WO2010098950A1 - One-part structural epoxy resin adhesives containing dimerized fatty acid/epoxy resin adduct and a polyol - Google Patents
One-part structural epoxy resin adhesives containing dimerized fatty acid/epoxy resin adduct and a polyol Download PDFInfo
- Publication number
- WO2010098950A1 WO2010098950A1 PCT/US2010/022979 US2010022979W WO2010098950A1 WO 2010098950 A1 WO2010098950 A1 WO 2010098950A1 US 2010022979 W US2010022979 W US 2010022979W WO 2010098950 A1 WO2010098950 A1 WO 2010098950A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- structural adhesive
- epoxy resin
- weight
- adhesive
- rubber
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 104
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 103
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 65
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 50
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 31
- 239000000194 fatty acid Substances 0.000 title claims abstract description 31
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 31
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 31
- 229920005862 polyol Polymers 0.000 title abstract description 19
- 150000003077 polyols Chemical class 0.000 title abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000012745 toughening agent Substances 0.000 claims abstract description 26
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 9
- 229920001971 elastomer Polymers 0.000 claims description 41
- 239000005060 rubber Substances 0.000 claims description 41
- 239000011258 core-shell material Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 14
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 41
- 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 29
- -1 epoxide compounds Chemical class 0.000 description 26
- 238000012360 testing method Methods 0.000 description 17
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 150000002118 epoxides Chemical class 0.000 description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 238000009472 formulation Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 229940106691 bisphenol a Drugs 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 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 11
- 229920000768 polyamine Chemical class 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 229920013646 Hycar Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000011257 shell material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000004825 One-part adhesive Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000006085 branching agent Substances 0.000 description 3
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- JXCGFZXSOMJFOA-UHFFFAOYSA-N chlorotoluron Chemical compound CN(C)C(=O)NC1=CC=C(C)C(Cl)=C1 JXCGFZXSOMJFOA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 201000004440 congenital dyserythropoietic anemia Diseases 0.000 description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 238000002156 mixing Methods 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
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000006254 rheological additive Substances 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZWOULFZCQXICLZ-UHFFFAOYSA-N 1,3-dimethyl-1-phenylurea Chemical compound CNC(=O)N(C)C1=CC=CC=C1 ZWOULFZCQXICLZ-UHFFFAOYSA-N 0.000 description 1
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical class O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- OVENINIFSWEPGA-UHFFFAOYSA-N 2-aminopropyl prop-2-enoate Chemical compound CC(N)COC(=O)C=C OVENINIFSWEPGA-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
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical group CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
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- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- DGJMPUGMZIKDRO-UHFFFAOYSA-N cyanoacetamide Chemical compound NC(=O)CC#N DGJMPUGMZIKDRO-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910000267 dualite Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- TZILQVJDAVFKLE-UHFFFAOYSA-N hexan-3-yl 2-methylprop-2-enoate Chemical group CCCC(CC)OC(=O)C(C)=C TZILQVJDAVFKLE-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229960003396 phenacemide Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
-
- 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
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/18—Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
-
- 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
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Definitions
- This invention relates to epoxy-based structural adhesives.
- Epoxy resin based adhesives are used in many applications. In the automotive industry, epoxy resin adhesives are used in many bonding applications, including metal- metal bonding in frame and other structures in automobiles. Some of these adhesives must strongly resist failure during vehicle collision situations. Adhesives of this type are sometimes referred to as “crash durable adhesives", or "CDAs”.
- CDAs and other epoxy adhesives are usually formulated into either "one-part” or "two-part” formulations.
- the adhesive formulation is divided into two parts, one of which contains the epoxide compounds and the other of which contains the epoxide curing agents.
- the two parts have to be mixed together at the time of their use.
- the requirement for mixing means that some means must be provided to meter the parts accurately to obtain the proper mix ratios, and to ensure that the parts are mixed adequately so the formulation can cure consistently to form a cured adhesive having fully developed properties.
- a one-part adhesive formulation allows one to avoid the metering and mixing steps at the point of application.
- a one-part formulation all components of the adhesive formulation, including the epoxides and the curing agents, are formed into a single blend. Curing is effected in most cases by exposing the formulation to elevated temperatures. Because all of the reactive components are present in the one-part formulation, there is a tendency for the adhesive to cure prematurely. These adhesives are commonly manufactured and packaged weeks or months before they will be used, and they must remain in an uncured state throughout that period of time. Premature curing causes the product viscosity to increase, which can make it difficult to apply to a substrate. In extreme cases, the product becomes completely unusable.
- latent curing agents and catalysts are available, and they are commonly used in one-part adhesive formulations.
- the latent materials are in some cases solid materials that have melting temperatures of 8O 0 C or more. They can be dispersed into the adhesive formulation in the form of solid particles that have little reactivity until they are heated and melted. In other cases, the latent materials may be encapsulated in a wax or polymeric shell. Heating melts or decomposes the encapsulant to release the active material.
- Another type of latent material has blocked functional groups. The blocked functional groups can be thermally deblocked to generate an active material.
- This invention is a one-part structural adhesive, comprising:
- the invention is also a method comprising applying the foregoing structural adhesive to the surfaces of two substrates, and curing the structural adhesive to form an adhesive bond between the two substrates. At least one and preferably both of the substrates are metals.
- the presence of the epoxy-functionalized fatty acid oligomer and the polyol in combination has been found to make the one-part structural adhesive more storage stable.
- the adhesive has a reduced tendency to build viscosity over time when maintained under ordinary storage conditions. Under ordinary storage conditions, the adhesive is maintained in a sealed container so as to exclude contact with moisture and other chemicals, at a temperature from about 0 to about 5O 0 C, i.e., below the expected curing temperature for the formulation.
