ZA200102837B - Impact-resistant epoxide resin compositions. - Google Patents
Impact-resistant epoxide resin compositions. Download PDFInfo
- Publication number
- ZA200102837B ZA200102837B ZA200102837A ZA200102837A ZA200102837B ZA 200102837 B ZA200102837 B ZA 200102837B ZA 200102837 A ZA200102837 A ZA 200102837A ZA 200102837 A ZA200102837 A ZA 200102837A ZA 200102837 B ZA200102837 B ZA 200102837B
- Authority
- ZA
- South Africa
- Prior art keywords
- composition
- component
- dianhydride
- compositions
- adhesive
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 68
- 229920000647 polyepoxide Polymers 0.000 title claims description 59
- 239000003822 epoxy resin Substances 0.000 title claims description 49
- 230000001070 adhesive effect Effects 0.000 claims description 60
- 239000000853 adhesive Substances 0.000 claims description 55
- -1 benzenetricarboxylic anhydride Chemical class 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 24
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 23
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 16
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 235000013824 polyphenols Nutrition 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 13
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000007859 condensation product Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000003981 vehicle Substances 0.000 claims description 10
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010276 construction Methods 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004849 latent hardener Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002357 guanidines Chemical class 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 238000000518 rheometry Methods 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- XLXVRIOQCHHBTC-UHFFFAOYSA-N 2,2-bis(phenoxycarbonyl)propanedioic acid Chemical compound C=1C=CC=CC=1OC(=O)C(C(O)=O)(C(=O)O)C(=O)OC1=CC=CC=C1 XLXVRIOQCHHBTC-UHFFFAOYSA-N 0.000 claims description 2
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 2
- YOURXVGYNVXQKT-UHFFFAOYSA-N oxacycloundecane-2,11-dione Chemical compound O=C1CCCCCCCCC(=O)O1 YOURXVGYNVXQKT-UHFFFAOYSA-N 0.000 claims description 2
- ZJHUBLNWMCWUOV-UHFFFAOYSA-N oxocane-2,8-dione Chemical compound O=C1CCCCCC(=O)O1 ZJHUBLNWMCWUOV-UHFFFAOYSA-N 0.000 claims description 2
- RMIBXGXWMDCYEK-UHFFFAOYSA-N oxonane-2,9-dione Chemical compound O=C1CCCCCCC(=O)O1 RMIBXGXWMDCYEK-UHFFFAOYSA-N 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000004382 potting Methods 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical class NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 claims 1
- 150000004984 aromatic diamines Chemical class 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 125000002897 diene group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000007769 metal material Substances 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 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 21
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000004593 Epoxy Substances 0.000 description 11
- 239000004848 polyfunctional curative Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000004831 Hot glue Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 229920001515 polyalkylene glycol Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004823 Reactive adhesive Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 229920013646 Hycar Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 229920006332 epoxy adhesive Polymers 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000014593 oils and fats Nutrition 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical class NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N methylguanidine Chemical compound CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- JFINOWIINSTUNY-UHFFFAOYSA-N pyrrolidin-3-ylmethanesulfonamide Chemical compound NS(=O)(=O)CC1CCNC1 JFINOWIINSTUNY-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- NQOFYFRKWDXGJP-UHFFFAOYSA-N 1,1,2-trimethylguanidine Chemical compound CN=C(N)N(C)C NQOFYFRKWDXGJP-UHFFFAOYSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- UTCOUOISVRSLSH-UHFFFAOYSA-N 1,2-Anthracenediol Chemical class C1=CC=CC2=CC3=C(O)C(O)=CC=C3C=C21 UTCOUOISVRSLSH-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N 1,2-dimethylguanidine Chemical compound CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 1
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- NBNGHXWJFSMASY-UHFFFAOYSA-N 2,3,4-tris(dimethylamino)phenol Chemical compound CN(C)C1=CC=C(O)C(N(C)C)=C1N(C)C NBNGHXWJFSMASY-UHFFFAOYSA-N 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QFRHTANKIYQYLO-UHFFFAOYSA-N 2-ethyl-2-methylimidazole Chemical compound CCC1(C)N=CC=N1 QFRHTANKIYQYLO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000006596 Alder-ene reaction Methods 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000005510 Diuron Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Chemical class 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229920001079 Thiokol (polymer) Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4253—Rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/52—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof
Description
CL @
Impact-resistant Epoxide Resin Compositions
This invention relates to mixtures of special copolymers having at least one glass transition temperature of -30°C or lower and phenol- terminated polyamides or polyimides, mixtures of these components with epoxy resins and/or adducts of epoxy resins with the copolymer having a low glass transition temperature and/or the polyamide or the polyimide and heat-activatable latent hardeners for the resin components and optionally accelerators, fillers, thixotropicizing agents and other typical additives. The invention also relates to a process for the production of these compositions and to their use as a reactive adhesive.
