auch Umformungen ermöglichen sollen. Die Schrift führt zwar aus, daß die Verbindung des Metallgitters mit den Deckblechen grundsätzlich durch Klebvorgänge geschehen kann, jedoch soll sie vorzugsweise durch Verschweißprozesse erfolgen. Nähere Angaben über geeignete Klebstoffe sind dieser Schrift nicht zu entnehmen.From DE-A-3935120 a method for the production of multilayer composite panels is known, in which this composite panel consists of a cover and base plate and in between a web material made of wire or a metal grid as web material, which prior to its connection to the outer Metal plates is deformed by flattening its lattice nodes. This creates enlarged connection areas between the metal grid and the metal panels, which should also enable reshaping. Although the document states that the connection of the metal grid to the cover plates can in principle be done by adhesive processes, it should preferably be done by welding processes. This document does not provide any further information on suitable adhesives.
Die WO 00/13890 beschreibt geklebte Mehrschicht-Verbundplatten und Verfahren zur Herstellung von Mehrschicht-Verbundplatten, die aus zwei äußeren Metallplatten bestehen, welche als obere und untere Basisplatten dienen und welche an eine deformierbare verbindende Zwischenschicht gebunden sind. Dabei wird das in der Zwischenschicht liegende verformbare Stegmaterial mit der
Deckel- und Bodenplatte mittels eines aufschäumenden Klebers verbunden, der die im Verbund verbleibenden Hohlräume ausfüllt. Das zwischen den Metallplatten liegende Stegmaterial kann als dabei aus einem Streckmetallgitter, einem Drahtgitter oder einem Stegblech bestehen und es kann eine mehrlagige Abfolge aus Streckmetallgittern, Drahtgittern, Stegblechen mit für den Kleber undurchlässigen oder durchlässigen Zwischenblechen beinhalten. Eine Lehre über geeignete Zusammensetzungen des Klebers ist dieser Schrift nicht zu entnehmen.WO 00/13890 describes glued multilayer composite panels and methods for producing multilayer composite panels which consist of two outer metal plates which serve as upper and lower base plates and which are bonded to a deformable connecting intermediate layer. The deformable web material lying in the intermediate layer is covered with the Lid and base plate connected by means of a foaming adhesive that fills the voids remaining in the composite. The web material lying between the metal plates can consist of an expanded metal mesh, a wire mesh or a web plate, and it can include a multi-layer sequence of expanded metal meshes, wire meshes, web plates with intermediate plates that are impermeable or permeable to the adhesive. There is no teaching of suitable compositions of the adhesive in this document.
Angesichts dieses Standes der Technik haben sich die Erfinder die Aufgabe gestellt, Bindemittel bereitzustellen, die zur Herstellung von mehrschichtigen Laminaten geeignet sind, insbesondere für Laminate, die aus äußeren Metallblechen und einer Zwischenschicht aufgebaut sind.In view of this prior art, the inventors have set themselves the task of providing binders which are suitable for the production of multilayer laminates, in particular for laminates which are composed of outer metal sheets and an intermediate layer.
Die erfindungsgemäße Lösung der Aufgabe ist den Ansprüchen zu entnehmen, sie besteht im wesentlichen in der Bereitstellung von mehrschichtigen Laminaten die aus zwei äußeren Metallblechen und einer Zwischenschicht aus einer Bindemittelmatrix und ggf. einem darin eingebundenen Flächengebilde herstellt werden können, wobei die Bindemittel-Zusammensetzung ein vulkanisierbares Kautschukmaterial auf der Basis mindestens eines flüssigen Elastomeren mit reaktiven Gruppen ist.The solution to the problem according to the invention can be found in the claims, it consists essentially in the provision of multilayer laminates which can be produced from two outer metal sheets and an intermediate layer from a binder matrix and, if appropriate, a sheet-like structure incorporated therein, the binder composition being a vulcanizable one Rubber material based on at least one liquid elastomer with reactive groups.
In einer besonders bevorzugten Ausführungsform ist das Bindemittel so zusammengesetzt, daß es die Herstellung von Gewichts-optimierten, leichten Laminaten mit akustischer und / oder versteifender Wirkung gestattet. Hierzu kann das Bindemittelsystem beispielsweise " chemische " Treibmittel enthalten, oder expandierbare Mikrohohlkugeln oder expandierte Mikrohohlkugeln.In a particularly preferred embodiment, the binder is composed such that it enables the production of weight-optimized, lightweight laminates with an acoustic and / or stiffening effect. For this purpose, the binder system can contain, for example, "chemical" blowing agents, or expandable hollow microspheres or expanded hollow microspheres.
Ein weiterer Gegenstand ist ein Verfahren zur Herstellung des vorgenannten mehrschichtigen Laminats, das die folgenden wesentlichen Verfahrenschritte beinhaltet: a) Auftragen der erfindungsgemäß zu verwendenden, vulkanisierbarenAnother subject is a process for the production of the aforementioned multilayer laminate, which comprises the following essential process steps: a) application of the vulcanisable to be used according to the invention
Kautschuk - Zusammensetzung mit Hilfe einer Breitschlitzdüse oder einemRubber composition using a slot die or a
Walzenauftragsgerät auf eine Blechtafel,
b) ggf. Aufbringen des Flächengebildes auf die Kautschuk - Zusammensetzung, c) Fügen der zweiten Blechtafel, d) ggf. Verpressen des Verbundes auf den vorbestimmten Abstand, e) Aushärten der Kautschuk-Klebemittelschicht durch Erwärmung des Verbundes auf Temperaturen zwischen 80 °C - 250°C, vorzugsweise zwischen 160 °C und 200 °C.Roller application device on a metal sheet, b) if applicable, applying the fabric to the rubber composition, c) joining the second sheet of metal, d) if necessary pressing the composite to the predetermined distance, e) curing the rubber adhesive layer by heating the composite to temperatures between 80 ° C. 250 ° C, preferably between 160 ° C and 200 ° C.
Der letztgenannte Schritt e) kann ggf. auch mehrstufig erfolgen. Dazu kann die Bindemittel - Zusammensetzung in einer ersten Aushärtungsstufe vorgehärtet werden. Anschließend kann das Mehrschicht - Laminat an sich bekannten Umformungsprozessen und Ausstanzprozessen unterworfen werden, so daß beispielsweise vorgeformte Karosseriebauteile aus dem Laminat herstellbar sind, die in einem späteren Arbeitsschritt mit herkömmlichen Fügungsverfahren wie Kleben und / oder Schweißen, Nieten, Schrauben, Bördeln zusammengefügt werden. Die endgültige Aushärtung der Bindemittelschicht erfolgt dann in einem späteren Verfahrenschritt z.B. im Lackofen nach der Elektrotauchlackierung der Rohkarosse eines Fahrzeugs.The last-mentioned step e) can optionally also be carried out in several stages. For this purpose, the binder composition can be precured in a first curing stage. The multilayer laminate can then be subjected to known forming processes and punching processes, so that, for example, preformed body components can be produced from the laminate, which are joined in a later work step using conventional joining methods such as gluing and / or welding, riveting, screwing, flanging. The final hardening of the binder layer then takes place in a later process step e.g. in the paint oven after electro-painting the body shell of a vehicle.
In einer anderen Ausführungsform des erfindungsgemäßen Verfahrens erfolgt der Auftrag der vulkanisierbaren Kautschuk - Zusammensetzung nicht direkt auf eine Blechtafel sondern in einer Art "Transferverfahren" auf einen Zwischenträger. Dieser Zwischenträger kann eine antiadhäsiv ausgerüstete Abdeckfolie sein, es kann aber auch das (verstärkende) Flächengebilde der Zwischenschicht für das Mehrschichtlaminat sein. In der letztgenannten Ausführungsform kann die Bindemittelschicht für die Zwischenlagerung mit einer Abdeckfolie versehen sein, die ggf. vor dem Aufbringen des Bindemittel-beschichteten Flächengebildes auf die Blechtafeln entfernt wird.In another embodiment of the method according to the invention, the vulcanizable rubber composition is not applied directly to a metal sheet, but in a type of "transfer method" to an intermediate carrier. This intermediate carrier can be an anti-adhesive cover film, but it can also be the (reinforcing) flat structure of the intermediate layer for the multilayer laminate. In the last-mentioned embodiment, the binder layer for the intermediate storage can be provided with a cover film which, if necessary, is removed before the binder-coated fabric is applied to the metal sheets.