- the reduced tendency of the product to build viscosity under these conditions translates straightforwardly into a longer shelf life, as more time is required until the product viscosity increases so much that the product is no longer useful.
- a wide range of epoxy resins can be used as a non-rubber-modified epoxy resin, including those described at column 2 line 66 to column 4 line 24 of U.S. Patent 4,734,332, incorporated herein by reference.
- the epoxy resin will contain an average of at least 2.0 epoxide groups per molecule.
- Suitable epoxy resins include the diglycidyl ethers of polyhydric phenol compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (l,l-bis(4-hydroxylphenyl)-l-phenyl ethane), bisphenol F, bisphenol K and tetramethylbiphenol; diglycidyl ethers of aliphatic glycols and polyether glycols such as the diglycidyl ethers of C2-24 alkylene glycols and poly(ethylene oxide) or poly(propylene oxide) glycols; polyglycidyl ethers of phenol-formaldehyde novolac resins, alkyl substituted phenol-formaldehyde resins (epoxy novolac resins), phenol- hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene- phenol resins and dicyclopentadiene-sub
- Suitable epoxy resins include diglycidyl ethers of bisphenol A resins such as are sold by Dow Chemical under the designations D.E.R.® 330, D.E.R.® 331, D.E.R.® 332, D.E.R.® 383, D.E.R. 661 and D.E.R.® 662 resins.
- diglycidyl ethers of polyglycols that are useful include those sold as D.E.R.® 732 and D.E.R.® 736 by Dow Chemical. Epoxy novolac resins can be used. Such resins are available commercially as
- a cycloaliphatic epoxide includes a saturated carbon ring having an epoxy oxygen bonded to two vicinal atoms in the carbon ring, as illustrated by the following structure IV: wherein R is an aliphatic, cycloaliphatic and/or aromatic group and n is a number from 1 to 10, preferably from 2 to 4.
- R is an aliphatic, cycloaliphatic and/or aromatic group
- n is a number from 1 to 10, preferably from 2 to 4.
- the cycloaliphatic epoxide is a monoepoxide.
- Di- or polyepoxides are formed when n is 2 or more. Mixtures of mono-, di- and/or polyepoxides can be used.
- Cycloaliphatic epoxy resins as described in U.S. Patent No.
- Cycloaliphatic epoxy resins of particular interest are (3,4-epoxycyclohexyl-methyl)-3,4- epoxy-cyclohexane carboxylate, bis-(3,4-epoxycyclohexyl) adipate, vinylcyclohexene monoxide and mixtures thereof.
- Other suitable epoxy resins include oxazolidone-containing compounds as described in U. S. Patent No. 5,112,932.
- an advanced epoxy-isocyanate copolymer such as those sold commercially as D.E.R. 592 and D.E.R. 6508 (Dow Chemical) can be used.
- the non-rubber-modified epoxy resin preferably is a bisphenol-type epoxy resin or mixture thereof with up to 20 percent by weight of another type of epoxy resin.
- the most preferred epoxy resins are bisphenol-A based epoxy resins and bisphenol-F based epoxy resins. These can have average epoxy equivalent weights of from about 170 to 600 or more, preferably from 225 to 400.
- An especially preferred non-rubber-modified epoxy resin is a mixture of a diglycidyl ether of a polyhydric phenol, preferably bisphenol-A or bisphenol-F, having an epoxy equivalent weight of from 170 to 299, especially from 170 to 225, and a second diglycidyl ether of a polyhydric phenol, again preferably bisphenol-A or bisphenol-F, this one having an epoxy equivalent weight of at least 300, preferably from 310 to 600.
- the proportions of the two resins are preferably such that the mixture of the two resins has an average epoxy equivalent weight of from 225 to 400.
- the mixture optionally may also contain up to 20%, preferably up to 10%, of one or more other non-rubber-modified epoxy resins.
- a non-rubber-modified epoxy resin preferably will constitute at least about 25 weight percent of the structural adhesive, more preferably at least about 30 weight percent, and still more preferably at least about 35 part weight percent.
- the non- rubber-modified epoxy resin may constitute up to about 60 weight percent of the structural adhesive, more preferably up to about 50 weight percent.
- These amounts include any non-rubber-modified epoxy resin that may be brought into the composition with other components that contain an epoxy resin as, as for example, a diluent or excess, unreacted reagent.
- the elastomeric toughener is a liquid or low-melting elastomeric material which contains urethane and/or urea groups and has terminal capped isocyanate groups.
- the elastomeric toughener suitably contains, on average, from about 1.5, preferably from about 2.0, to about 8, preferably to about 6, more preferably to about 4, capped isocyanate groups per molecule.
- the elastomeric toughener has capped isocyanate groups.
- the capping groups may be, for example, a phenolic compound, an aminophenolic compound, a primary or secondary aliphatic or cycloaliphatic amine, a benzyl alcohol, an aromatic or heteroaromatic amine, a benzyl amine or a thiol compound.
- the capping or blocking group may contain additional functional groups (such as phenolic OH groups) which do not react with epoxy groups under ordinary storage conditions, but the capping or blocking group may instead be devoid of such groups.
- the toughener contains at least one internal segment that provides elastomeric character. It may contain two or more such segments. This segment may be a polyether segment or a segment of a butadiene homopolymer or copolymer. Segments of both types may be present in the toughener. Each polyether segment or segment of a butadiene homopolymer or copolymer preferably has a weight of from 800 to 5000 daltons, preferably from 1500 to 4000 daltons.
- the elastomeric toughener may also contain residues of a branching agent, a chain extender, or both.
