CA2788739A1 - Epoxy resin composition with reduced toxicity - Google Patents
Epoxy resin composition with reduced toxicity Download PDFInfo
- Publication number
- CA2788739A1 CA2788739A1 CA2788739A CA2788739A CA2788739A1 CA 2788739 A1 CA2788739 A1 CA 2788739A1 CA 2788739 A CA2788739 A CA 2788739A CA 2788739 A CA2788739 A CA 2788739A CA 2788739 A1 CA2788739 A1 CA 2788739A1
- Authority
- CA
- Canada
- Prior art keywords
- epoxy
- component
- equivalent weight
- epichlorohydrin
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 50
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 231100000419 toxicity Toxicity 0.000 title description 2
- 230000001988 toxicity Effects 0.000 title description 2
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 50
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 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 claims abstract description 39
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 27
- 229920003986 novolac Polymers 0.000 claims abstract description 24
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 15
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims description 73
- 125000003700 epoxy group Chemical group 0.000 claims 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 claims description 29
- 238000009472 formulation Methods 0.000 claims description 19
- 239000000470 constituent Substances 0.000 claims description 18
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 238000005304 joining Methods 0.000 claims description 3
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012766 organic filler Substances 0.000 claims description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical group O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 150000002924 oxiranes Chemical class 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 18
- 239000000853 adhesive Substances 0.000 description 16
- 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 14
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 14
- 239000000945 filler Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- -1 cyclic tertiary amines Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002372 labelling Methods 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical class CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 2
- SUNXFMPZAFGPFW-UHFFFAOYSA-N 2-methyl-5-(1-sulfanylpropan-2-yl)cyclohexane-1-thiol Chemical compound SCC(C)C1CCC(C)C(S)C1 SUNXFMPZAFGPFW-UHFFFAOYSA-N 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- QEBJRRFIWCWPMA-UHFFFAOYSA-N diethyl-bis(sulfanyl)-$l^{4}-sulfane Chemical class CCS(S)(S)CC QEBJRRFIWCWPMA-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 230000000622 irritating effect Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000002110 toxicologic effect Effects 0.000 description 2
- 231100000027 toxicology Toxicity 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- MBROVJJNUFAJQC-UHFFFAOYSA-N 2,2-dimethylbutane;2,2,2-tris(sulfanyl)acetic acid Chemical compound CCC(C)(C)C.OC(=O)C(S)(S)S MBROVJJNUFAJQC-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 description 1
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 235000003276 Apios tuberosa Nutrition 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000010744 Arachis villosulicarpa Nutrition 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 206010012442 Dermatitis contact Diseases 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003974 aralkylamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- IBARAOFMHIVQQI-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.COC(=O)C(C)=C.CCCCOC(=O)C=C IBARAOFMHIVQQI-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 208000010247 contact dermatitis Diseases 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- FFHWGQQFANVOHV-UHFFFAOYSA-N dimethyldioxirane Chemical compound CC1(C)OO1 FFHWGQQFANVOHV-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004050 homopiperazines Chemical class 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 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
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
-
- 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
- C08G59/66—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
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Abstract
The present specification provides two-component compositions whose first component is a mixture of reactive epoxy resins and optionally further formulating ingredients, comprising, based on the mass of all the epoxy resins, a) at least 10% by weight of an epoxide-group-containing reaction product of epichlorohydrin with polypropylene glycol, having an epoxide equivalent weight of at least 250 g/eq, and b) at least 10% by weight of an epoxide-group-containing reaction product of epichlorohydrin with a novolak resin, having an epoxide equivalent weight of at least 175 g/eq, and whose second component comprises at least one epoxy resin hardener containing thiol groups.
Description
"EPOXY RESIN COMPOSITION WITH REDUCED TOXICITY"
[0002] The present invention relates to a two-component adhesive based on a specific epoxy resin system. The epoxy resin system according to the present invention makes it possible to provide, without the use of components that are categorized as toxic, irritating, or sensitizing and that would require corresponding labeling under European law, adhesives that are equivalent in quality to conventional adhesives in terms of utilization properties.
[0003] Epoxy-based resin systems have been successfully used for some time as adhesives or repair compounds for consumers, hobbyists, and craftsmen, and in the aviation, automotive, or electrical industry, as adhesives or sealants or for the coating of surfaces, or as resin systems with a number of different materials for the manufacture of composite materials. Hardenable formulations that contain epoxy/hardener mixtures are suitable in particular as structural adhesives. One important property of the unhardened resin system is its viscosity, which is significant in terms of handling and processability.