Die erfindungsgemäß verwendete Bindemittelmatrix besteht im Wesentlichen aus heißhärtenden, reaktiven Zusammensetzungen auf der Basis von natürlichen und / oder synthetischen Kautschuken (d.h. olefinische Doppelbindung enthaltenden Elastomeren) und Vulkanisationsmitteln, die mindestens einen der folgenden Stoffe enthalten:
- einen oder mehrere Flüssigkautschuke und/oder Festkautschuke oder Elastomere,The binder matrix used according to the invention essentially consists of heat-curing, reactive compositions based on natural and / or synthetic rubbers (ie elastomers containing olefinic double bonds) and vulcanizing agents which contain at least one of the following substances: one or more liquid rubbers and / or solid rubbers or elastomers,
- feinteilige Pulver aus thermoplastischen Polymeren,- fine-particle powders made of thermoplastic polymers,
- Vulkanisationsmittel, Vulkanisationsbeschleuniger, Katalysatoren,- vulcanizing agents, vulcanization accelerators, catalysts,
- Füllstoffe,- fillers,
- Klebrigmacher und/oder Haftvermittler,- tackifiers and / or adhesion promoters,
- Treibmittel,- blowing agent,
- Extenderöle,- extender oils,
- Alterungsschutzmittel,- anti-aging agents,
- Rheologiehilfsmittel.- Rheology aids.
Geeignete einkomponentige Bindemittel sind z.B. in der WO 96/23040 beschrieben, geeignete zweikomponentige Bindemittel sind z.B. in der EP-A- 356715 offenbart. Die Lehre dieser Schriften in Bezug auf die Kautschuk- Zusammensetzungen ist ausdrücklich Bestandteil der vorliegenden Anmeldung.Suitable one-component binders are e.g. described in WO 96/23040, suitable two-component binders are e.g. in EP-A-356715. The teaching of these documents with regard to the rubber compositions is expressly part of the present application.
Die Flüssigkautschuke oder Elastomere können dabei aus der folgenden Gruppe der Homo- und/oder Copolymeren ausgewählt werden:The liquid rubbers or elastomers can be selected from the following group of homo- and / or copolymers:
Polybutadiene, insbesondere die 1 ,4- und 1 ,2-Polybutadiene, Polybutene, Polyisobutylene, 1 ,4- und 3,4-Polyisoprene, Styrol-Butadien-Copolymere, ButadienAcrylnitril-Copolymere, wobei diese Polymeren endständige und/oder (statistisch verteilte) seitenständige funktionelle Gruppen haben können. Beispiele für derartige funktionelle Gruppen sind Hydroxy-, Amino-, Carboxyl-, Carbonsäureanhydrid- oder Epoxygruppen. Das Molekulargewicht dieser Flüssigkautschuke ist typischerweise unterhalb von 20000, vorzugsweise zwischen 900 und 10000. Der Anteil an Flüssigkautschuk an der Gesamtzusammensetzung hängt dabei von der erwünschten Rheologie der ungehärteten Zusammensetzung und den erwünschten mechanischen Eigenschaften der ausgehärteten Zusammensetzung ab. Der Anteil an flüssigem Kautschuk oder Elastomer variiert normalerweise zwischen 5 und 50 Gew.% der Gesamtformulierung. Dabei hat es sich als zweckmäßig erwiesen, vorzugsweise Mischungen von Flüssigkautschuken unterschiedlicher Molekulargewichte und
unterschiedlicher Konfiguration in bezug auf die restlichen Doppelbindungen einzusetzen. Zur Erzielung optimaler Haftung auf den diversen Substraten wird in den besonders bevorzugten Formulierungen anteilig einePolybutadienes, in particular the 1, 4- and 1, 2-polybutadienes, polybutenes, polyisobutylenes, 1, 4- and 3,4-polyisoprenes, styrene-butadiene copolymers, butadiene-acrylonitrile copolymers, these polymers being terminal and / or (statistically distributed ) may have lateral functional groups. Examples of such functional groups are hydroxyl, amino, carboxyl, carboxylic anhydride or epoxy groups. The molecular weight of these liquid rubbers is typically below 20,000, preferably between 900 and 10,000. The proportion of liquid rubber in the overall composition depends on the desired rheology of the uncured composition and the desired mechanical properties of the cured composition. The proportion of liquid rubber or elastomer normally varies between 5 and 50% by weight of the total formulation. It has proven to be advantageous, preferably mixtures of liquid rubbers of different molecular weights and different configuration in relation to the remaining double bonds. To achieve optimum adhesion to the various substrates, a proportion is used in the particularly preferred formulations
Flüssigkautschukkomponente mit Hydroxylgruppen bzw. Säureanhydridgruppen eingesetzt. Mindestens einer der Flüssigkautschuke sollte einen hohen Anteil an cis-1 ,4-Doppelbindungen, ein weiterer einen hohen Anteil an Vinyl- doppelbindungen enthalten.Liquid rubber component with hydroxyl groups or acid anhydride groups used. At least one of the liquid rubbers should contain a high proportion of cis-1,4 double bonds, another a high proportion of vinyl double bonds.
Geeignete Festkautschuke haben im Vergleich zu den Flüssigkautschuken ein signifikant höheres Molekulargewicht (MW=100000 oder höher), Beispiele für geeignete Kautschuke sind Polybutadien, vorzugsweise mit einem sehr hohen Anteil an cis-1 ,4-Doppelbindungen (typischerweise über 95%), Styrolbutadienkautschuk, Butadienacrylnitrilkautschuk, synthetischer oder natürlicher Isoprenkautschuk, Butylkautschuk oder Polyurethankautschuk.Suitable solid rubbers have a significantly higher molecular weight (MW = 100,000 or higher) compared to the liquid rubbers, examples of suitable rubbers are polybutadiene, preferably with a very high proportion of cis-1,4 double bonds (typically over 95%), styrene-butadiene rubber, Butadiene acrylonitrile rubber, synthetic or natural isoprene rubber, butyl rubber or polyurethane rubber.
Ein Zusatz von feinverteilten thermoplastischen Polymerpulvern bringt eine signifikante Verbesserung der Zugscherfestigkeit unter Beibehaltung einer sehr hohen Bruchdehnung, wie sie bisher für Strukturklebstoffe ungewöhnlich war. So lassen sich Zugscherfestigkeiten von über 15 MPa erreichen, wobei die Bruchdehnung deutlich über 15 %, sehr häufig über 20 % liegt. Die hochfesten Strukturklebstoffe auf der Basis von Epoxidharzen weisen selbst als flexibilisierte Klebstoffformulierungen nur Bruchdehnungen von unter 5 % auf. Als Polymerpulver eignen sich eine Vielzahl von thermoplastischen Polymerpulvern, beispielhaft genannt sei Vinylacetat, entweder als Homopolymer oder als Copolymer mit Ethylen so wie anderen Olefinen und Acrylsäurederivaten, Polyvinylchlorid, Vinylchlorid-Λ/inylacetat-Copolymere, Styrolcopolymere, wie sie z.B. in der DE-A-4034725 beschrieben sind, Polymethylmethacrylat sowie dessen Copolymeren mit anderen (Meth)acrylsäureestern und funktioneilen Comonomeren, wie sie beispielsweise in der DE-C-2454235 beschrieben sind, oder Polyvinylacetale wie z.B. das Polyvinylbutyral. Obwohl die Teilchengröße bzw. Teilchengrößenverteilung der Polymerpulver nicht besonders kritisch zu sein scheint, sollte die mittlere Teilchengröße unter 1mm, vorzugsweise unter 350 μm, ganz besonders bevorzugt zwischen 100 und 20 μm liegen. Ganz besonders
bevorzugt werden Polyvinylacetat bzw. Copolymere auf Basis EthylenvinylacetatThe addition of finely divided thermoplastic polymer powders brings a significant improvement in tensile shear strength while maintaining a very high elongation at break, which was previously unusual for structural adhesives. This enables tensile shear strengths of over 15 MPa to be achieved, with the elongation at break being clearly over 15%, very often over 20%. The high-strength structural adhesives based on epoxy resins, even as flexible adhesive formulations, only have elongations at break of less than 5%. A large number of thermoplastic polymer powders are suitable as polymer powders, for example vinyl acetate, either as a homopolymer or as a copolymer with ethylene, such as other olefins and acrylic acid derivatives, polyvinyl chloride, vinyl chloride Λ / inyl acetate copolymers, styrene copolymers, as described, for example, in DE-A -4034725 are described, polymethyl methacrylate and its copolymers with other (meth) acrylic acid esters and functional comonomers, as described for example in DE-C-2454235, or polyvinyl acetals such as polyvinyl butyral. Although the particle size or particle size distribution of the polymer powders does not appear to be particularly critical, the average particle size should be less than 1 mm, preferably less than 350 μm, very particularly preferably between 100 and 20 μm. Most notably polyvinyl acetate or copolymers based on ethylene vinyl acetate are preferred
(EVA). Die Menge des zugesetzten thermoplastischen Polymerpulvers richtet sich nach dem gewünschten Festigkeitsbereich, sie liegt zwischen 2 und 20 Gew.% bezogen auf die Gesamtzusammensetzung, ein besonders bevorzugter Bereich sind 10 bis 15%.(EVA). The amount of thermoplastic polymer powder added depends on the desired strength range, it is between 2 and 20% by weight, based on the total composition, a particularly preferred range is 10 to 15%.