- Branching agents for purposes of this invention, are polyol or polyamine compounds having a molecular weight of up to 750, preferably from 50 to 500, and at least three hydroxyl, primary amino and/or secondary amino groups per molecule. Branching agents provide branching to the toughener, and are useful to increase the functionality (i.e., number of capped isocyanate groups per molecule) of the toughener.
- Chain extenders for purposes of this invention, are polyol or polyamine compounds having a molecular weight of up to 750, preferably from 50 to 500, and two hydroxyl, primary amino and/or secondary amino groups per molecule.
- Chain extenders help to increase the molecular weight of the elastomeric toughener without increasing functionality.
- the elastomeric toughener suitably has a number average molecular weight from at least 3000, preferably at least 5000, to about 30,000, preferably to about 20,000 and more preferably to about 15,000. Molecular weights as used herein are determined according to GPC analysis, taking into account peaks in excess of 1000.
- the polydispersity ratio of weight average molecular weight to number average molecular weight
- the elastomeric toughener should be soluble or dispersible in the remainder of the reactive components of the structural adhesive.
- Suitable elastomeric tougheners and methods for preparing them are described, for example, in U. S. Patent Nos. 5,202,390, 5,232,996, 5,278,257 and 6,660,805, U. S.
- the elastomeric toughener can be represented by the idealized structure (I)
- p represents the average number of capped isocyanate groups per molecule, p is suitably at least 1.5, preferably at least 2, to 8, preferably to 6, more preferably to 4.
- Each A in structure I represents the residue, after removal of a hydrogen atom, of a capping group.
- Y is the residue of an isocyanate-terminated prepolymer after removal of the terminal isocyanate groups.
- Y contains at least one elastomeric segment. Each elastomeric segment preferably has a relatively high molecular weight, preferably a molecular weight of at least 800 daltons.
- the number average molecular weight of the elastomeric segment may be as high as 15000 daltons, and is preferably from 1500 to 10000 daltons, in each case.
- This elastomeric segment is preferably linear or at most slightly branched.
- the elastomeric segment(s) each may be a polyether segment or a segment of a butadiene homopolymer or copolymer, as described before.
- the Y group may contain one or more segments of each type.
- the Y group may contain urethane and/or urea groups, and may in addition contain residues (after removal of hydroxyl or amino groups, as the case may be) of one or more crosslinkers or chain extenders.
- Chain extenders may be aromatic or aliphatic diols, diamines or hydroxylamines.
- the reactive toughener can be prepared by forming an isocyanate-terminated prepolymer, and then capping the terminal isocyanate groups with one or more capping agents.
- the isocyanate-terminated prepolymer can be prepared by reaction of one or more polyol or polyamine compounds with a stoichiometric excess of a polyisocyanate compound, preferably a diisocyanate compound. At least one of the polyol or polyamine compounds imparts elastomeric properties to the toughener.
- the polyisocyanate may be an aromatic polyisocyanate, but it is preferably an aliphatic polyisocyanate such as isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated methylene diphenylisocyanate (Hi 2 MDI), and the like.
- the polyol or polyamine is made up of or contains at least one relatively high weight elastomeric segment as described before.
- a mixture of polyols or polyamines it is also possible to use a mixture of polyols or polyamines to make the prepolymer. It is preferred that at least 50%, more preferably at least 80%, and even more preferably at least 90%, by weight of the polyol or polyamine materials used to make the prepolymer contain or are made up of at least one relatively high weight elastomeric segment as described before.
- the polyisocyanate compound can be reacted all at once with the mixture to produce the prepolymer in a single step.
- the polyisocyanate may be reacted with each polyol or polyamine compound sequentially, or with various subsets thereof. The latter approach is often useful to produce a prepolymer having a more defined molecular structure.
- the proportions of starting materials are suitably selected so that the prepolymer has an isocyanate content of from 0.5 to 6% by weight, more preferably from 1 to 5% by weight and even more preferably from 1.5 to 4% by weight.
- isocyanate equivalent weight a preferred range is from 700 to 8400, a more preferred range is from
- the elastomeric toughener is then prepared from the prepolymer by reacting the isocyanate prepolymer with one or more capping agents.
- the proportions of starting materials are selected so that at least one mole of capping agent is provided per equivalent of isocyanate group on the prepolymer. Such a ratio of starting materials allows for the capping reaction to proceed until the isocyanate groups are essentially all consumed, without significantly advancing the prepolymer.
- Suitable capping agents include secondary amine compounds such as dialkyl amines like diisopropyl amine, diethylamine, di-t-butylamine, di-n-butylamine and the like.
- Suitable capping agents include compounds that contain at least one phenolic hydroxyl group, i.e., a hydroxyl group bonded directly to a carbon atom of an aromatic ring.
- the phenolic compound may have two or more phenolic hydroxyl groups, but preferably contains only one phenolic hydroxyl group.
- the phenolic compound may contain other substituent groups, but these preferably are not reactive with an isocyanate group under the conditions of the capping reaction. Alkenyl groups, especially allyl groups, are of particular interest.
- substituent groups include alkyl groups, which may be linear, branched or cycloalkyl; aromatic groups such as phenyl, alkyl-substituted phenyl, alkenyl -substituted phenyl and the like; aryl- substituted alkyl groups; and phenol-substituted alkyl groups, wherein the phenol substituent group may itself be unsubstituted or substituted.
- Suitable phenolic compounds include phenol, cresol, allylphenol (especially o-allylphenol), resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (l,l-bis(4- hydroxylphenyl)-l-phenyl ethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol and o,o'-diallyl-bisphenol A.