Reactive epoxy-based hotmelt adhesives are known. In machine and vehicle construction and especially in the construction of aircraft, railway vehicles and motor vehicles, components of various metals and/or composite materials are increasingly being joined together with the aid of adhesives. Epoxy adhesives are widely used for high-strength structural bonding, more particularly as heat-curing one-component adhesives which, in many cases, are also formulated as reactive hotmelts. Reactive hotmelts are adhesives which are solid at room temperature and which soften and behave like a thermoplastic material at temperatures of up to about 80 to 90°C. lt is only at relatively high temperatures of about 100°C and higher that the latent hardeners present in these hotmelt adhesives are thermally activated so that irreversible curing to a thermoset occurs. To join the components together, for example in the vehicle industry, the adhesive is first applied warm to at least one substrate surface, after which the parts to be joined are then fitted together. The adhesive then solidifies on cooling and, through this physical solidification, establishes adequate handling resistance, i.e. a temporary bond. The parts thus joined together are further treated in various washing, phosphating and dip painting baths.
@®
It is only after this that the adhesive is cured at relatively high temperatures in an oven.
Conventional adhesives and hotmelt adhesives based on epoxy resins are hard and brittle in the cured state. Although the bonds obtained with them are generally characterized by very high tensile shear strength, the adhesives flake off under peel, impact or impact/peel stress, particularly at relatively low temperatures, so that loss of bond strength readily occurs when the adhesive joint is subjected to that kind of stress. Accordingly, numerous proposals have already been put forward with a view to so modifying epoxy resins by flexible additives that their brittleness is clearly reduced. One known process is based on the use of special rubber/epoxy resin adducts which are incorporated as heterodisperse phase in the epoxy resin matrix so that the epoxies become more impact-resistant. These epoxy resin compositions are also referred to as “toughened”. Another known modification of epoxy resins of the above-mentioned type consists in the reaction of a carboxyl-terminated polybutadiene-co-acrylonitrile copolymer with an epoxy resin. This rubber/epoxy adduct is then dispersed in one or more different epoxy resins. The reaction of the epoxy resin with the carboxyl-containing butadiene/acrylonitrile rubber has to be conducted in such a way that the adduct is not prematurely cured. Although correspondingly modified epoxy resin compositions already represent a clear improvement over unmodified epoxy resins in relation to their impact strength, their behavior under peel or impact/peel stress is still not satisfactory.
EP-A-0 343 676 describes hotmelt adhesive compositions made up of a mixture of several epoxy resins, a phenolic resin and 4a polyurethane/epoxy adduct. The polyurethane/epoxy adduct present therein consists of a reaction product of several polyalkylene glycol homopolymers and copolymers containing primary and secondary OH groups, a diisocyanate and at least one epoxy resin. According to the oe document in question, these hotmelt adhesive compositions show improved shear resistance, peel strength and impact strength in relation to various commercial one-component hotmelt adhesive compositions.
Unfortunately, there is no reference to the adhesive properties of the cured adhesive joint at low temperatures.
US-A-5 290 857 describes an epoxy resin adhesive composition containing an epoxy resin and a powder-form core/shell polymer and a heat-activatable hardener for the epoxy resin. The powder-form core/shell polymer is composed of a core containing an acrylate or methacrylate copolymer with a glass transition temperature of -30°C or lower and a shell containing an acrylate or methacrylate copolymer which contains crosslinking monomer units and which has a glass transition temperature of 70°C or higher, the ratio by weight of the core to the shell being between 10:1 and 1:4. These compositions are said to have excellent adhesive properties, such as peel strength, tensile shear strength and T-peel strength, and also good partial gellability. No mention is made of the properties of bonds with these adhesives at low temperatures.
Similarly, US-A-5,686,509 describes an adhesion-strengthening cCompOoSIuoN T0r epoxy resins consisunyg or powaer-1orim copolymer paruvies ionically crosslinked with a mono- or divalent metal cation. The core of the core/shell polymer is composed of a diene monomer and optionally crosslinking monomer units and has a glass transition temperature of -30°C or lower. The shell copolymer has a glass transition temperature of at least 70°C and is made up of acrylate or methacrylate monomer units and radically polymerizable unsaturated carboxylic acid units. The adhesive composition is said to contain 15 to 60 parts by weight of the adhesion- strengthening copolymer powder and 3 to 30 parts by weight of a heat- activatable hardening agent to 100 parts of epoxy resin. These compositions are recommended for use as structural adhesives for automobile parts. No mention is made of the low temperature properties of
® corresponding bonds.
EP-A-0 308 664 describes epoxy resin compositions which contain an epoxide adduct of a carboxyl-containing copolymer based on butadiene/acrylonitrile or similar butadiene copolymers and a reaction product of an elastomeric isocyanate-terminated prepolymer soluble or dispersible in epoxy resins with a polyphenol or aminophenol and subsequent reaction of this adduct with an epoxy resin. In addition, these compositions may contain one or more epoxy resins. Furthermore, aminofunctional hardeners, polyaminoamides, polyphenols, polycarboxylic acids and their anhydrides or catalytic hardeners and optionally accelerators are proposed for hardening these compositions. The compositions in question are said to be suitable as adhesives which can have high strength, a high glass transition temperature, high peel strength, high impact strength or high tear propagation resistance according to their particular composition.
Similarly, EP-A-0 353 190 describes epoxy resin compositions containing an adduct of an epoxy resin and a carboxylated butadiene/acrylonitrile copolymer and a reaction product of a hydroxyl-, mercapto- or amino-terminated polyalkylene glycol with a phenol carboxylic acid with subsequent reaction of the phenolic group with an epoxy resin.