Da die Vernetzungs- bzw. Härtungsreaktion der Kautschukzusammensetzung einen entscheidenden Einfluß auf die Zugscherfestigkeit und auf die Reißdehnung der ausgehärteten Klebstoff-Zusammensetzung hat, muß das Vulkanisationssystem besonders sorgfältig ausgewählt und abgestimmt werden. Es eignen sich eine Vielzahl von Vulkanisationssystemen sowohl auf der Basis von elementarem Schwefel als auch Vulkanisationssysteme ohne elementarem Schwefel, zu letzterem zählen die Vulkanisationssysteme auf der Basis zu Thiuramdisulfiden. Es können auch Vulkanisationssysteme ohne Schwefelverbindungen eingesetzt werden. Zu letzterem zählen die Vulkanisationssysteme auf der Basis von organischen Peroxiden, polyfunktionellen Aminen, Chinonen, p- Benzochinondioxim, p-Nitrosobenzol und Dinitrosobenzol oder auch die Vernetzung mit (blockierten) Diisocyanaten. Besonders bevorzugt sind Vulkanisationssysteme auf der Basis von elementarem Schwefel und organischen Vulkanisationsbeschleunigern sowie Zinkverbindungen. Der pulverförmige Schwefel wird dabei in Mengen von 1 bis 15 Gew.%, bezogen auf die Gesamtzusammensetzung eingesetzt, besonders bevorzugt werden Mengen zwischen 4 und 8 % eingesetzt. Als organische Beschleuniger eignen sich die Dithiocarbamate (in Form ihrer Ammonium- bzw. Metallsalze), Xanthogenate, Thiuram-Verbindungen (Monosulfide und Disulfide), Thiazolverbindungen, Aldehyd/Aminbeschleuniger (z.B. Hexamethylentetramin) sowieSince the crosslinking or curing reaction of the rubber composition has a decisive influence on the tensile shear strength and on the elongation at break of the cured adhesive composition, the vulcanization system must be selected and coordinated with particular care. A large number of vulcanization systems based on elemental sulfur as well as vulcanization systems without elemental sulfur are suitable, the latter being the vulcanization systems based on thiuram disulfides. Vulcanization systems without sulfur compounds can also be used. The latter include vulcanization systems based on organic peroxides, polyfunctional amines, quinones, p-benzoquinone dioxime, p-nitrosobenzene and dinitrosobenzene, or crosslinking with (blocked) diisocyanates. Vulcanization systems based on elemental sulfur and organic vulcanization accelerators and zinc compounds are particularly preferred. The powdered sulfur is used in amounts of 1 to 15% by weight, based on the total composition, and amounts of between 4 and 8% are particularly preferably used. Suitable organic accelerators are the dithiocarbamates (in the form of their ammonium or metal salts), xanthates, thiuram compounds (monosulfides and disulfides), thiazole compounds, aldehyde / amine accelerators (e.g. hexamethylene tetramine) and
Guanidinbeschleuniger, ganz besonders bevorzugt wird Dibenzothiazyldisulfid (MBTS). Diese organischen Beschleuniger werden in Mengen zwischen 2 und 8 Gew.% bezogen auf die Gesamtformulierung, bevorzugt zwischen 3 und 6 % eingesetzt. Bei den als Beschleuniger wirkenden Zinkverbindungen kann zwischen den Zinksalzen von Fettsäuren, Zinkdithiocarbamaten, basischen Zinkcarbonaten sowie insbesondere feinteiligem Zinkoxid gewählt werden. Der Gehalt an Zinkverbindungen liegt im Bereich zwischen 1 und 10 Gew.%, vorzugsweise zwischen 3 und 7 Gew.%. Zusätzlich können weitere typische Kautschuk-
Vulkanisationshilfsmittel wie z.B. Fettsäuren (z.B. Stearinsäure) in der Formulierung vorhanden sein.Guanidine accelerator, dibenzothiazyl disulfide (MBTS) is very particularly preferred. These organic accelerators are used in amounts of between 2 and 8% by weight, based on the overall formulation, preferably between 3 and 6%. In the zinc compounds acting as accelerators, a choice can be made between the zinc salts of fatty acids, zinc dithiocarbamates, basic zinc carbonates and, in particular, finely divided zinc oxide. The content of zinc compounds is in the range between 1 and 10% by weight, preferably between 3 and 7% by weight. In addition, other typical rubber Vulcanization aids such as fatty acids (eg stearic acid) may be present in the formulation.
Obwohl die erfindungsgemäß zu verwendenden Zusammensetzungen aufgrund des Gehaltes an Flüssigkautschuk mit funktioneilen Gruppen in aller Regel bereits eine sehr gute Haftung auf den zu verklebenden Substraten haben, können, falls erforderlich, Klebrigmacher und/oder Haftvermittler zugesetzt werden. Hierzu eignen sich beispielsweise Kohlenwasserstoffharze, Phenolharze, Terpen- Phenolharze, Resorcinharze oder deren Derivate, modifizierte oder unmodifizierte Harzsäuren bzw. -ester (Abietinsäurederivate), Polyamine, Polyamino-amide, Anhydride und Anhydrid-enthaltende Copolymere. Auch der Zusatz von Polyepoxidharzen in geringen Mengen (<1 Gew.%) kann bei manchen Substraten die Haftung verbessern. Hierfür werden dann jedoch vorzugsweise die festen Epoxidharze mit einem Molekulargewicht deutlich über 700 in feingemahlener Form eingesetzt, so daß die Formulierungen trotzdem im wesentlichen frei von Epoxyharzen sind, insbesondere solchen mit einem Molekulargewicht unter 700. Falls Klebrigmacher bzw. Haftvermittler eingesetzt werden, hängt deren Art und Menge von der Polymerzusammensetzung des Kleb-/ Dichtstoffes, von der gewünschten Festigkeit der gehärteten Zusammensetzung und von dem Substrat, auf welches die Zusammensetzung appliziert wird, ab. Typische klebrigmachende Harze (Tackifier) wie z.B. die Terpenphenolharze oder Harzsäurederivate, werden normalerweise in Konzentrationen zwischen 5 und 20 Gew.% verwendet, typische Haftvermittler wie Polyamine, Polyaminoamide oder Resorcinderivate werden im Bereich zwischen 0,1 und 10 Gew.% verwendet.Although the compositions to be used according to the invention generally already have very good adhesion to the substrates to be bonded due to the content of liquid rubber with functional groups, if necessary, tackifiers and / or adhesion promoters can be added. For this purpose, for example, hydrocarbon resins, phenolic resins, terpene-phenolic resins, resorcinol resins or their derivatives, modified or unmodified resin acids or esters (abietic acid derivatives), polyamines, polyamino amides, anhydrides and anhydride-containing copolymers are suitable. The addition of polyepoxide resins in small amounts (<1% by weight) can also improve the adhesion on some substrates. For this purpose, however, the solid epoxy resins with a molecular weight of significantly more than 700 are preferably used in finely ground form, so that the formulations are nevertheless essentially free of epoxy resins, in particular those with a molecular weight of less than 700. If tackifiers or adhesion promoters are used, their nature depends and the amount of the polymer composition of the adhesive / sealant, the desired strength of the cured composition and the substrate to which the composition is applied. Typical tackifying resins (tackifiers) such as the terpene phenolic resins or resin acid derivatives are normally used in concentrations between 5 and 20% by weight, typical adhesion promoters such as polyamines, polyaminoamides or resorcinol derivatives are used in the range between 0.1 and 10% by weight.
Zum Erzielen der Aufschäumung während des Härtungsvorganges können prinzipiell alle gängigen Treibmittel verwendet werden, beispielhaft genannt seien organische Treibmittel aus der Klasse der Azoverbindungen, N-Nitro- soverbindungen, Sulfonylhydrazide oder Sulfonylsemicarbazide. Für die erfindungsgemäß zu verwendenden Azoverbindungen seien beispielhaft das Azobisisobutyronitril und insbesondere das Azodicarbonamid genannt, aus der Klasse der Nitrosoverbindungen sei beispielhaft das Di-Nitroso- pentamethylentetramin genannt, aus der Klasse der Sulfohydrazide das 4,4'-
Oxybis(benzolsulfonsäurehydrazid), das Diphenylsulfon-3,3'-disulfohydrazid oder das Benzol-1 ,3-disulfohydrazid und aus der Klasse der Semicarbazide das p-In principle, all common blowing agents can be used to achieve foaming during the curing process, examples being organic blowing agents from the class of azo compounds, N-nitroso compounds, sulfonylhydrazides or sulfonylsemicarbazides. Examples of the azo compounds to be used according to the invention include azobisisobutyronitrile and in particular azodicarbonamide, from the class of nitroso compounds the di-nitroso-pentamethylenetetramine is mentioned, from the class of sulfohydrazides 4,4'- Oxybis (benzenesulfonic acid hydrazide), the diphenylsulfone-3,3'-disulfohydrazide or the benzene-1,3-disulfohydrazide and from the class of the semicarbazides the p-
Toluolsulfonylsemicarbazid genannt. An die Stelle der vorgenannten Treibmittel können auch die sogenannten expandierbaren Mikrohohlkugeln ("expandable microspheres"), d.h. nicht expandierte thermoplastische Polymerpulver treten, die mit niedrigsiedenden organischen Flüssigkeiten getränkt bzw. gefüllt sind.Called toluenesulfonyl semicarbazide. In place of the aforementioned blowing agents, the so-called expandable microspheres, i.e. Unexpanded thermoplastic polymer powders occur that are soaked or filled with low-boiling organic liquids.