Important material properties of the hardened formulations are, among others, adhesive power (often determined as tensile shear strength) and modulus of elasticity.
Important material properties of the hardened formulations are, among others, adhesive power (often determined as tensile shear strength) and modulus of elasticity.
[0004] Reactive epoxy resin systems of the existing art often contain constituents that have been categorized as toxic, irritating, sensitizing, and/or hazardous to water resources, and can result, for example, in contact dermatitis during processing. According to European law, such preparations must be provided with the corresponding hazard label (e.g. C, Xn, Xi, N). For reasons of environmental protection, safety, and industrial hygiene, there is a desire for reactive epoxy resin-containing preparations that do not require labeling under European law and that exhibit a reduced sensitizing potential, but that meet technical requirements with regard to processability and adhesive properties.
[0005] It is known that reactive epoxy resins having a molar weight above 700 g/mol are not sensitizing and are not subject to labeling requirements.
Examples thereof are high-molecular-weight solids based on DGEBA
(diglycidyl ethers of bisphenol A), and liquid epoxy-terminated polyethers with a high epoxy equivalent weight. These do not, however exhibit the viscosity properties necessary for processing prior to curing, and/or the necessary strength properties after curing. High-molecular-weight solid epoxy novolacs have the high epoxy functionality necessary for high strength (and, correspondingly, a low epoxy equivalent weight), but are not processable because of their high viscosity at room temperature.
Examples thereof are high-molecular-weight solids based on DGEBA
(diglycidyl ethers of bisphenol A), and liquid epoxy-terminated polyethers with a high epoxy equivalent weight. These do not, however exhibit the viscosity properties necessary for processing prior to curing, and/or the necessary strength properties after curing. High-molecular-weight solid epoxy novolacs have the high epoxy functionality necessary for high strength (and, correspondingly, a low epoxy equivalent weight), but are not processable because of their high viscosity at room temperature.
[0006] An object of the present invention was therefore to develop a hardenable epoxy resin that is advantageous in toxicological and dermatological terms and nevertheless has no disadvantages in the context of utilization properties, in particular viscosity during processing and/or strength after curing.
[0007] It has now been found, surprisingly, that suitable mixtures of different reactive epoxy resins result in the desired property combination of freedom from labeling requirements, processability, and adhesive properties.
[0008] A first subject of the present invention is therefore a two-component composition whose first component is a mixture of reactive epoxy resins and optionally further formulation constituents which contains, based on the mass of all epoxy resins, a) at least 10 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, and b) at least 10 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and whose second component contains at least one thiol group-containing hardener for epoxy resins.
[0009] According to the present invention, a "reactive epoxy resin" is understood as a prepolymer that has an average epoxy functionality greater than 1. Because of the reactive epoxy groups, the prepolymer can be reacted with further molecules (called "hardeners") that are reactive with respect to epoxy groups, and thereby be "cured" or "hardened."
[0010] The composition according to the present invention contains, as a first component a) essential to the invention, at least 10 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq.
[0011] In a preferred embodiment, the composition according to the present invention contains 10 to 60 wt% of component a). A quantity range from 30 to 45 wt% is especially preferred. The quantity indications refer in each case to the mixture of all epoxy resins, without the further formulation constituents.
[0012] In the context of the work on which this invention is based, it was possible to show that epoxy group-containing reaction products of epichlorohydrin with polypropylene glycol having an epoxy equivalent weight of at least 300 g/eq exhibit particularly advantageous properties.
[0013] Particularly preferred components a) are, according to the present invention, the reactive epoxy resins marketed by the Dow company under the commercial designations DER 732 (EEW 310 to 330 g/eq) and DER 732P
(EEW 310 to 330 g/eq).
(EEW 310 to 330 g/eq).
[0014] It is particularly advantageous according to the present invention if corresponding epoxy group-containing reaction products of epichlorohydrin with polypropylene glycol having an epoxy equivalent weight of less than 300 g/eq are contained in the compositions at a proportion of at most 3 wt%, in particular at most 1 wt%, based in each case on the first component made up of a mixture of reactive epoxy resins and optionally further formulation constituents.
[0015] As a second component b) essential to the invention, the composition according to the present invention contains at least 10 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq.
[0016] In a preferred embodiment, the composition according to the present invention contains 10 to 85 wt% of component b). A quantity range from 30 to 45 wt% is especially preferred. The quantity indications refer in each case to the mixture of all epoxy resins, without the further formulation constituents.