According to EP-A-0 353 190, these compositions are suitable for the production of adhesives, adhesive films, patches, sealing compounds, paints or matrix resins.
According to the teaching of EP-A-0 354 498 or EP-A-0 591 307, reactive hotmelt adhesive compositions can be produced from a resin component, at least one heat-activatable latent hardener for the resin component and optionally accelerators, fillers, thixotropicizing agents and other typical additives, the resin component being obtainable by the reaction of an epoxy resin solid at room temperature and an epoxy resin liquid at room temperature with one or more linear or branched amino-
terminated polyoxypropylenes. The epoxy resins are said to be used in such a quantity, based on the amino-terminated polyoxypropylene, that an excess of epoxy groups, based on the amino groups, is guaranteed.
These adhesive compositions have a high peel resistance in the T-peel test which they retain even at low temperatures.
The problem addressed by the present invention was further to improve reactive adhesives of the type mentioned at the beginning to the extent that they would have adequate flexibility and increased peel strength not only at room temperature but also - and in particular - at low temperatures below 0°C. In particular, they would show high peel strength at low temperatures and under sudden stress so that, even in the event of a crash, structurally bonded parts would meet modern safety standards in vehicle construction. These improvements would be obtained without any deterioration in peel strength at high temperatures or in tensile shear strength. In addition, the reactive adhesives would have to exhibit adequate wash-out resistance immediately after application and before final curing. To that end, the adhesive compositions would have to lend themselves as hotmelts to formulation as a highly viscous adhesive suitable tor warm application. Another possibility would be to formulate the compositions as an adhesive that could be gelled by a thermal preliminary reaction in a so-called “white body oven” or by induction heating of the joined parts.
The solution provided by the invention to the problem as stated above is defined in the claims and consists essentially in the provision of compositions which contain
A) a copolymer having at least one glass transition temperature of -30°C or lower and epoxy-reactive groups,
B) a reaction product of a di- or polyamine with a carboxylic anhydride and a polyphenol or aminophenol and
C) atleastone epoxy resin.
®
Components A), B) and C) may also be mixtures of compounds of the type mentioned. Components A) and B) are preferably reacted with a large stoichiometric excess of epoxy resins in separate reactions and then optionally mixed with other epoxy resins, heat-activatable hardeners and/or other additives.
Examples of the copolymers of component A) are 1,3-diene polymers containing carboxyl groups and other polar ethylenically unsaturated comonomers. The diene may be butadiene, isoprene or chloroprene and is preferably butadiene. Examples of polar ethylenically unsaturated comonomers are acrylic acid, methacrylic acid, lower alkyl esters of acrylic or methacrylic acid, for example metnyl or ethyi esters thereof, amides of acrylic or methacrylic acid, fumaric acid, itaconic acid, maleic acid or lower alkyl esters or semiesters thereof or maleic acid or itaconic anhydride, vinyl esters, such as for example vinyl acetate or - more particularly - acrylonitrile or methacrylonitrile. Most particularly preferred copolymers A) are carboxyl-terminated butadiene/acrylonitrile copolymers (CTBN) which are commercially available in liquid form under the name of
Hycar from B.F. Goodrich. These copolymers have molecular weights of 2,000 to 5,000 and acrylonitrile contents of 10% to 30%. Actual examples are Hycar CTBN 1300 X 8, 1300 X 13 or 1300 X 15.
The core/shell polymers known from US-A-5,290,857 and from US-
A-5,686,509 may also be used as component A). The core monomers should have a glass transition temperature of or below -30°C and may be selected from the group of diene monomers as mentioned above or suitable acrylate or methacrylate monomers. The core polymer may optionally contain crosslinking monomer units in small quantities. The shell is made up of copolymers which have a glass transition temperature of at least 60°C. The shell is preferably made up of lower alkyl acrylate or methacrylate monomer units (methyl! or ethyl esters) and polar monomers, such as (meth)acrylonitrile, (meth)acrylamide, styrene or radical-
Se polymerizable unsaturated carboxylic acids or carboxylic anhydrides.
However, the adducts of epoxy resins and the liquid CTBN rubbers mentioned above are particularly preferred for component A).
Component B) may be represented by the following formula I:
R'-—[N---(C=0)---X---(C=0)---Y-=-R*-~(Z)rr]n (
LA in which m=1or2, n=2or3,
R' is an amino-terminated residue of a polyalkylene glycol after removal of the functional groups,
R? = H, Cy alkyl, aryl or -(C=0)-; where R? = -(C=0)-, the two carbonyl groups, the nitrogen and X form a five-membered cyclic imide ring,
X = Cos alkyl or the residue of an aromatic carboxylic anhydride or dianhydride after removal of the cyclic anhydride group(s),
Y = -0-, -S- or -NR*-, where R* = H or Cy alkyl or phenyl,
R?® is a carbocyclic-aromatic or araliphatic m+1-functional residue with groups Z directly attached to the aromatic ring and Z= 0, H or -NHR?.