Derartige "Microspheres" sind beispielsweise in der EP-A-559254, der EP-A-Such "microspheres" are described, for example, in EP-A-559254, EP-A-
586541 oder der EP-A-594598 beschrieben. Obwohl nicht bevorzugt, können auch bereits expandierte Mikrohohlkugeln verwendet bzw. mit verwendet werden.586541 or EP-A-594598. Although not preferred, hollow microspheres which have already been expanded can also be used or also used.
Gegebenenfalls können diese expandierbaren / expandierten Mikrohohlkugeln in beliebigem Mengenverhältnis mit den oben genannten "chemischen" Treibmitteln kombiniert werden. Die chemischen Treibmittel werden in schäumbarenIf necessary, these expandable / expanded hollow microspheres can be combined in any quantity ratio with the above-mentioned "chemical" blowing agents. The chemical blowing agents are in foamable
Zusammensetzungen in Mengen zwischen 0,1 und 3 Gew.%, vorzugsweise zwischen 0,2 und 2 Gew. %, die Mikrohohlkugeln zwischen 0,1 und 4 Gew. %, vorzugsweise zwischen 0,2 und 2 Gew. % verwendet.Compositions in amounts between 0.1 and 3% by weight, preferably between 0.2 and 2% by weight, using hollow microspheres between 0.1 and 4% by weight, preferably between 0.2 and 2% by weight.
Vorzugsweise sind die erfindungsgemäß zu verwendenden Zusammensetzungen frei von Weichmachern für das thermoplastische Polymer. Insbesondere sind sie frei von Phthalsäureestern. Es kann jedoch notwendig sein, die Rheologie der ungehärteten Zusammensetzung und/oder den mechanischen Eigenschaften der gehärteten Zusammensetzung durch die Zugabe von sogenannten Extenderölen, d.h. aliphatischen, aromatischen oder naphtenischen Ölen, zu beeinflussen. Vorzugsweise geschieht diese Beeinflussung jedoch durch die zweckmäßige Auswahl der niedrigmolekularen Flüssigkautschuke oder durch die Mitverwendung von niedermolekularen Polybutenen oder Polyisobutylenen. Falls Extenderöle eingesetzt werden, werden Mengen im Bereich zwischen 2 und 15 Gew.% verwendet.The compositions to be used according to the invention are preferably free from plasticizers for the thermoplastic polymer. In particular, they are free from phthalic acid esters. However, the rheology of the uncured composition and / or the mechanical properties of the cured composition may need to be adjusted by the addition of so-called extender oils, i.e. aliphatic, aromatic or naphthenic oils. However, this influencing preferably takes place through the appropriate selection of the low molecular weight liquid rubbers or through the use of low molecular weight polybutenes or polyisobutylenes. If extender oils are used, amounts in the range between 2 and 15% by weight are used.
Die Füllstoffe können aus einer Vielzahl von Materialien ausgewählt werden, insbesondere sind hier zu nennen Kreiden, natürliche gemahlene oder gefällte Calciumcarbonate, Calcium-Magnesium-Carbonate, Silicate, Schwerspat, Graphit sowie Ruß. Auch blättchenförmige Füllstoffe, wie z.B. Vermiculit, Glimmer, Talk oder ähnliche Schichtsilikate, sind als Füllstoffe geeignet. Es kann ggf.
zweckmäßig sein, daß zumindest ein Teil der Füllstoffe oberflächenvorbehandelt ist, insbesondere hat sich bei den verschiedenen Calciumcarbonaten bzw. Kreiden eine Beschichtung mit Stearinsäure zur Verminderung der eingetragenen Feuchtigkeit und zur Verminderung der Feuchtigkeitsempfindlichkeit der ausgehärteten Zusammensetzung als zweckmäßig erwiesen. Zusätzlich enthalten die erfindungsgemäßen Zusammensetzungen in der Regel zwischen 1 und 20 Gew.%, vorzugsweise zwischen 5 und 15 Gew.% Calciumoxid. Der Gesamtanteil an Füllstoffen in der Formulierung kann zwischen 10 und 70 Gew.% variieren, der Vorzugsbereich liegt zwischen 25 und 60 Gew.%.The fillers can be selected from a large number of materials, in particular chalks, naturally ground or precipitated calcium carbonates, calcium magnesium carbonates, silicates, heavy spar, graphite and carbon black. Flake-like fillers, such as, for example, vermiculite, mica, talc or similar sheet silicates, are also suitable as fillers. It may It should be expedient that at least some of the fillers have been surface-pretreated. In particular, a coating with stearic acid has proven to be expedient for the various calcium carbonates or chalks in order to reduce the moisture introduced and to reduce the sensitivity to moisture of the cured composition. In addition, the compositions according to the invention generally contain between 1 and 20% by weight, preferably between 5 and 15% by weight, calcium oxide. The total proportion of fillers in the formulation can vary between 10 and 70% by weight, the preferred range is between 25 and 60% by weight.
Gegen den thermischen, thermooxidativen oder Ozonabbau der erfindungsgemäßen Zusammensetzungen können konventionelle Stabilisatoren, wie z.B. sterisch gehinderte Phenole oder Aminderivate eingesetzt werden, typische Mengenbereiche für diese Stabilisatoren sind 0,1 bis 5 Gew.%.Against the thermal, thermooxidative or ozone depletion of the compositions according to the invention, conventional stabilizers such as sterically hindered phenols or amine derivatives are used, typical quantity ranges for these stabilizers are 0.1 to 5% by weight.
Obwohl die Rheologie der erfindungsgemäßen Zusammensetzungen normalerweise durch die Auswahl der Füllstoffe und das Mengenverhältnis der niedermolekularen FIüssig-Kautschuke in den gewünschten Bereich gebracht werden kann, können konventionelle Rheologiehilfsmittel wie z.B. pyrogene Kieselsäuren, Bentone oder fibrillierte oder Pulpkurzfasem im Bereich zwischen 0,1 und 7 % zugesetzt werden. Außerdem können weitere konventionelle Hilfsund Zusatzmittel in den erfindungsgemäßen Zusammensetzungen Verwendung finden.Although the rheology of the compositions according to the invention can normally be brought into the desired range by the selection of the fillers and the quantitative ratio of the low-molecular liquid rubbers, conventional rheological aids such as e.g. pyrogenic silicas, bentones or fibrillated or pulp short fibers in the range between 0.1 and 7% can be added. In addition, other conventional auxiliaries and additives can be used in the compositions according to the invention.
In der organischen Bindemittelmatrix der Zwischenschicht des Laminates befindet sich in der Regel eingebunden ein Flächengebilde. Für dieses Flächengebilde können im Prinzip eine Vielzahl von Materialien verwendet werden, beispielhaft erwähnt seien "Nonwovens", Vliese, Gewebe, Gewirke auf der Basis einer Vielzahl von Kunststoff - Fasern wie z.B. Polyesterfasern, Polypropylenfasern, Polyamidfasern, Kohlenstofffasern oder auch Glasfasern. In einer besonders bevorzugten Ausführungsform können diese Flächengebilde aus einem Streckmetallgitter, einem Drahtgitter, einem Stegblech- oder einem Lochblech bestehen. Derartige metallische Flächengebilde sind beispielsweise aus der WO
00/13890 oder aus der DE-A-3935120 bekannt. Die dort genanntenIn the organic binder matrix of the intermediate layer of the laminate there is usually a flat structure embedded. In principle, a large number of materials can be used for this flat structure, examples being “nonwovens”, nonwovens, woven fabrics, knitted fabrics based on a large number of plastic fibers, such as polyester fibers, polypropylene fibers, polyamide fibers, carbon fibers or glass fibers. In a particularly preferred embodiment, these flat structures can consist of an expanded metal grid, a wire grid, a web plate or a perforated plate. Such metallic fabrics are for example from WO 00/13890 or known from DE-A-3935120. The ones mentioned there
Flächengebilde für Zwischenschichten von Mehrschichtlaminaten sind ausdrücklich Bestandteil dieser Anmeldung.Flat structures for intermediate layers of multilayer laminates are expressly part of this application.