[0017] In the context of the work on which this invention is based, it was possible to show that epoxy group-containing reaction products of epichlorohydrin with a novolac having an epoxy equivalent weight of at least 180 g/eq, and in particular of at least 190 g/eq, exhibit particularly advantageous properties.
[0018] Novolacs preferred according to the present invention are the polycondensation products of formaldehyde with phenol and/or cresol.
[0019] It has furthermore proven to be advantageous if the reaction products of epichlorohydrin and novolac have an epoxy functionality of at least 3, in particular of at least 3.5.
[0020] Reaction products of epichlorohydrin and novolac which have an epoxy equivalent weight of at least 175 g/eq and simultaneously an epoxy functionality of at least 3 were found to be particularly convincing in terms of the objects stated according to the present invention. Reaction products of epichlorohydrin and novolac having an epoxy equivalent weight of at least 180 g/eq and an epoxy functionality of at least 3, in particular reaction products of epichlorohydrin and novolac having an epoxy equivalent weight of at least 190 g/eq and an epoxy functionality of at least 3.5, are particularly preferred.
[0021] The desired property combination of processability prior to curing, and adhesion strength after curing, are most effectively achieved thereby.
[0022] Particularly preferred components b) are, according to the present invention, the reactive epoxy resins marketed under the commercial designations DEN 439 (EEW 191 to 210 g/eq, functionality 3.8; Dow), Araldite ECN 1299 (cresol-formaldehyde novolac, EEW 235 g/eq, functionality 2.5 to 5.5; Huntsman), Epikote 154 (EEW 176 to 181 g/eq; Hexion). DEN 439 is very particularly preferred according to the present invention.
[0023] It is particularly advantageous according to the present invention if corresponding reaction products of epichlorohydrin with novolac having an epoxy equivalent weight of less than 175 g/eq are contained at a proportion of at most 3 wt%, in particular at most 1 wt%, based in each case on the first component made up of the mixture of reactive epoxy resins and optionally further formulation constituents.
[0024] In order to ensure optimum processability of the compositions according to the present invention, it has proven particularly advantageous according to the present invention if the epoxy-containing compositions have viscosities below 3000 Pas. Epoxy-containing preparations having a viscosity below 500 PaS are very particularly preferred. Viscosity measurements are accomplished according to the present invention at 25 C using a rheometer and the following viscosity-dependent settings:
- at a viscosity < 0.25 Pa*s, measurement was performed using a cone and plate (0.04 /25 mm) at a shear rate of 0 to 100/s;
- viscosities > 0.25 Pa*s and < 10,000 Pa*s were measured using parallel plates (25 mm/25 mm) at a shear rate of 0 to 100/s; and - viscosities > 10,000 Pa*s were measured using parallel plates (25 mm/25 mm) and at an angular frequency of 100 rad/s.
According to the present invention, a measurement at a "shear rate of 0 to 100/s" is understood as a measurement in which the shear speed is increased, within 100 s, from 0/s to 100/s. The shear speed is then held constant for 30 s, and then the result is determined.
- at a viscosity < 0.25 Pa*s, measurement was performed using a cone and plate (0.04 /25 mm) at a shear rate of 0 to 100/s;
- viscosities > 0.25 Pa*s and < 10,000 Pa*s were measured using parallel plates (25 mm/25 mm) at a shear rate of 0 to 100/s; and - viscosities > 10,000 Pa*s were measured using parallel plates (25 mm/25 mm) and at an angular frequency of 100 rad/s.
According to the present invention, a measurement at a "shear rate of 0 to 100/s" is understood as a measurement in which the shear speed is increased, within 100 s, from 0/s to 100/s. The shear speed is then held constant for 30 s, and then the result is determined.
[0025] A further essential property of the agents according to the present invention is the so-called tensile shear strength. This is determined by means of the following experimental setup:
[0026] Two sandblasted, cold-rolled steel specimens are wetted with the adhesive to be tested, on an overlap area of 2.5 cm2 with a layer thickness of 0.2 mm, and bonded. After corresponding curing, the tensile shear strength of the adhesive is tested in accordance with DIN EN 1465 at a rate of 15 mm/min.
[0027] It has proven to be advantageous according to the present invention if the adhesives exhibit, after they have cured, a tensile shear strength above 8 MPa, in particular above 10 MPa. The speed of the curing process plays no essential role in this context.
[0028] As a third component essential to the invention, the composition according to the present invention contains at least one thiol group-containing hardener for epoxy resins.