Component B) is a reaction product of a di- or polyamine and a carboxylic anhydride, the stoichiometric ratio being selected so that the carboxylic anhydride is preferably in a two-fold excess over the amino groups, after which the remaining carboxylic anhydride groups or carboxylic acid groups are reacted with a polyphenol or aminophenol in a stoichiometric excess so that the condensation product bears terminal phenolic or amino groups. This condensation product is generally mixed directly into the compositions according to the invention although it may also be reacted with a large stoichiometric excess of epoxy resins so that an epoxy-terminated condensation product is formed.
®
In principle, a large number of diamines or polyamines may be used for the condensation although amino-terminated polyalkylene glycols, more particularly di- or trifunctional amino-terminated polypropylene glycols, polyethylene glycols or copolymers of propylene glycol and ethylene glycol, are preferably used. These glycols are also known under the name of “Jeffamine” (Huntsman). The amino-terminated polyoxytetramethylene glycols, also known as Poly-THF, are also particularly suitable. Other suitable synthesis components are amino-terminated polybutadienes. The amino-terminated polyalkylene glycols have molecular weights of 400 to 5,000.
Examples of suitable carboxylic anhydrides are maleic, succinic, glutaric, adipic, pimelic, suberic, azelaic or sebacic anhydride or, more particularly, anhydrides or dianhydrides of aromatic carboxylic acids or hydrogenation products thereof, such as phthalic anhydride, benzenetricarboxylic anhydride, tetrahydrophthalic dianhydride, mellophanic dianhydride, pyromeliitic dianhydride, 1,8:4,5- and 2,3:6,7- naphthalenetetracarboxylic dianhydride, perylene dianhydride, biphenyl tetracarboxylic acid dianhydride, diphenylether tetracarboxylic dianhydride, diphenylmethane tetracarboxylic dianhydride, 2,2-diphenylpropane tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride and mixtures thereof.
Besides the carboxylic anhydrides mentioned above, maleinized oils and fats may also be used as anhydride components for the preparation of condensation product B). Maleinized oils and fats and low molecular weight polyenes are known to be prepared by ene reaction or by free radical reaction of maleic anhydride with unsaturated compounds.
The polyphenols or aminophenols to be used for condensation product B) are either aromatic di- or trihydroxy compounds derived from a mono- or polynuclear carbocyclic-aromatic radical or the corresponding aminohydroxy compounds. The aromatic rings may either be condensed or attached to one another by binding links or by a covalent bond.
Examples of the compounds mentioned first are hydroquinone, resorcinol, pyrocatechol, isomers of dihydroxynaphthalene (pure isomers or mixture of several isomers), isomers of dihydroxyanthracene and the corresponding aminohydroxy compounds. The polyphenols or aminophenols, which are derived from carbocyclic-aromatic compounds of which the aromatic nuclei are attached by binding links, may be represented by the following general formula ll:
Z---AR---B---AR---Z (ny in which Z is as defined above,
AR is a mononuclear aromatic radical which may optionally be further substituted by alkyl or alkenyl radicals,
B stands for the binding link which may be selected from the group consisting of a covalent bond, -CR°R®-, -O-, -S-, -SO,-, -CO-, -COO-, -CONR’- and SiR®R®- where R®, R® and R’ independently of one another represent hydrogen, -CF3 or Cy alkvl or R® and R® toaether with the common C atom form a cycloaliphatic radical with 5 to7 ring C atoms, R® and R® represent Cis alkyl. The two groups B and Z in formula II independently of one another may be located in the ortho, meta or para position. Particularly preferred compounds corresponding to formula Il are 4 4’-dihydroxydiphenyl or the bisphenols A and/or F.
Suitable epoxy resins for component C) or for forming the epoxy adduct or for mixing components A) and B) are any of a number of polyepoxides which contain at least two 1,2-epoxy groups per molecule.
The epoxy equivalent of these polyepoxides may be between 150 and 4,000. Basically, the polyepoxides may be saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic polyepoxide compounds. Examples of suitable polyepoxides include the polyglycidyl
® . ethers which are obtained by reaction of epichlorohydrin or epibromohydrin with a polyphenol in the presence of alkali. Polyphenols suitable for this purpose are, for example, resorcinol, pyrocatechol, hydroquinone, bisphenol A (bis-(4-hydroxyphenyl)-2,2-propane)), bisphenol F (bis(4- hydroxyphenyl)methane), bis-(4-hydroxyphenyl)1,1-isobutane, 4.4'- dihydroxybenzophenone, bis-(4-hydroxyphenyl)-1,1-ethane, 1,5-hydroxy- naphthalene.
Other polyepoxides suitable in principle are the polyglycidyl ethers of polyalcohols or diamines. These polyglycidyl ethers are derived from polyalcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, triethylene glycol, pentane-1,5- diol, hexane-1,6-diol or trimethylo! propane.
Other polyepoxides are polyglycidyl esters of polycarboxylic acids, for example reaction products of glycidol or epichlorohydrin with aliphatic or aromatic polycarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, terephthalic acid or dimer fatty acid.
Other epoxides are derived from the epoxidation products of olefinically unsaturated cycloaliphatic compounds or from native oils and fats.