Die beiden äußeren Metallbleche haben dabei eine Dicke zwischen 0,1 und 0,5 mm, vorzugsweise zwischen 0,2 und 0,3 mm. Dabei können diese Bleche normale Stahlbleche, aber auch nach den diversen Verzinkungsverfahren veredelte Stahlbleche sei, genannt sein hier die elektrolytisch verzinkten, feuerverzinkten Blechen sowie die entsprechenden thermisch nachbehandelten oder verzinkten oder nachträglich phosphatierten Stahlbleche sowie Aluminiumbleche oder auch Magnesiumbleche.The two outer metal sheets have a thickness between 0.1 and 0.5 mm, preferably between 0.2 and 0.3 mm. These sheets can be normal steel sheets, but also steel sheets that have been refined by the various galvanizing processes, here are the electrolytically galvanized, hot-dip galvanized sheets and the corresponding thermally post-treated or galvanized or subsequently phosphated steel sheets as well as aluminum sheets or magnesium sheets.
Das Laminat hat dabei eine Gesamt - Schichtstärke zwischen 1 mm und 2 mm, vorzugsweise zwischen 1 ,2 und 1 ,8 mm.The laminate has a total layer thickness between 1 mm and 2 mm, preferably between 1.2 and 1.8 mm.
Wie eingangs erwähnt, werden die oben genannten 1- oder 2-komponentigen hitzehärtenden Kleb-/Dichtstoff - Zusammensetzungen zur Herstellung von Mehrschichtlaminaten verwendet, die vorzugsweise Rohbau in der Automobilindustrie eingesetzt werden. Die Härtung der Zusammensetzungen soll in einem Temperaturbereich zwischen 80 und 240 °C in etwa 10 bis 35 min. , ggf. zweistufig, stattfinden. Vorzugsweise finden im Rohbau Temperaturen zwischen 160 und 200 °C Verwendung. Ein entscheidender Vorteil der erfindungsgemäß verwendeten Zusammensetzungen ist, daß auch hier alle Vorteile der an sich bekannten Kautschuk-basierenden Kleb-/Dichtstoffe genutzt werden können, d.h. weisen eine gute alterungs-beständige Haftung auf den diversen verzinkten Stählen wie z.B. elektrolytisch verzinkten, feuerverzinkten sowie den entsprechenden thermisch nachbehandelten oder verzinkten und nachträglich phosphatierten Stahlblechen sowie unverzinkten Stählen und Aluminium auf, auch wenn die Substrate noch mit den diversen Korrosionsschutz- und/oder Tiefziehölen versehen sind.As mentioned at the beginning, the above-mentioned 1- or 2-component heat-curing adhesive / sealant compositions are used for the production of multilayer laminates, which are preferably used for the body-in-white in the automotive industry. The curing of the compositions should be in a temperature range between 80 and 240 ° C in about 10 to 35 minutes. , possibly in two stages. Temperatures between 160 and 200 ° C are preferably used in the shell. A decisive advantage of the compositions used according to the invention is that here too all advantages of the rubber-based adhesives / sealants known per se can be used, i.e. have good aging-resistant adhesion on various galvanized steels such as electrolytically galvanized, hot-dip galvanized and the corresponding thermally post-treated or galvanized and subsequently phosphated steel sheets, as well as non-galvanized steels and aluminum, even if the substrates are still provided with the various anti-corrosion and / or deep-drawing cavities.
Die erfindungsgemäße verwendeten Zusammensetzungen haben dabei die folgenden bevorzugten Zusammensetzungen :
Gew. - Prozent Chemische BezeichnungThe compositions used according to the invention have the following preferred compositions: % By weight Chemical name
3,0-10,0 eis 1 ,4 Polybutadien, fest3.0-10.0 ice 1, 4 polybutadiene, solid
3,0-8,0 Zinkoxid3.0-8.0 zinc oxide
2,0-20 Calciummoxid2.0-20 calcium oxide
0,1-2,0 2,2 Methylen-bis-(4 Methyl-6-tert.-Butylphenol)0.1-2.0 2.2 methylene-bis- (4 methyl-6-tert-butylphenol)
0,5-5,0 Russ0.5-5.0 Russ
0-2,0 Mikrohohlkugeln0-2.0 hollow microspheres
5,0-40,0 Calciumcarbonat5.0-40.0 calcium carbonate
5,0-40,0 Calciumcarbonat, gecoatet mit Stearat5.0-40.0 calcium carbonate, coated with stearate
5,0-20,0 Polybutadien flüssig, MW ca. 1800, eis - 1 ,4 ca. 72 %5.0-20.0 polybutadiene liquid, MW approx. 1800, ice - 1, 4 approx. 72%
5,0-30,0 Polybutadien mit aktiven Carboxylgruppen, MW ca. 17005.0-30.0 polybutadiene with active carboxyl groups, MW approx. 1700
2,0-40,0 niedermolekulares, sterospez. Polybutadien-Öl, MW 1800, vinyl 50%2.0-40.0 low molecular weight, sterospec. Polybutadiene oil, MW 1800, vinyl 50%
1 ,0-10,0 Schwefel1, 0-10.0 sulfur
0,2-5,0 MBTS0.2-5.0 MBTS
2,0-10,0 EVA-Copolymer, Tg ca. 40 °C2.0-10.0 EVA copolymer, Tg approx. 40 ° C
0-5,0 Magnesiumoxid0-5.0 magnesium oxide
In den nachfolgenden Ausführungsbeispielen soll die Erfindung näher erläutert werden, wobei die Auswahl der Beispiele keine Beschränkung des Erfindungs-
gegenstandes darstellen soll, sie sollen nur in modellhafter Weise konkrete Ausführungsbeispiel illustrieren. Wenn nicht anders angegeben, sind bei Zusammensetzungen alle Mengenangaben Gewichtsteile.The invention is to be explained in more detail in the following exemplary embodiments, the selection of the examples not limiting the invention. should represent the object, they should only illustrate concrete exemplary embodiment in a model manner. Unless stated otherwise, all amounts are by weight for compositions.
BeispieleExamples
In den nachfolgenden Beispielen 1 bis 3 werden die Zusammensetzungen von 3 Kautschuk-Klebstoffen aufgeführt, die für die Herstellung von mehrschichtigen Laminaten verwendet wurden.Examples 1 to 3 below list the compositions of 3 rubber adhesives used in the manufacture of multilayer laminates.