- capping agents include hydroxy-functional acrylate or methacrylate compounds that have one or more, especially one, hydroxyl group. Hydroxyl-functional acrylate and methacrylate compounds are preferred.
- suitable capping agents of this type are 2-hydroxyethylacrylate, 2-hydroxypropylacrylate, A- hydroxybutylacrylate, 2-hydroxybutylacrylate, 2-aminopropylacrylate, 2- hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 4-hydroxybutylmethacrylate, 2-hydroxybutylmethacrylate, and the like.
- Hydroxyl-functional epoxides are another useful type of capping agent. Suitable hydroxy-functional epoxides are compounds that have at least one epoxy group and one or more, especially one, hydroxyl group per molecule. The hydroxyl group should be significantly more reactive with an isocyanate group than the epoxide group(s). The hydroxyl groups are preferably bonded directly to an aliphatic carbon atom. The hydroxyl-functional epoxide is preferably devoid of aromatic groups. A preferred hydroxyl-functional epoxide is glycidol.
- the toughener should constitute at least 5 weight percent of the adhesive composition. Better results are typically seen when the amount of toughener is at least 8 weight percent or at least 10 weight percent.
- the toughener may constitute up to 45 weight percent thereof, preferably up to 30 weight percent and more preferably up to 25 weight percent.
- the amount of toughener that is needed to provide good properties, particularly good low temperature properties, in any particular adhesive composition may depend somewhat on the other components of the composition, and may depend somewhat on the molecular weight of the toughener.
- the epoxy-functionalized fatty acid oligomer is an oligomeric unsaturated fatty acid, in which the carboxylic acid groups have been capped or otherwise converted to introduce terminal epoxide groups.
- the oligomeric fatty acid may have a degree of polymerization of from about 2 to about 4.
- the starting fatty acid may have, for example, from 14 to 24 carbon atoms, with fatty acids having from 16 to 18 carbon atoms being preferred.
- the oligomer preferably is hydrogenated to remove any residual carbon-carbon double bonds that may be present after the oligomerization reaction.
- Useful oligomeric fatty acids include the so-called "dimer fatty acid" products that are readily commercially available.
- the epoxy-functionalized fatty acid oligomer can be prepared by capping the carboxylic acid groups with a polyepoxide, including any of the epoxy resin materials described hereinbefore. Polyphenols such as bisphenol A or bisphenol F are especially preferred for this purpose. It is preferred to conduct the capping reaction with at least one mole of the polyepoxide per equivalent of carboxylic acid groups in the oligomeric fatty acid, in order to cap the carboxylic acid groups without significant chain extension.
- a greater excess of the polyepoxide is more preferred, as this leads to a product that includes the epoxy-functionalized fatty acid oligomer and some quantity of excess, unreacted polyepoxide.
- the epoxy-functionalized fatty acid oligomer should constitute from about 0.4 to
- the weight of the epoxy-functionalized fatty acid oligomer does not include any excess, unreacted polyepoxide that may be present. Any such excess polyepoxide counts as part of the non-rubber-modified portion of the structural adhesive.
- the weight of the epoxy-functionalized fatty acid oligomer can be calculated as the weight of the starting fatty acid oligomer plus the weight of one mole of the polyepoxide per equivalent of the fatty acid oligomer used in the capping reaction.
- the structural adhesive also contains a crystalline or semi-crystalline polyester polyol having a molecular weight of from 500 to 10000, preferably from 1000 to 4000.
- the polyol has a crystalline melting temperature of from 40 to 125 0 C. It may contain from about 1.8 to 4, preferably from 1.8 to 2.5 hydroxyl groups per molecule, on average.
- Suitable polyester polyols include those available commercially from Evonik Industries under the trade name DynacollTM. Specific polyester polyol products include DynacollTM 7300, DynacollTM 7380 and DynacollTM 7381.
- the polyol suitably constitutes from 2 to 10 percent of the weight of the adhesive composition. A preferred amount is from 3 to 7 percent by weight.
- the structural adhesive also contains a curing agent. The curing agent is selected together with any catalysts such that the adhesive cures rapidly when heated to a temperature of 8O 0 C or greater, preferably 14O 0 C or greater, but cures very slowly if at all at room temperature ( ⁇ 22°C) and temperatures up to at least 5O 0 C.
- Suitable curing agents include materials such as boron trichloride/amine and boron trifluoride/amine complexes, dicyandiamide, melamine, diallylmelamine, guanamines such as acetoguanamine and benzoguanamine, aminotriazoles such as 3-amino-l,2,4-triazole, hydrazides such as adipic dihydrazide, stearic dihydrazide, isophthalic dihydrazide, semicarbazide, cyanoacetamide, and aromatic polyamines such as diaminodiphenylsulphones.
- dicyandiamide, isophthalic acid dihydrazide, adipic acid dihydrazide and/or 4,4'-diaminodiphenylsulphone is particularly preferred.
- the curing agent is used in an amount sufficient to cure the composition. Typically, enough of the curing agent is provided to consume at least 80% of the epoxide groups present in the composition. A large excess of that amount needed to consume the epoxide groups is generally not needed.
- the curing agent constitutes at least about 1.5 weight percent of the structural adhesive, more preferably at least about 2.5 weight percent and even more preferably at least 3.0 weight percent.
- the curing agent preferably constitutes up to about 15 weight percent of the structural adhesive composition, more preferably up to about 10 weight percent, and most preferably up to about 8 weight percent.
- the structural adhesive will in most cases contain a catalyst to promote the cure of the adhesive, i.e., the reaction of epoxy groups with epoxide-reactive groups on the curing agent and other components of the adhesive.