The epoxy resins obtained by reaction of bisphenol A or bisphenol F are most particularly preferred. Mixtures of liquid and solid epoxy resins are generally used, the liquid epoxy resins preferably being based on bisphenol A and having a sufficiently low molecular weight. Epoxy resins liquid at room temperature which generally have an epoxy equivalent weight of 150 to about 220 and more particularly in the range from 182 to 192 are particularly preferred for the adduct formation of components A) and B).
The hardness of the reactive adhesive in the cooled state, i.e. in particular after application to the substrate to be joined, but before curing, depends on the degree of condensation and hence molecular weight of
. @® component B) in particular and on the ratio of solid epoxy resin to liquid epoxy resin. The higher the degree of condensation (and hence the molecular weight) of condensation product B) and the greater the proportion of solid epoxy resin in the composition, the harder the cooled semicrystalline adhesive will be.
Suitable heat-activatable or latent hardeners for the epoxy resin binder system of components A), B) and C) are guanidines, substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, cyclic tertiary amines, aromatic amines and/or mixtures thereof. The hardeners may be stoichiometrically included in the curing reaction although they may also be catalytically active. Examples of substituted guanidines are methyl guanidine, dimethyl guanidine, trimethyl guanidine, tetramethyl guanidine, methyl isobiguanidine, dimethyl isobiguanidine, tetramethyl isobiguanidine, hexamethyl isobiguanidine, heptamethyl isobiguanidine and, most particularly, cyanoguanidine (dicyanodiamide).
Alkylated benzoguanamine resins, benzoguanamine resins or methoxymethyl ethoxymethyl benzoguanamine are mentioned as representatives of suitable guanamine derivatives. The selection criterion for the one-component heat-curing hotmelt adhesives is of course their low solubility at room temperature in the resin system so that solid finely ground hardeners are preferred, dicyanodiamide being particularly suitable. The composition is thus guaranteed a long shelf life.
Catalytically active substituted ureas may be used in addition to or instead of the hardeners mentioned above. These substituted ureas are, in particular, p-chlorophenyl-N,N-dimethyl urea (Monuron), 3-phenyl-1,1- dimethyl urea (Fenuron) or 3,4-dichlorophenyl-N,N-dimethyl urea (Diuron).
In principle, catalytically active tertiary aryl or alkyl amines, for example benzyl dimethyl amine, tris(dimethylamino)phenol, piperidine or piperidine derivatives, may also be used, but often have too high a solubility in the adhesive system so that the one-component system is not guaranteed
® useful shelf life in their case. In addition, various, preferably solid imidazole derivatives may be used as catalytically active accelerators. 2-Ethyl-2- methyl imidazole, N-butyl imidazole, benzimidazole and N-Ci.o-alkyl imidazoles or N-arylimidazoles are mentioned as representatives of such accelerators.
In addition, the adhesives according to the invention contain fillers known per se such as, for example, the various ground or precipitated chalks, carbon black, calcium-magnesium carbonates, heavy spar and, in particular, silicate fillers of the aluminium-magnesium-calcium silicate type, for example wollastonite, chlorite.
The adhesive compositions according to the invention may also contain other typical auxiliaries and additives such as, for example, plasticizers, reactive diluents, rheology aids, wetting agents, antiagers, stabilizers and/or pigments.
The adhesives according to the invention may be formulated on the one hand as one-component adhesives which in turn may be formulated both as highly viscous adhesives designed form warm application and as heat-activatable hotmelt adhesives. These adhesives may also be formulated as one-component pregellable adhesives, in which case the compositions contain either fine-particle thermoplastic powders such as, for example, polymethacrylates, polyvinyl butyral or other thermoplastic (co)polymers or the curing system is so adapted that a two-stage curing process occurs, the gelling step effecting only partial curing of the adhesive and final curing in vehicle construction taking place, for example, in one of the paint ovens, preferably the cathodic electrodeposition oven.
The adhesive compositions according to the invention may also be formulated as two-component epoxy adhesives where the two reaction components are only mixed just before application, curing then taking place at room temperature or moderately elevated temperature. The second reaction component may be selected from the reaction components known o : ® per se for two-component epoxy adhesives, for example di- or polyamines, amino-terminated polyalkylene glycols (for example Jeffamine, Amino-Poly-
THF) or polyaminoamides. Other reactants may be mercaptofunctional prepolymers such as, for example, the liquid Thiokol polymers. Basically, the epoxy compositions according to the invention may also be cured with carboxylic anhydrides as the second reaction component in two-component adhesive formulations.
Besides the applications mentioned at the beginning, the adhesive compositions according to the invention may also be used as potting compounds in the electrical or electronics industries and as die-attach adhesives in electronics for bonding components to circuit boards. Other possible applications for the compositions according to the invention are as matrix materials for composite materials such as, for example, fiber- reinforced composites.
However, a most particularly preferred application for the adhesives according to the invention is structural bonding in vehicle construction.
The quantity ratios between the individual components may vary within relatively wide limits, depending on the requirements the adhesive is expected to satisfy in regard to its application properties, flexibility, impact peel strength or tensile strength. Typical ranges for the key components are: e component A) 5-25% by weight, preferably 1-20% by weight e component B): 5-30% by weight, preferably 5-20% by weight eo component C): 10-45% by weight, preferably 15-30% by weight; this component may be composed of one or more liquid and/or solid epoxy resins in which case it may optionally contain low molecular weight epoxides as reactive diluents o fillers: 10-40% by weight e hardener component (for heat-curable one-component systems): 1-10% by weight, preferably 3-8% by weight
® e accelerator: 0.01-3% by weight, preferably 0.1 to 0.8% by weight » rheology aid (thixotropicizing agent): 0.5-5% by weight.