Beispiel 1 :Example 1 :
Strukturklebstoff auf KautschukbasisStructural rubber-based adhesive
3,75 eis 1 ,4 Polybutadien, fest3.75 ice 1, 4 polybutadiene, solid
4,00 Zinkoxid4.00 zinc oxide
4,95 Calciumoxid4.95 calcium oxide
0,50 2,2 Methylen - bis -(4 Methyl-6-tert. - Butylphenol)0.50 2.2 methylene - bis - (4 methyl-6-tert.-butylphenol)
0,50 Russ0.50 Russ
0,20 Mikrohohlkugeln0.20 hollow microspheres
24,60 Calciumcarbonat24.60 calcium carbonate
14,30 Calciumcarbonat, gecoatet mit Stearat14.30 calcium carbonate, coated with stearate
13,50 Polybutadien flüssig, MW ca.1800, eis -1 ,4 ca. 72%13.50 polybutadiene liquid, MW approx. 1800, ice -1, 4 approx. 72%
10,00 Polybutadien mit aktiven Hydroxylgruppen, MW 280010.00 polybutadiene with active hydroxyl groups, MW 2800
5,00 niedermolekulares,sterospez. PB-ÖI, MW 1800, vinyl 50%5.00 low molecular weight, sterospec. PB-ÖI, MW 1800, vinyl 50%
7,25 Schwefel7.25 sulfur
0,95 MBTS0.95 MBTS
10,00 Polyvinylacetat, EVA-Copolymer, Tg ca. 40°C10.00 polyvinyl acetate, EVA copolymer, Tg approx. 40 ° C
0,50 Imidazol0.50 imidazole
Beispiel 2:
Unterfütterungsklebstoff auf KautschukbasisExample 2: Relining adhesive based on rubber
9,00 eis 1 ,4 Polybutadien, fest9.00 ice 1, 4 polybutadiene, solid
4,00 Zinkoxid4.00 zinc oxide
4,95 Calciumoxid4.95 calcium oxide
0,50 2,2 Methylen - bis -(4 Methyl-6-tert. - Butylphenol)0.50 2.2 methylene - bis - (4 methyl-6-tert.-butylphenol)
3,00 Leitfähigkeitsruß3.00 conductivity black
21 ,90 Calciumcarbonat21, 90 calcium carbonate
10,05 Calciumcarbonat, gecoatet mit Stearat10.05 calcium carbonate coated with stearate
23,00 Polybutadien flüssig, MW ca.1800, eis -1 ,4 ca. 72%23.00 liquid polybutadiene, MW approx. 1800, ice -1, 4 approx. 72%
4,00 Polybutadien mit aktiven Carboxylgruppen, MW 17004.00 polybutadiene with active carboxyl groups, MW 1700
4,80 Schwefel4.80 sulfur
4,80 MBTS4.80 MBTS
4,00 Phenol-Novolak-Hexamin-Harz4.00 phenol novolak hexamine resin
6,00 Talkum6.00 talc
Beispiel 3:Example 3:
2 K-System auf Kautschukbasis gemäß der Lehre der EP 3567152-component system based on rubber according to the teaching of EP 356715
A-Komponente:A component:
4,00 Zinkoxid4.00 zinc oxide
4,55 Calciumoxid4.55 calcium oxide
0,50 2,2 Methylen - bis -(4 Methyl-6-tert. - Butylphenol)0.50 2.2 methylene - bis - (4 methyl-6-tert.-butylphenol)
0,50 Russ0.50 Russ
7,00 Alkylsulfonsäureester des Phenols7.00 alkyl sulfonic acid ester of phenol
0,50 Polyetherpolyol0.50 polyether polyol
38,45 Graphit38.45 graphite
14,00 Polybutadien flüssig, MW ca.1800, eis -1 ,4 ca. 72%
21 ,00 Polybutadien mit aktiven Hydroxylgruppen, MW 280014.00 liquid polybutadiene, MW approx. 1800, ice -1, 4 approx. 72% 21, 00 polybutadiene with active hydroxyl groups, MW 2800
1 ,00 Hexamethylenbisthiosulfat1, 00 hexamethylene bisthiosulfate
4,00 Schwefel4.00 sulfur
4,00 MBTS4.00 MBTS
1 ,00 Tetramethylenmethylendiamin1,00 tetramethylene methylenediamine
B-KomponenteComponent B
6,00 Zinkoxid6.00 zinc oxide
4,95 Calciumoxid4.95 calcium oxide
0,50 2,2 Methylen - bis -(4 Methyl-6-tert. - Butylphenol)0.50 2.2 methylene - bis - (4 methyl-6-tert.-butylphenol)
24,00 Graphit24.00 graphite
14,00 Polybutadien flüssig, MW ca.1800, eis -1 ,4 ca. 72%14.00 liquid polybutadiene, MW approx. 1800, ice -1, 4 approx. 72%
53,55 Polybutadien mit aktiven Carboxylgruppen, MW 170053.55 polybutadiene with active carboxyl groups, MW 1700
1 ,00 Hexamethylenbisthiosulfat1, 00 hexamethylene bisthiosulfate
6,00 Schwefel6.00 sulfur
4,00 MBTS4.00 MBTS
Für die Herstellung der Mehrschicht-Laminate wurden zum einen Aluminiumbleche und zum anderen verzinkte Stahlbleche (Elozink) mit Blechstärken von 0,25 mm verwendet. Dazu wurde zunächst wurde zunächst auf ein Blech jeweils der vorgenannte Klebstoff aufgetragen, danach wurde als Flächengebilde ein Streckmetall der Stärke 0,25 mm gemäß der Lehre der WO 00/13890 aufgelegt und anschließend ein zweites Bleche darüber gefügt und der gesamte Verbund so verpresst, daß die Zwischenschicht zwischen den Aussenblechen eine Schichtstärke von etwa 0,25 mm aufwies. Anschließend wurde der Verbund für 30 min. bei 180 °C ausgehärtet. Danach wurden die nachfolgend aufgeführten Messergebnisse ermittelt.On the one hand, aluminum sheets and on the other, galvanized steel sheets (Elozink) with sheet thicknesses of 0.25 mm were used for the production of the multilayer laminates. For this purpose, the aforementioned adhesive was first applied to a sheet, then an expanded metal with a thickness of 0.25 mm was placed as a flat structure in accordance with the teaching of WO 00/13890 and then a second sheet was placed over it and the entire composite was pressed in such a way that the intermediate layer between the outer sheets had a layer thickness of approximately 0.25 mm. The composite was then for 30 min. cured at 180 ° C. The measurement results listed below were then determined.
Meßergebnisse:
Test Beispiel 1 Beispiel 2 Beispiel 3 AluminiumMeasurement results: Test Example 1 Example 2 Example 3 Aluminum
/ Elozink/ Elozink
(Vergleich)(Comparison)
Zugscherfestigkeit: (30'180°C) 12,5 MPa 2,2 MPa 1 ,50 MPa n.a.Tensile shear strength: (30 ' 180 ° C) 12.5 MPa 2.2 MPa 1.50 MPa na
3 Punkt Biegetest/ mm3 point bending test / mm
(Aluminium)(Aluminum)
2mm 50 20 23 42mm 50 20 23 4
4mm 62 37 44 74mm 62 37 44 7
6mm 66 45 56 106mm 66 45 56 10
7mm 67 47 60 127mm 67 47 60 12
3 Punkt Biegetest/ mm3 point bending test / mm
(Elozink)(Elozink)
2mm 68 42 16 62mm 68 42 16 6
4mm 81 52 33 114mm 81 52 33 11
6mm 85 58 45 156mm 85 58 45 15
7mm 87 60 50 17
7mm 87 60 50 17
Verlustfaktor d in Abhängigkeit der Erregerfrequenz kHz Strukturklebstoff gemäß Beispiel 1Loss factor d as a function of the excitation frequency kHz structural adhesive according to example 1
1 kHz 3kHz1 kHz 3 kHz
Massivstahl (Referenz): 0,01 0,02Solid steel (reference): 0.01 0.02
Stahl/Stahl mit Beispiel 1 0,075 0,16Steel / steel with Example 1 0.075 0.16
Stahl/Alu mit Beispiel 1 0,12 0,20Steel / aluminum with example 1 0.12 0.20
Aus den oben aufgeführten Standard kräften (in N) des Drei-Punktbiegetestes gemäß DIN 53293 wird ersichtlich, daß die Festigkeits- und Verformungseigenschaften bei Verwendung aller drei Klebstoffe ausgezeichnete Werte liefert. Zum Vergleich wurde ein Verbund ohne Verklebung herangezogen, bei dem die drei Schichten Aussenbleche/Streckmetall durch punktförmige Verschweißung miteinander verbunden wurden. Hieraus wird deutlich, daß die Festigkeits- und Verformungseigenschaften der erfindungsgemäßen Mehrschicht- Laminate um ein vielfaches höher sind als ohne Verwendung der Verklebung.From the standard forces listed above (in N) of the three-point bending test according to DIN 53293 it can be seen that the strength and deformation properties provide excellent values when using all three adhesives. For comparison, a composite without gluing was used, in which the three layers of outer sheet metal / expanded metal were joined together by spot welding. From this it is clear that the strength and deformation properties of the multilayer laminates according to the invention are many times higher than without using the adhesive.
Gleichzeitig werden die guten akustischen Eigenschaften der Laminate dokumentiert durch den Verlustfaktor d im Vergleich zu normalem einschichtigen Massivstahl deutlich.
At the same time, the good acoustic properties of the laminates are documented by the loss factor d compared to normal single-layer solid steel.
Claims
1. Mehrschichtiges Laminat herstellbar, aus zwei äußeren Metallblechen und einer Zwischenschicht aus einer Bindemittelmatrix sowie ggf. einem in das Bindemittel eingebundenen Flächengebilde, dadurch gekennzeichnet, daß die Bindemittel-Zusammensetzung ein vulkanisierbares Kautschukmaterial auf der Basis mindestens eines flüssigen Elastomeren mit reaktiven Gruppen enthält.1. Multi-layer laminate can be produced, from two outer metal sheets and an intermediate layer from a binder matrix and, if appropriate, a sheet-like structure incorporated in the binder, characterized in that the binder composition contains a vulcanizable rubber material based on at least one liquid elastomer with reactive groups.
2. Laminat nach Anspruch 1 , dadurch gekennzeichnet, daß mindestens ein Kautschuk ein flüssiges Polyen aus der Gruppe bestehend aus 1 ,2- Polybutadien, 1 ,4-Polybutadien, Polyisopren, Polybuten, Polyisobutylen, Co- polymere des Butadiens und/oder Isoprens mit Styrol und/oder Acrylnitril, Co- polymere von Acrylsäureestern mit Dienen ist, wobei das Molekulargewicht des flüssigen Polyens im Bereich von 900 bis etwa 40000 liegt.2. Laminate according to claim 1, characterized in that at least one rubber is a liquid polyene from the group consisting of 1,2-polybutadiene, 1,4-polybutadiene, polyisoprene, polybutene, polyisobutylene, copolymers of butadiene and / or isoprene Is styrene and / or acrylonitrile, copolymers of acrylic acid esters with dienes, the molecular weight of the liquid polyene being in the range from 900 to about 40,000.