- the catalyst may be encapsulated or otherwise be a latent type which becomes active only upon exposure to elevated temperatures.
- preferred epoxy catalysts are ureas such as p-chlorophenyl-N,N- dimethylurea (Monuron), 3-phenyl-l,l-dimethylurea (Phenuron), 3,4-dichlorophenyl- N, N- dimethylurea (Diuron) , N- (3 -chloro-4- methylphenyl) -N', N'- dimethylurea
- tert-acryl- or alkylene amines like benzyldimethylamine, 2,4,6- tris(dimethylaminomethyl)phenol, piperidine or derivates thereof, imidazole derivates, in general C1-C12 alkylene imidazole or N-arylimidazols, such as 2-ethyl-2- methylimidazol, or N-butylimidazol, 6-caprolactam
- a preferred catalyst is 2,4,6- tris(dimethylaminomethyl)phenol integrated into a poly(p-vinylphenol) matrix (as described in European patent EP 0 197 892).
- the catalyst is present in an amount of at least about 0.1 weight percent of the structural adhesive, and more preferably at least about 0.5 weight percent.
- the catalyst constitutes up to about 2 weight percent of the structural adhesive, more preferably up to about 1.0 weight percent, and most preferably up to about 0.7 weight percent.
- the structural adhesive of the invention may contain various other optional components.
- a rubber- modified epoxy resin for purposes of this invention is a reaction product of an epoxy resin and at least one liquid rubber that has epoxide-reactive groups, such as amino or preferably carboxyl groups.
- the resulting adduct has reactive epoxide groups which can be cured further when the structural adhesive is cured.
- It is preferred that at least a portion of the liquid rubber has a glass transition temperature (T g ) of -4O 0 C or lower, especially -5O 0 C or lower.
- each of the rubbers (when more than one is used) has a glass transition temperature of -25 0 C or lower.
- the rubber T g may be as low as - 100 0 C or even lower.
- the liquid rubber is preferably a homopolymer or copolymer of a conjugated diene, especially a diene/nitrile copolymer.
- the conjugated diene rubber is preferably butadiene or isoprene, with butadiene being especially preferred.
- the preferred nitrile monomer is acrylonitrile.
- Preferred copolymers are butadiene-acrylonitrile copolymers.
- Carboxyl-terminated rubbers are preferred.
- the molecular weight (M n ) of the rubber is suitably from about 2000 to about 6000, more preferably from about 3000 to about 5000.
- Suitable carboxyl-functional butadiene and butadiene/acrylonitrile rubbers are commercially available from Noveon under the tradenames Hycar ® 2000X162 carboxyl- terminated butadiene homopolymer, Hycar ® 1300X31, Hycar ® 1300X8, Hycar ® 1300X13, Hycar ® 1300X9 and Hycar ® 1300X18 carboxyl-terminated butadiene/acrylonitrile copolymers.
- a suitable amine-terminated butadiene/acrylonitrile copolymer is sold under the tradename Hycar ® 1300X21.
- the rubber is formed into an epoxy-terminated adduct by reaction with an excess of a polyepoxide.
- a ratio of at least one mole of polyepoxide per equivalent of epoxy- reactive groups on the rubber is preferred.
- the rubber and an excess of the polyepoxide are mixed together with a polymerization catalyst and heated to a temperature of about 100 to about 25O 0 C in order to form the adduct.
- Suitable catalysts include those described before.
- Preferred catalysts for forming the rubber-modified epoxy resin include phenyl dimethyl urea and triphenyl phosphine.
- Preferred polyepoxides are liquid or solid glycidyl ethers of a bisphenol such as bisphenol A or bisphenol F.
- the rubber-modified epoxy resin(s), if present at all, may constitute about 1 weight percent of the structural adhesive or more, preferably at least about 2 weight percent.
- the rubber-modified epoxy resin may constitute up to about 25 weight percent of the structural adhesive, more preferably up to about 20 weight percent, and even more preferably up to about 15 weight percent.
- the structural adhesive of the invention may contain one or more core-shell rubbers.
- the core-shell rubber is a particulate material having a rubbery core.
- the rubbery core preferably has a T g of less than -2O 0 C, more preferably less than -5O 0 C and even more preferably less than -7O 0 C.
- the T g of the rubbery core may be below -100 0 C.
- the core-shell rubber also has at least one shell portion that preferably has a T g of at least 5O 0 C.
- core it is meant an internal portion of the core-shell rubber.
- the core may form the center of the core- shell particle, or an internal shell or domain of the core- shell rubber.
- a shell is a portion of the core- shell rubber that is exterior to the rubbery core.
- the shell portion (or portions) typically forms the outermost portion of the core- shell rubber particle.
- the shell material is preferably grafted onto the core or is crosslinked or both.
- the rubbery core may constitute from 50 to 95%, especially from 60 to 90%, of the weight of the core-shell rubber particle.
- the core of the core- shell rubber may be a polymer or copolymer of a conjugated diene such as butadiene, or a lower alkyl acrylate such as n-butyl-, ethyl-, isobutyl- or 2- ethylhexylacrylate.
- the core polymer may in addition contain up to 20% by weight of other copolymerized monounsaturated monomers such as styrene, vinyl acetate, vinyl chloride, methyl methacrylate, and the like.
- the core polymer is optionally crosslinked.
- the core polymer optionally contains up to 5% of a copolymerized graft-linking monomer having two or more sites of unsaturation of unequal reactivity, such as diallyl maleate, monoallyl fumarate, allyl methacrylate, and the like, at least one of the reactive sites being non-conjugated.
- a copolymerized graft-linking monomer having two or more sites of unsaturation of unequal reactivity, such as diallyl maleate, monoallyl fumarate, allyl methacrylate, and the like, at least one of the reactive sites being non-conjugated.