As mentioned at the beginning, the requirements modern structural adhesives are expected to meet in vehicle construction continue to
S increase because more and more structural elements - including those with load-bearing functions - are being joined by bonding processes. As already stated in the article by G. Loétting and S. Singh entitled: “Anforderungen an Klebstoffe fiir Strukturverbindungen im
Karosseriebau” Adhesion 1988, No. 9, pages 19 to 26, the adhesives are expected on the one hand to fulfil production aspects of practical relevance, including automatable application in short cycle times, adhesion to oil-covered metal panels, adhesion to various types of metal panels and compatibility with the process conditions on the paint line (resistance to washing and phosphating baths, curability during stoving of the CED primer, resistance to the following painting and drying operations). In addition, modern structural adhesives have to exhibit improving strength and deformation properties, even in the cured state. These include the high corrosion resistance and flexural strength of the structural components and the deformability of the bond under mechanical stress. High deformability of the structural components guarantees a considerable safety advantage in the event of a crash. This crash behavior can best be determined by determining the impact energy for cured bonds; sufficiently high values for impact energy or impact/peel energy are desirable both at high temperatures of up to +90°C and in particular at low temperatures down to -40°C. High tensile shear strength should also be achieved. Both strengths should be achieved on a large number of substrates, mainly oil- covered metal panels, for example steel bodywork panels, steel plate galvanized by various methods, panels of various aluminium alloys or even magnesium alloys and steel plates coated by coil coating with organic coatings of the “Bonazinc” or “Granocoat” type. As shown in the following
Examples, the adhesive compositions according to the invention surprisingly satisfy these requirements to a very high degree.
The following Examples are intended to illustrate the invention. All quantities in connection with the compositions are parts by weight, unless otherwise indicated.
General procedure for producing component A)
A carboxy-terminated poly(butadiene-co-acrylonitrile) (Hycar CTBN 1300 X 13) was reacted for 3 hours with stirring under nitrogen at 140°C with an approximately 10-molar excess of a liquid DGEBA epoxy resin until the reaction was constant.
General procedure for preparing condensation product B)
In a stirrable and heatable tank reactor, 1 mole of the carboxylic anhydride or dicarboxylic anhydride were reacted under nitrogen for 3 to 4 hours at 120°C to 160°C with 0.4 to 0.7 mole of an amino-terminated polyalkylene glycol, the polyamine being introduced into the reactor first and heated initially to 130°C. The adduct thus formed was reacted with about 1.1 to 1.5 moles of a polyphenol until the reaction was constant. The progress of the reaction was followed by gel permeation chromatography (GPC). This phenol-terminated polymer was then mixed with an epoxy resin, preferably a diglycidyl ether of bisphenol A (DGBEA).
General production of the adhesive
In a kneader, components A), B) and a liquid epoxy resin and a solid epoxy resin were mixed to homogeneity at room temperature or optionally at 80°C in the presence of the fillers, hardeners, accelerators and rheology aids and the resulting mixture was poured into the storage containers optionally while still warm. }
Examples 1 to 6
The condensation products B) listed in Table 1 were prepared from
Jeffamine-D-2000 (polyoxypropylenediamine, molecular weight 2000), pyromeliitic dianhydride and resorcinol by the general method for preparing the condensation product B).
Table 1.
D-2000 i 229.5 222.0 El 2376 | 200.0
PMSA 48.0 | 420) 480
D-2000 = Jeffamine D-2000
PMSA = pyromellitic dianhydride
Component A) was prepared from Hycar CTBN 1300 X13 and a liquid DGBEA resin by the method described above. The resulting composition contained 40% butyl rubber and had an epoxy equivalent weight of 900 and a viscosity at 80°C of 200 Pa.s.
Examples 7 to 12
Adhesive compositions according to the invention were prepared from components B) of to Examples 1 to 6, component A) and a liquid
DGEBA resin (epoxy equivalent weight 189), fillers, dicyanodiamide as hardener and accelerators and hydrophobic silica as thixotropicizing agent.
The compositions are set out in Table 2.
. , ®
Table 2. Adhesives according to the invention
EE OE EI EE cE TL NN I I
Crmentoae | [®s
CompreneaGanges || ws]
Corrente | | [|W
CrpreaaEaes || || [9s]
Corrente | | | | |_
Wollastonite filler
Silica: Carbosil-TS-720-
The adhesive properties of the Examples according to the invention and the adhesive properties of known adhesives are compared in Table 3.