3. Laminat nach Anspruch 2, dadurch gekennzeichnet, daß das oder die flüssige(n) Polyen(e) zusätzlich terminale und/oder statistisch verteilte Carboxylgruppen, Carbonsäureanhydridgruppen, Hydro-xylgruppen, Aminogruppen, Mercaptogruppen oder Epoxygruppen als funktionelle Gruppen enthält.3. Laminate according to claim 2, characterized in that the liquid (s) polyene (s) additionally contains terminal and / or randomly distributed carboxyl groups, carboxylic acid anhydride groups, hydroxyl groups, amino groups, mercapto groups or epoxy groups as functional groups.
4. Laminat nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Bindemittel zusätzlich mindestens einen Festkautschuk in einer Menge von 1.5 bis 9 Gew.%, vorzugsweise 4 bis 6 Gew.%, bezogen auf die Gesamtzusammensetzung, enthält.4. Laminate according to at least one of the preceding claims, characterized in that the binder additionally contains at least one solid rubber in an amount of 1.5 to 9% by weight, preferably 4 to 6% by weight, based on the total composition.
5. Laminat nach Anspruch 4, dadurch gekennzeichnet, daß sie einen oder mehrere Festkautschuke aus der Gruppe cis-1 ,4-Polybutadien, Styrol- Butadien-Kautschuk, synthetischer Isoprenkautschuk, Naturkautschuk, Ethylen-Propylen-Dien-Kautschuk (EPDM), Nitrilkautschuk, Butylkautschuk, Acrylkautschuk enthält. 5. Laminate according to claim 4, characterized in that it contains one or more solid rubbers from the group cis-1, 4-polybutadiene, styrene-butadiene rubber, synthetic isoprene rubber, natural rubber, ethylene-propylene-diene rubber (EPDM), nitrile rubber , Butyl rubber, acrylic rubber contains.
6. Laminat nach mindestens einem der vorhergehenden Ansprüche , dadurch gekennzeichnet, daß das Vulkanisationssystem aus 1 Gew.% bis 15 Gew.%, vorzugsweise 5 Gew.% bis 10 Gew.% pulverförmigem Schwefel, 2 Gew.% bis 8 Gew.%, vorzugsweise 3 Gew.% bis 6 Gew.% organischem Beschleuniger und 1 Gew.% bis 8 Gew.%, vorzugsweise 2 Gew.% bis 6 Gew.% Zinkverbindungen, vorzugsweise Zinkoxid besteht, wobei die Gew.% auf die Gesamtzusammensetzung bezogen sind.6. Laminate according to at least one of the preceding claims, characterized in that the vulcanization system from 1% by weight to 15% by weight, preferably 5% by weight to 10% by weight of powdered sulfur, 2% by weight to 8% by weight, preferably 3% by weight to 6% by weight of organic accelerator and 1% by weight to 8% by weight, preferably 2% by weight to 6% by weight of zinc compounds, preferably zinc oxide, the% by weight based on the total composition.
7. Laminat nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Bindemittel zusätzlich thermoplastische Polymerpulver ausgewählt aus Vinylacetat- Homo- oder Copolymer, Ethylenvinylacetat-Copolymer, Vinylchlorid- Homo- oder Copolymer, Styrol- Homo- oder Copolymer, (Meth)acrylat- Homo- oder Copolymer oder Polyvinylbutyral oder eine Mischung aus zwei oder mehreren dieser Polymeren enthält, die eine mittlere Korngröße von unter 1 mm, vorzugsweise unter 350 μm, ganz besonders bevorzugt unter 100 μm haben.7. Laminate according to at least one of the preceding claims, characterized in that the binder additionally thermoplastic polymer powder selected from vinyl acetate homo- or copolymer, ethylene vinyl acetate copolymer, vinyl chloride homo- or copolymer, styrene homo- or copolymer, (meth) acrylate - Homo- or copolymer or polyvinyl butyral or a mixture of two or more of these polymers, which have an average grain size of less than 1 mm, preferably less than 350 microns, most preferably less than 100 microns.
8. Laminat nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Bindemittelsystem Treibmittel enthält, ausgewählt aus expandierbaren Microhohlkugeln oder aus der Gruppe der organischen Treibmittel Azoverbindungen, insbesondere Azobisisobutyronitril oder Azodicarbonamid, der Nitrosoverbindungen, insbesondere Di-Nitrosopenta- methylentetramin, der Sulfohydrazide, insbesondere das 4,4'- Oxybis(benzolsulfonsäurehydrazid), und der Semicarbazide, insbesondere das p-Toluolsulfonylsemicarbazid.8. Laminate according to at least one of the preceding claims, characterized in that the binder system contains blowing agents selected from expandable hollow microspheres or from the group of organic blowing agents azo compounds, in particular azobisisobutyronitrile or azodicarbonamide, the nitroso compounds, in particular di-nitrosopentamethylenetetramine, the sulfohydrazides, in particular the 4,4'-oxybis (benzenesulfonic acid hydrazide), and the semicarbazides, in particular the p-toluenesulfonylsemicarbazide.
9. Laminat nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Bindemittelsystem zusätzlich Füllstoffe, expandierte Microhohlkugeln, Rheologiehilfsmittel, Extenderöle, Haftvermittler und/oder Alterungsschutzmittel enthält. 9. Laminate according to at least one of the preceding claims, characterized in that the binder system additionally contains fillers, expanded hollow microspheres, rheology aids, extender oils, adhesion promoters and / or anti-aging agents.
10.Laminat nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die zwei äußeren Metallbleche eine Dicke zwischen 0,1 und 0,5 mm, vorzugsweise zwischen 0,2 und 0,3 mm haben.10. Laminate according to at least one of the preceding claims, characterized in that the two outer metal sheets have a thickness between 0.1 and 0.5 mm, preferably between 0.2 and 0.3 mm.
11. Laminat nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Flächengebilde ein Streckmetallgitter, ein Drahtgitter, ein Stegblech oder ein Lochblech ist.11. Laminate according to at least one of the preceding claims, characterized in that the fabric is an expanded metal mesh, a wire mesh, a web plate or a perforated plate.
12. Laminat nach Anspruch 10, dadurch gekennzeichnet, daß das Flächengebilde eine Dicke zwischen 0,7 und 1 ,2 mm, vorzugsweise von etwa 1 mm hat.12. Laminate according to claim 10, characterized in that the fabric has a thickness between 0.7 and 1, 2 mm, preferably of about 1 mm.
13. Laminat nach Anspruch 9 bis 11 , dadurch gekennzeichnet, daß das Flächengebilde mit den beiden äußeren Blechen in elektrisch leitender Verbindung steht.13. Laminate according to claim 9 to 11, characterized in that the fabric is in electrically conductive connection with the two outer sheets.
14. Laminat nach Anspruch 9 bis 12, dadurch gekennzeichnet, daß die Gesamtschichtstärke des Laminats zwischen 1 mm und 2 mm, vorzugsweise zwischen 1 ,2 und 1 ,8 mm liegt.14. Laminate according to claim 9 to 12, characterized in that the total layer thickness of the laminate is between 1 mm and 2 mm, preferably between 1, 2 and 1, 8 mm.