- the core polymer may also be a silicone rubber. These materials often have glass transition temperatures below -100 0 C.
- Core-shell rubbers having a silicone rubber core include those commercially available from Wacker Chemie, Kunststoff, Germany, under the trade name GenioperlTM.
- the shell polymer which is optionally chemically grafted or crosslinked to the rubber core, is preferably polymerized from at least one lower alkyl methacrylate such as methyl-, ethyl- or t-butyl methacrylate.
- a particularly preferred type of core-shell rubber is of the type described in EP 1 632 533 Al.
- the core-shell rubber is preferably dispersed in a polymer or an epoxy resin, also as described in EP 1 632 533 Al.
- Preferred core-shell rubbers include those sold by Kaneka Corporation under the designation Kaneka Kane Ace, including Kaneka Kane Ace MX 156 and Kaneka Kane Ace MX 120 core-shell rubber dispersions.
- the products contain the core-shell rubber particles pre-dispersed in an epoxy resin, at a concentration of approximately 25%.
- the epoxy resin contained in those products will form all or part of the non-rubber-modified epoxy resin component of the structural adhesive of the invention.
- the core-shell rubber particles can constitute from 0 to 15 weight percent of the structural adhesive.
- the total rubber content of the structural adhesive of the invention can range from as little as 0 weight percent to as high as 30 weight percent.
- a preferred rubber content for a crash durable adhesive is from 1 weight percent to as much as 20 weight percent, preferably from 2 to 15 weight percent and more preferably from 4 to 15 weight percent.
- Total rubber content is calculated for purposes of this invention by determining the weight of core- shell rubber, plus the weight contributed by the liquid rubber portion of any rubber-modified epoxy resin as may be used. No portion of the elastomeric toughener is considered in calculating total rubber content.
- the weight of unreacted (non-rubber-modified) epoxy resins and/or other carriers, diluents, dispersants or other ingredients that may be contained in the core-shell rubber product or rubber-modified epoxy resin is not included.
- the weight of the shell portion of the core-shell rubber is counted as part of the total rubber content for purposes of this invention.
- At least one filler, rheology modifier and/or pigment is preferably present in the structural adhesive. These can perform several functions, such as (1) modifying the rheology of the adhesive in a desirable way, (2) reducing overall cost per unit weight, (3) absorbing moisture or oils from the adhesive or from a substrate to which it is applied, and/or (4) promoting cohesive, rather than adhesive, failure.
- Examples of these materials include calcium carbonate, calcium oxide, talc, carbon black, textile fibers, glass particles or fibers, aramid pulp, boron fibers, carbon fibers, mineral silicates, mica, powdered quartz, hydrated aluminum oxide, bentonite, wollastonite, kaolin, fumed silica, silica aerogel or metal powders such as aluminum powder or iron powder.
- Another filler of particular interest is a microballon having an average particle size of up to 200 microns and density of up to 0.2 g/cc. The particle size is preferably about 25 to 150 microns and the density is preferably from about 0.05 to about 0.15 g/cc.
- the microballoons can be of the expanded or the heat expandable types. Heat expandable microballoons which are suitable for reducing density include those commercially available from Dualite Corporation under the trade designation DualiteTM, and those sold by Akzo Nobel under the trade designation ExpancelTM.
- Fillers, pigment and rheology modifiers are preferably are used in an aggregate amount of about 2 parts per hundred parts of adhesive composition or greater, more preferably about 5 parts per hundred parts of adhesive composition or greater. They preferably are present in an amount of up to about 25 weight percent of the structural adhesive, more preferably up to about 20 weight percent, and most preferably up to about 15 weight percent.
- the structural adhesive can further contain other additives such as diluents, plasticizers, extenders, pigments and dyes, fire-retarding agents, thixotropic agents, expanding agents, flow control agents, adhesion promoters and antioxidants.
- Suitable expanding agents include both physical and chemical type agents.
- the adhesive may also contain a thermoplastic powder such as polyvinylbutyral as a gelling agent for a pregelling process.
- Storage stability can be evaluated by storing the structural adhesive under a nitrogen atmosphere at 23 0 C or 3O 0 C for 24 weeks, and measuring the viscosity of the adhesive before and after storage. Evaluations at 23 0 C model typical indoor storage conditions, as in a typical climate-controlled warehouse setting. Evaluations at 3O 0 C model conditions that might be encountered during warehousing and transportation during warmer months of the year, and thus represents more stringent aging conditions.
- the structural adhesive of the invention often exhibits in increase in viscosity from 0% to 150%, more typically from 50 to 100%, over the 24-week period.
- the structural adhesive of the invention often exhibits in increase in viscosity from 0% to 300%, more typically from 100 to 250%, over the 24- week period.
- a suitable measuring device is a Bohlin rheometer CS-50 cone-plate 4° angle 20 mm cone-diameter, or equivalent device.
- the viscosity measurements using this device are taken by ramping the shear rate up from 0.1 to 10 reciprocal seconds and back. Viscosity is taken at a shear rate of 10 reciprocal seconds during the ramp up.
- the adhesive composition can be applied by any convenient technique. It can be applied cold or be applied warm if desired. It can be applied by extruding it from a robot into bead form on the substrate, it can be applied using mechanical application methods such as a caulking gun, or any other manual application means, and it can also be applied using jet spraying methods such as a steaming method or a swirl technique.
- the swirl technique is applied using an apparatus well known to one skilled in the art such as pumps, control systems, dosing gun assemblies, remote dosing devices and application guns.