The adhesive of Comparison Example 1 was Terokal 5051 of Henkel
Teroson which had been made in accordance with the teaching of EP-A-0 354 498. The adhesive of Comparison Example 2 was Betamate 1044/3 made by Gurit Essex. It is assumed that this adhesive had been produced in accordance with the teaching of EP-A-0 308 664 o
Table 3. Adhesive properties
Sa 134] 162] 103 8] 04 28
GIL
500 h SST 23c 17.0 cf 17.0 cf 189d [170d [na ]193cf | 188 1000 h SST | 19.1¢ | 17.9¢f | 14.5 cf 18.2 cf | 16.6 cf na. | 5c | 16.7 cf
Impact: impact peel test to ISO 11343 at 2 m/sec
RT: room temperature
TSS: tensile shear strength to DIN 53283
TSS: salt spray test to DIN 50021 cf: cohesive fracture pattern 100% unless otherwise indicated scf: cohesive fracture pattern with partial film residue on a substrate
As these test results show, the impact peel energy to ISO 11343 of the adhesives according to the invention is several times higher than that of the known adhesives. At very low temperatures in particular, the impact peel energy of the adhesives according to the invention is clearly better than that of the known adhesives without any deterioration in tensile shear strength or ageing behavior in the salt spray test.
Claims (19)
- } 3 a PCT/EP99/07 143 i 19 New Claims' 1. A composition obtainable by reacting a carboxylic anhydride or : carboxylic dianhydride with a diamine or polyamine and a polyphenol or aminophenol, characterized in that the stoichiometric ratio is selected so that the carboxylic anhydride is preferably in a two-fold excess over the amino groups, after which the remaining carboxylic anhydride groups or carboxylic acid groups are reacted with a polyphenol or aminophenol in a stoichiometric excess so that the condensation product bears terminal phenolic or amino groups.
- 2. Compositions containing A) a copolymer having at least one glass transition temperature of -30°C or lower and epoxy-reactive groups, B) a reaction product obtainable by reacting a carboxylic anhydride or dianhydride with a diamine or polyamine and a polyphenol or aminophenol in accordance with claim 1 and C) atleast one epoxy resin. N
- 3. Compositions as claimed in claim 2, characterized in that component A) is a butadiene-based copolymer.
- 4. ‘Compositions as claimed in claim 2 or 3, characterized in that component A) is a carboxyl-containing copolymer based on buta- diene/acrylonitrile, ~~ butadiene/(meth)acrylates, a butadiene/acrylo- : nitrile/styrene copolymer or a butadiene/(meth)acrylate/styrene copolymer.
- 5. A composition as claimed in claim 2, characterized in that : component A) is a core/shell polymer of which the core polymer is a diene polymer or a (meth)acrylate polymer with a glass transition temperature of -30°C or lower and which may optionally be crosslinked with 0.01 to 5% by weight of a diolefinic comonomer and of which the shell polymer has a glass transition temperature of 60°C or higher and is obtained from monomers from the group consisting of alkyl. (meth)acrylate, (meth)acrylonitrile, (methyl) styrene and olefinically unsaturated carboxylic AMENDED SHEET REPLACEMENT SHEET: : PCT/EP99/07 143 fo 20 acids or carboxylic anhydrides or mixtures thereof.
- 6. Compositions as claimed in at least one of the preceding claims, characterized in that an adduct of an epoxy resin and a copolymer according to claims 2 to 5 is used as component A).
- 7. A composition as claimed in at least one of the preceding claims, characterized in that component b) is prepared by condensation from a) a carboxylic anhydride selected from maleic, succinic, glutaric, adipic. pimelic, suberic, azelaic or sebacic anhydride or phthalic anhydride, benzenetricarboxylic anhydride, mellophanic dianhydride, pyromellitic dianhydride, 1,8:4,5- and 2,3:6,7-naphthalenetetracarboxylic dianhydride, perylene dianhydride, biphenyl tetracarboxylic dianhydride, diphenylether tetracarboxylic dianhydride, diphenyl- methane tetracarboxylic dianhydride, 2,2-diphenylpropane tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride and mixtures thereof and b) a polyamine selected from polyethylene glycol, polypropylene glycol, polyoxytetramethylene or polybutadiene diamine or triamine and c) a polyphenol or aminophenol.
- 8. A composition_as_claimed_in_claims_2_to_7,_characterized_in_that component B) according to claim 7 is dissolved in a liquid polyepoxide.
- 9. A composition as claimed in claims 1 to 5, characterized in that component B) according to claim 7 is reacted with a stoichiometric excess of a polyepoxide.
- 10. A composition as claimed in at least one of the preceding claims, characterized in that, in addition to components A), B) and C), it contains A) a latent hardener from the group consisting of dicyanodiamide, guanamines, guanidines, aminoguanidines, solid aromatic diamines and/or a hardening accelerator and B) optionally plasticizers, reactive diluents, rheology aids, fillers, wetting agents and/or antiagers and/or stabilizers. AMENDED SHEET. ‘REPLACEMENT SHEET.{ 4 PCT/EP99/07143
- 11. A process for hardening components A), B), C), D) and optionally E) according to claim 10 by heating the composition to temperatures of 80°C to 210°C and preferably to temperatures of 120°C to 180°C.
- 12. The use of the compositions claimed in claim 10 as a high-strength high-impactstructural adhesive in vehicle construction, aircraft construction or rail vehicle construction.
- 13. The use of the compositions claimed in claim 10 for the production of composite materials, as potting compounds in the electrical and electronics industries and as a die-attach adhesive in the production of circuit boards in the electronics industry.