15Nerfahren zur Herstellung eines mehrschichtigen Laminates gemäß Anspruch 1 bis 14 gekennzeichnet durch die folgenden wesentlichen Verfahrensschritte a) Auftragen einer vulkanisierbaren Kautschukzusammensetzung nach mindestens einem der Ansprüche 1 bis 8 mit Hilfe einer Breitschlitzdüse oder einem Walzenauftragsgerät auf eine Blechtafel, b) Aufbringen des Flächengebildes auf die Kautschukzusammensetzung c) Fügen der zweiten Blechtafel d) Gegebenenfalls Verpressen des Verbunds auf den vorbestimmten Abstand e) Aushärten der Kautschuk-Klebemittelschicht durch Erwärmung des Verbundes auf Temperaturen zwischen 80° C und 250° C , vorzugsweise zwischen 160° C und 200° C Process for the production of a multilayer laminate according to claims 1 to 14, characterized by the following essential process steps a) applying a vulcanizable rubber composition according to at least one of claims 1 to 8 with the aid of a slot die or a roller applicator to a metal sheet, b) applying the sheet material to the rubber composition c) joining the second sheet of metal d) optionally pressing the composite to the predetermined distance e) curing the rubber adhesive layer by heating the composite to temperatures between 80 ° C and 250 ° C, preferably between 160 ° C and 200 ° C
6. Verwendung von mehrschichtigen Laminaten gemäß Anspruch 15 zur Herstellung von Leichtbau-Teilen für den Maschinen-, Fahrzeug- oder Gerätebau, insbesondere für den Automobilbau. 6. Use of multi-layer laminates according to claim 15 for the production of lightweight parts for machine, vehicle or equipment construction, in particular for automobile construction.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10062859A DE10062859A1 (en) | 2000-12-16 | 2000-12-16 | Multilayer composite materials with organic rubber-based interlayers |
DE10062859 | 2000-12-16 | ||
PCT/EP2001/014385 WO2002047901A1 (en) | 2000-12-16 | 2001-12-07 | Multi-layered composite material with organic sandwich layers based on rubber |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1343630A1 true EP1343630A1 (en) | 2003-09-17 |
Family
ID=7667494
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01991803A Withdrawn EP1343630A1 (en) | 2000-12-16 | 2001-12-07 | Multi-layered composite material with organic sandwich layers based on rubber |
Country Status (5)
Country | Link |
---|---|
US (1) | US20040076841A1 (en) |
EP (1) | EP1343630A1 (en) |
AU (1) | AU2002231673A1 (en) |
DE (1) | DE10062859A1 (en) |
WO (1) | WO2002047901A1 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030211308A1 (en) * | 2001-02-02 | 2003-11-13 | Khandpur Ashish K | Adhesive for bonding to low surface energy surfaces |
DE10060816A1 (en) * | 2000-12-07 | 2002-06-20 | Henkel Kgaa | Multi-layer molded body with locally limited reinforcement elements |
DE10062009A1 (en) * | 2000-12-13 | 2002-07-04 | Henkel Teroson Gmbh | Multi-layer sandwich materials with organic intermediate layers based on epoxy |
DE10062860A1 (en) * | 2000-12-16 | 2002-06-27 | Henkel Teroson Gmbh | Rubber compositions with plastisol-like flow behavior |
DE10163252A1 (en) * | 2001-12-21 | 2003-07-10 | Henkel Teroson Gmbh | Surface stiffening rubber systems |
DE102004016308A1 (en) * | 2004-04-02 | 2005-10-20 | Henkel Kgaa | adhesive |
JP5028409B2 (en) * | 2005-04-26 | 2012-09-19 | シロー インダストリーズ インコーポレイテッド | Acrylate-rate sound reducing material and method for producing the same |
DE102006038322A1 (en) | 2006-08-15 | 2008-02-21 | Tesa Ag | Punching in particular for the permanent closing of holes |
US7834090B2 (en) * | 2007-08-03 | 2010-11-16 | The Gates Corporation | Rubber composition and vibration damper using the rubber composition |
WO2009081877A1 (en) * | 2007-12-20 | 2009-07-02 | Kuraray Co., Ltd. | Thermoplastic polymer composition and molded article composed of the same |
DE102009028607A1 (en) | 2009-08-18 | 2011-02-24 | Henkel Ag & Co. Kgaa | Rubber composition with high elasticity |
CN102947134B (en) | 2010-06-16 | 2015-09-02 | 夏伊洛工业公司 | The method of panel assembly and forming surface board component |
US8403390B2 (en) | 2011-03-10 | 2013-03-26 | Shiloh Industries, Inc. | Vehicle panel assembly and method of attaching the same |
US20170204620A9 (en) | 2012-05-10 | 2017-07-20 | Michael Freedman & Associates, Inc. | Multi-layer acoustical flooring tile and method of manufacture |
DE102013216778A1 (en) | 2013-08-23 | 2015-02-26 | Tesa Se | Punching in particular for the permanent closing of holes |
DE102013216782A1 (en) * | 2013-08-23 | 2015-02-26 | Tesa Se | Punching in particular for the permanent closing of holes |
WO2016108686A1 (en) * | 2014-12-29 | 2016-07-07 | Redeahold Apeldoorn B.V. | Construction material |
US11214676B2 (en) * | 2019-04-05 | 2022-01-04 | Fina Technology, Inc. | Polyenes for curable liquid rubber-based compositions |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3841958A (en) * | 1971-09-02 | 1974-10-15 | R Delorme | Reinforced structural element and method of making the same |
JPS4865168A (en) * | 1971-12-06 | 1973-09-08 | ||
US4313996A (en) * | 1979-05-21 | 1982-02-02 | The Dow Chemical Company | Formable metal-plastic-metal structural laminates |
US4412031A (en) * | 1983-02-18 | 1983-10-25 | Nippon Zeon Co., Ltd. | Modified rubber composition employing a compound containing a carboxyl and an aldehyde group |
US4707397A (en) * | 1984-05-21 | 1987-11-17 | Bridgestone Corporation | Vibration damping metal panels |
FR2635110B1 (en) * | 1988-08-05 | 1990-11-09 | Saim Adhesifs Insonorisants Mo | PREGELIFIABLE ADHESIVE |
US4987194A (en) * | 1988-10-07 | 1991-01-22 | Kuraray Company, Limited | Block copolymers and composition containing the same |
DE3834818C1 (en) * | 1988-10-13 | 1989-11-09 | Teroson Gmbh, 6900 Heidelberg, De | |
US5259908A (en) * | 1988-10-20 | 1993-11-09 | Henkel Kommanditgesellschaft Auf Aktien | Heat vulcanizable adhesives and a method for bonding |
ATE105853T1 (en) * | 1990-02-05 | 1994-06-15 | Ppg Industries Inc | CURABLE RUBBER BASED STRUCTURAL ADHESIVE. |
DE4122849A1 (en) * | 1991-07-10 | 1993-01-14 | Bostik Gmbh | ADHESIVE / LUBRICANT ON RUBBER BASE |
US5290857A (en) * | 1991-09-04 | 1994-03-01 | Nippon Zeon Co., Ltd. | Epoxy resin adhesive composition |
US5140051A (en) * | 1991-11-22 | 1992-08-18 | Quantum Chemical Corporation | Foaming agent with alcohol activator and method for producing non-chalking polymers |
JP3655646B2 (en) * | 1993-05-24 | 2005-06-02 | 日産自動車株式会社 | Adhesive reinforcing agent for epoxy resin and epoxy resin-based structural adhesive composition for automobile containing the reinforcing agent |
DE19502381A1 (en) * | 1995-01-26 | 1996-08-01 | Teroson Gmbh | Structural raw rubber-based adhesives |
DE19719004C2 (en) * | 1997-05-06 | 2001-05-17 | Krupp Vdm Gmbh | Sheet-like, cold-formable material composite |
DE19839931A1 (en) * | 1998-09-02 | 2000-03-09 | Daimler Chrysler Ag | Glued multi-layer composite panels and method for producing multi-layer composite panels |
DE10060816A1 (en) * | 2000-12-07 | 2002-06-20 | Henkel Kgaa | Multi-layer molded body with locally limited reinforcement elements |
DE10062009A1 (en) * | 2000-12-13 | 2002-07-04 | Henkel Teroson Gmbh | Multi-layer sandwich materials with organic intermediate layers based on epoxy |
-
2000
- 2000-12-16 DE DE10062859A patent/DE10062859A1/en not_active Ceased
-
2001
- 2001-12-07 US US10/450,735 patent/US20040076841A1/en not_active Abandoned
- 2001-12-07 AU AU2002231673A patent/AU2002231673A1/en not_active Abandoned
- 2001-12-07 EP EP01991803A patent/EP1343630A1/en not_active Withdrawn
- 2001-12-07 WO PCT/EP2001/014385 patent/WO2002047901A1/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO0247901A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2002047901A1 (en) | 2002-06-20 |
AU2002231673A1 (en) | 2002-06-24 |
DE10062859A1 (en) | 2002-06-27 |
US20040076841A1 (en) | 2004-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2002047901A1 (en) | Multi-layered composite material with organic sandwich layers based on rubber | |
EP0827522B1 (en) | Heat-setting rubber foams with high structural strength | |
EP2001952B1 (en) | Bonding agents and sealants based on liquid rubbers | |
WO1998018853A1 (en) | Sulphur-free expanding, hot hardening shaped parts | |
DE602004002652T2 (en) | Method for reinforcing a steel plate with a polymer-rubber mixture | |
EP1999223B1 (en) | High strength adhesives with impact peel strength | |
EP0805841A1 (en) | Rubber-based adhesives used on raw structures | |
EP1346002B1 (en) | Multilayer metal sandwich materials comprising epoxy-based adhesive systems | |
EP1792727A2 (en) | Steel plate reinforcing sheet | |
DE202005022067U1 (en) | Injectable, low viscosity rubber damping compounds | |
WO2009000735A9 (en) | Single-component, hot-hardening reactive mixture | |
EP2467422B2 (en) | Rubber composition with high elasticity | |
EP1343839B1 (en) | Rubber composition comprising plastisol formed flow properties | |
WO1996016136A1 (en) | Elastomer products with acoustic attenuation properties | |
EP1456024B1 (en) | Rubber systems for reinforcing surfaces | |
EP1582572A1 (en) | Adhesives for joining connections | |
EP1343841A1 (en) | Odour-reduced sulphur cross-linked rubber masses |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20030610 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Extension state: RO SI |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH CY DE ES FR GB LI |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: HENKEL KGAA |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20060704 |