- the adhesive is applied to the substrate using a jet spraying or streaming process. Generally, the adhesive is applied to one or both substrates. The substrates are contacted such that the adhesive is located between the substrates to be bonded together.
- the structural adhesive is cured by heating to a temperature at which the curing agent initiates cure of the epoxy resin composition. Generally, this temperature is about 8O 0 C or above, preferably about 14O 0 C or above. The preferred temperature does not exceed 200 0 C.
- the adhesive of the invention can be used to bond a variety of substrates together including wood, metal, coated metal, aluminum, a variety of plastic and filled plastic substrates, fiberglass and the like. In one preferred embodiment, the adhesive is used to bond parts of automobiles together. Such parts can be steel, coated steel, galvanized steel, aluminum, coated aluminum, plastic and filled plastic substrates. An application of particular interest is bonding of automotive frame components to each other or to other components.
- the frame components are often metals such as cold rolled steel, galvanized metals, or aluminum.
- the components that are to be bonded to the frame components can also be metals as just described, or can be other metals, plastics, composite materials, and the like.
- Adhesion to brittle metals such as galvaneal is of particular interest in the automotive industry. Galvaneal tends to have a zinc-iron surface that is somewhat rich in iron content and is brittle for that reason.
- a particular advantage of this invention is that the cured adhesive bonds well to brittle metals such as galvaneal.
- Another application of particular interest is the bonding of aerospace components, particularly exterior metal components or other metal components that are exposed to ambient atmospheric conditions during flight.
- Assembled automotive frame members are usually coated with a coating material that requires a bake cure.
- the coating is typically baked at temperatures that may range from 14O 0 C to over 200 0 C. In such cases, it is often convenient to apply the structural adhesive to the frame components, then apply the coating, and cure the adhesive at the same time the coating is baked and cured.
- the adhesive composition once cured preferably has a Young's modulus of about 1000 MPa as measured according to DIN EN ISO 527-1.
- the Young's modulus is about 1200 MPa or greater, more preferably at least 1500 MPa.
- the cured adhesive demonstrates a tensile strength of about 20 MPa or greater, more preferably about 25 MPa or greater, and most preferably about 35 MPa or greater.
- the lap shear strength of a 1.5 mm thick cured adhesive layer on cold rolled steel (CRS) and galvaneal is about 15 MPa or greater, more preferably about 20 MPa or greater, and most preferably about 25 MPa or greater measured according to DIN EN 1465.
- the cured adhesive of the invention demonstrates excellent adhesive properties (such as lap shear strength and impact peel strength) over a range of temperatures down to -4O 0 C or lower.
- Epoxy Resin Mixture is a blend of a solid diglycidyl ether of bisphenol A
- StruktolTM 3614 is a reaction product of approximately 60% of a liquid diglycidyl ether of bisphenol F and 40% of Hycar 1300X13 rubber (a carboxy-terminated butadiene-acrylonitrile copolymer having a T g less than -4O 0 C, available from Noveon). It is commercially available from Schill & Seilacher.
- StruktolTM 3604 is a reaction product of approximately 60% a liquid diglycidyl ether of bisphenol A and 40% of Hycar 1300X8 rubber (a carboxy-terminated butadiene- acrylonitrile copolymer having a T g of about -52 0 C, available from Noveon). It is commercially available from Schill & Seilacher.
- the Toughener is an elastomeric toughener is an isocyanate-terminated polyurethane prepolymer prepared from a polyether polyol and an aliphatic diisocyanate, in which the isocyanate groups are capped with o,o-diallyl bisphenol A, and is made as described in Example 13 of EP 308 664.
- Polyester premix is a blend of 80 weight percent D.E.R.TM 330 epoxy resin and 20 weight percent of DynacollTM 7330 polyester polyol.
- DynacollTM 7330 polyester polyol is nominally difunctional and has a molecular weight of about 3500.
- D.E.R.TM 330 is a liquid diglycidyl ether of bisphenol A, available from The Dow Chemical Company. It has an epoxy equivalent weight of approximately 180.
- Epoxide-functional fatty acid oligomer is a reaction product of 12.5% of a 36 carbon atom, fully hydrogenated dimerized fatty acid (available from Sigma Aldrich) and 87.3% of D.E.R.330 epoxy resin.
- the reaction product contains about 25% by weight of an epoxide-capped fatty acid oligomer and about 75% by weight of excess, unreacted epoxy resin.
- Dynasilan A- 187 is an epoxy silane available from General Electric Silicones.
- AmicureTM CG- 1200G is a cyanoguanidine epoxy hardener available from Air Products and Chemicals.
- EP796 is tris (2,4,6-dimethylaminomethyl)phenol in a poly(vinylphenol) matrix.
- One-part, heat activated adhesives are prepared from the following formulations described in Table 1.
- Storage stability is evaluated by measuring the increase in the viscosity of each uncured adhesive over a period of 24 weeks, when stored under nitrogen at 23 0 C and at 3O 0 C. Viscosities are measured at 45°C by using a Bohlin rheometer CS-50 cone-plate 4° angle 20 mm cone-diameter. The shear rate is ramped up from 0.1 to 10 reciprocal seconds and back. Viscosity is taken at a shear rate of 10 reciprocal seconds during the ramp up. Results are as indicated in Table 2. Table 2
- Test coupons for the impact peel testing are 90 mm X 20 mm with a bonded area of 30 X 20 mm.
- the samples are prepared by wiping them with acetone.
- a 0.15 mm X 10 mm wide Teflon tape is applied to the coupons to define the bond area.
- the structural adhesive is then applied to the bond area of latter coupon and squeezed onto the first coupon to prepare each test specimen.
- the adhesive layer is 0.2 mm thick.