- 14. Aprocess for bonding metallic and/or composite materials comprising the following key process steps: Ld applying the adhesive composition claimed in claim 10 to at least one of the substrate surfaces to be joined, optionally after cleaning and/or surface treatment ° fitting together the parts to be joined ° optionally pregelling the adhesive composition and . curing the bond by heating the parts to temperatures of 80°C to 210°C and preferably to temperatures of 120°C to 180°C. -----
- 15. A composition as claimed in claim 1 or claim 2, substantially as herein described and illustrated.
- 16. A process as claimed in claim 11, substantially as herein described and illustrated.
- 17. Use as claimed in claim 12 or claim 13, substantially as herein described and illustrated.
- 18. A process as claimed in claim 14, substantially as herein described and illustrated.
- 19. Anew composition, a new process for hardening components, a new use of a composition as defined in claim 10, or a new process for bonding materials, substantially as herein described. AMENDED SHEET
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19845607A DE19845607A1 (en) | 1998-10-06 | 1998-10-06 | Impact-resistant epoxy resin compositions |
Publications (1)
Publication Number | Publication Date |
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ZA200102837B true ZA200102837B (en) | 2002-07-05 |
Family
ID=7883307
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200102837A ZA200102837B (en) | 1998-10-06 | 2001-04-05 | Impact-resistant epoxide resin compositions. |
Country Status (18)
Country | Link |
---|---|
EP (1) | EP1123348B1 (en) |
JP (1) | JP2002526618A (en) |
KR (1) | KR20010086403A (en) |
CN (1) | CN1328588A (en) |
AR (1) | AR022677A1 (en) |
AT (1) | ATE314425T1 (en) |
AU (1) | AU6197299A (en) |
BR (1) | BR9915911A (en) |
CA (1) | CA2346634A1 (en) |
CZ (1) | CZ20011222A3 (en) |
DE (2) | DE19845607A1 (en) |
ES (1) | ES2255761T3 (en) |
HU (1) | HUP0104052A2 (en) |
PL (1) | PL347571A1 (en) |
SK (1) | SK4562001A3 (en) |
TR (1) | TR200100964T2 (en) |
WO (1) | WO2000020483A2 (en) |
ZA (1) | ZA200102837B (en) |
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-
1998
- 1998-10-06 DE DE19845607A patent/DE19845607A1/en not_active Withdrawn
-
1999
- 1999-09-25 AU AU61972/99A patent/AU6197299A/en not_active Abandoned
- 1999-09-25 WO PCT/EP1999/007143 patent/WO2000020483A2/en active IP Right Grant
- 1999-09-25 KR KR1020017004288A patent/KR20010086403A/en not_active Application Discontinuation
- 1999-09-25 BR BR9915911-2A patent/BR9915911A/en not_active IP Right Cessation
- 1999-09-25 JP JP2000574591A patent/JP2002526618A/en active Pending
- 1999-09-25 HU HU0104052A patent/HUP0104052A2/en unknown
- 1999-09-25 SK SK456-2001A patent/SK4562001A3/en unknown
- 1999-09-25 TR TR2001/00964T patent/TR200100964T2/en unknown
- 1999-09-25 AT AT99948868T patent/ATE314425T1/en not_active IP Right Cessation
- 1999-09-25 DE DE59912991T patent/DE59912991D1/en not_active Expired - Fee Related
- 1999-09-25 CZ CZ20011222A patent/CZ20011222A3/en unknown
- 1999-09-25 CN CN99811801A patent/CN1328588A/en active Pending
- 1999-09-25 PL PL99347571A patent/PL347571A1/en unknown
- 1999-09-25 ES ES99948868T patent/ES2255761T3/en not_active Expired - Lifetime
- 1999-09-25 EP EP99948868A patent/EP1123348B1/en not_active Expired - Lifetime
- 1999-09-25 CA CA002346634A patent/CA2346634A1/en not_active Abandoned
- 1999-10-06 AR ARP990105057A patent/AR022677A1/en unknown
-
2001
- 2001-04-05 ZA ZA200102837A patent/ZA200102837B/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE59912991D1 (en) | 2006-02-02 |
ATE314425T1 (en) | 2006-01-15 |
CZ20011222A3 (en) | 2001-08-15 |
AU6197299A (en) | 2000-04-26 |
EP1123348B1 (en) | 2005-12-28 |
KR20010086403A (en) | 2001-09-10 |
SK4562001A3 (en) | 2001-10-08 |
ES2255761T3 (en) | 2006-07-01 |
JP2002526618A (en) | 2002-08-20 |
DE19845607A1 (en) | 2000-04-20 |
PL347571A1 (en) | 2002-04-08 |
BR9915911A (en) | 2001-08-14 |
HUP0104052A2 (en) | 2002-02-28 |
WO2000020483A3 (en) | 2000-07-13 |
CN1328588A (en) | 2001-12-26 |
CA2346634A1 (en) | 2000-04-13 |
TR200100964T2 (en) | 2002-10-21 |
AR022677A1 (en) | 2002-09-04 |
EP1123348A2 (en) | 2001-08-16 |
WO2000020483A2 (en) | 2000-04-13 |
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