- Duplicate samples are cured for 30 minutes at 18O 0 C.
- Duplicate test coupons are prepared and are evaluated for lap shear strength in accordance with DIN EN 1465. Testing is performed at a test speed of 10 mm/minute.
- Test samples are prepared using each adhesive.
- the bonded area in each case is 25 X 10 mm.
- the adhesive layer is 0.2 mm thick.
- Duplicate test specimens are cured at for 30 minutes at 18O 0 C.
Abstract
Description
Claims
Priority Applications (5)
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CN2010800094422A CN102333837A (en) | 2009-02-26 | 2010-02-03 | One-part structural epoxy resin adhesives containing dimerized fatty acid/epoxy resin adduct and a polyol |
EP10703751A EP2401339A1 (en) | 2009-02-26 | 2010-02-03 | One-part structural epoxy resin adhesives containing dimerized fatty acid/epoxy resin adduct and a polyol |
JP2011552055A JP2012519220A (en) | 2009-02-26 | 2010-02-03 | One-part epoxy resin adhesive containing dimerized fatty acid / epoxy resin adduct and polyol |
BRPI1005818A BRPI1005818A2 (en) | 2009-02-26 | 2010-02-03 | one-component structural adhesive and structural adhesive application method |
US13/146,198 US20110297317A1 (en) | 2009-02-26 | 2010-02-03 | One-part structural epoxy resin adhesives containing dimerized fatty acid/epoxy resin adduct and a polyol |
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EP (1) | EP2401339A1 (en) |
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2010
- 2010-02-03 BR BRPI1005818A patent/BRPI1005818A2/en not_active Application Discontinuation
- 2010-02-03 WO PCT/US2010/022979 patent/WO2010098950A1/en active Application Filing
- 2010-02-03 US US13/146,198 patent/US20110297317A1/en not_active Abandoned
- 2010-02-03 JP JP2011552055A patent/JP2012519220A/en not_active Withdrawn
- 2010-02-03 EP EP10703751A patent/EP2401339A1/en not_active Withdrawn
- 2010-02-03 KR KR1020117022313A patent/KR20110132399A/en not_active Application Discontinuation
- 2010-02-03 CN CN2010800094422A patent/CN102333837A/en active Pending
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US20130263995A1 (en) * | 2010-12-26 | 2013-10-10 | Andreas Lutz | Structural epoxy resin adhesives containing chain-extended elastomeric tougheners capped with phenol, polyphenol or aminophenol compounds |
US9181463B2 (en) * | 2010-12-26 | 2015-11-10 | Dow Global Technologies Llc | Structural epoxy resin adhesives containing chain-extended elastomeric tougheners capped with phenol, polyphenol or aminophenol compounds |
JP2014518922A (en) * | 2011-05-19 | 2014-08-07 | ダウ グローバル テクノロジーズ エルエルシー | Novel structural adhesives and their use |
US9346984B2 (en) | 2012-03-21 | 2016-05-24 | Dow Global Technologies Llc | Wash-off resistant epoxy adhesive composition and pre-gelled adhesive |
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JP2015517001A (en) * | 2012-03-23 | 2015-06-18 | ダウ グローバル テクノロジーズ エルエルシー | Fracture durability adhesive with high stress durability |
WO2015053289A1 (en) | 2013-10-11 | 2015-04-16 | 株式会社カネカ | Core-shell polymer-containing epoxy resin composition, cured product of same and method for producing same |
WO2015064561A1 (en) | 2013-10-29 | 2015-05-07 | 株式会社カネカ | Curable resin composition containing polymer fine particles and having improved storage stability |
EP3428214A1 (en) | 2013-10-29 | 2019-01-16 | Kaneka Corporation | Polymer fine particle-containing curable resin composition having improved storage stability |
WO2016014284A1 (en) | 2014-07-23 | 2016-01-28 | Dow Global Technologies Llc | Structural adhesives having improved wash-off resistance and method for dispensing same |
US10150893B2 (en) | 2014-07-23 | 2018-12-11 | Dow Global Technologies Llc | Structural adhesives having improved wash-off resistance and method for dispensing same |
WO2018156450A1 (en) * | 2017-02-26 | 2018-08-30 | Dow Global Technologies Llc | One-component toughened epoxy adhesives containing a mixture of latent curing agents |
US11274236B2 (en) | 2017-02-26 | 2022-03-15 | Ddp Specialty Electronic Materials Us, Llc | One-component toughened epoxy adhesives containing a mixture of latent curing agents |
US11359119B2 (en) | 2017-06-22 | 2022-06-14 | Sika Technology Ag | Method for connecting molded bodies by injecting a single-component heat-curing epoxy resin composition into cavities |
WO2019208569A1 (en) | 2018-04-27 | 2019-10-31 | 株式会社カネカ | Adhesion method employing polymer microparticle-containing curable resin composition having excellent workability, and laminate obtained using said adhesion method |
CN114276777A (en) * | 2021-12-27 | 2022-04-05 | 烟台德邦科技股份有限公司 | Reactive polyurethane hot melt adhesive and preparation method thereof |
WO2023240541A1 (en) | 2022-06-16 | 2023-12-21 | Sika Technology Ag | One-component thermosetting epoxy adhesive with improved adhesion |
Also Published As
Publication number | Publication date |
---|---|
US20110297317A1 (en) | 2011-12-08 |
BRPI1005818A2 (en) | 2016-03-08 |
KR20110132399A (en) | 2011-12-07 |
JP2012519220A (en) | 2012-08-23 |
CN102333837A (en) | 2012-01-25 |
EP2401339A1 (en) | 2012-01-04 |
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