[0029] According to the present invention, a "thiol group-containing hardener for epoxy resins" is understood as a compound that comprises at least two thiol groups per molecule. It is particularly preferred according to the present invention if the compound is one that is liquid at 22 C.
[0030] According to the present invention it may be preferred, in a specific embodiment, if the thiol group-containing hardener is a polymeric compound.
[0031] Thiol group-containing hardeners preferred according to the present invention are the compounds known by the commercial designations:
- Capcure 3-800, Capcure 3830-81, Capcure LOF, Capcure WR6, Capcure WR35, Capcure 40 SEC HV (Cognis), - GPM 800, GPM 800 LO, GPM 830 CB, GPM 845 MT, GPM 888, GPM 890 CB, GPM 891, GPM 895 FC (Gabriel Performance Products), - Karenz MT [pentaerythritol tetrakis(3-mercaptobutylate); CAS 31775-89-0]
(Showa Denko), - dipentenedimercaptan (CAS 4802-20-4), Mercaptized Soy Oil, PM 407, PM
358, Mercaptized Castor Oil: 805-C (Chevron Phillips), - Thiocure GDMA (glycol dimercaptoacetate; CAS 123-81-9), Thiocure TMPMA (trimethyl propane trimercaptoacetate; CAS 10193-96-1), Thiocure PETMA (pentaerythritol tetramercaptoacetate; CAS 10193-994), Thiocure TMPMP (trimethylopropane tris-3-mercaptopropionate; CAS 33007-83-9), Thiocure PETMP (pentaerythritol tetra-3-mercaptopropionate; CAS 7575-23-7), Thiocure ETTMP (ethoxylated trimethylpropane tris-3-mercaptopropionate (polymer), CAS 345352-19-4) (Bruno Bock).
- Capcure 3-800, Capcure 3830-81, Capcure LOF, Capcure WR6, Capcure WR35, Capcure 40 SEC HV (Cognis), - GPM 800, GPM 800 LO, GPM 830 CB, GPM 845 MT, GPM 888, GPM 890 CB, GPM 891, GPM 895 FC (Gabriel Performance Products), - Karenz MT [pentaerythritol tetrakis(3-mercaptobutylate); CAS 31775-89-0]
(Showa Denko), - dipentenedimercaptan (CAS 4802-20-4), Mercaptized Soy Oil, PM 407, PM
358, Mercaptized Castor Oil: 805-C (Chevron Phillips), - Thiocure GDMA (glycol dimercaptoacetate; CAS 123-81-9), Thiocure TMPMA (trimethyl propane trimercaptoacetate; CAS 10193-96-1), Thiocure PETMA (pentaerythritol tetramercaptoacetate; CAS 10193-994), Thiocure TMPMP (trimethylopropane tris-3-mercaptopropionate; CAS 33007-83-9), Thiocure PETMP (pentaerythritol tetra-3-mercaptopropionate; CAS 7575-23-7), Thiocure ETTMP (ethoxylated trimethylpropane tris-3-mercaptopropionate (polymer), CAS 345352-19-4) (Bruno Bock).
[0032] The following compounds are also thiol group-containing hardeners preferred according to the present invention:
- DMDO (3,6-dioxa-1,8-octanedithiol), - hardenable DMDO reaction product, - 3-oxa-1,5-pentanedithiol, - 1,2-ethanedithiol T, - 1,3-propanedithiol, - 1,2-propanedithiol, - 1,4-butanedithiol, - 1,3-butanedithiol, - 2,3-butanedithiol, - 1,5-pentanedithiol, - 1,3-pentanedithiol, - 1,6-hexanedithiol, - 1,3-dithio-3-methylbutane, - ethylcyclohexyldithiol (ECHDT), - methylcyclohexyldithiol, - methyl-substituted dimercaptodiethyl sulfide, - dimethyl-substituted dimercaptodiethyl sulfide, - 2,3-dimercapto-1-propanol, - bis-(4-mercaptomethylphenyl) ether, - 2,2'-thiodiethanethiol.
- DMDO (3,6-dioxa-1,8-octanedithiol), - hardenable DMDO reaction product, - 3-oxa-1,5-pentanedithiol, - 1,2-ethanedithiol T, - 1,3-propanedithiol, - 1,2-propanedithiol, - 1,4-butanedithiol, - 1,3-butanedithiol, - 2,3-butanedithiol, - 1,5-pentanedithiol, - 1,3-pentanedithiol, - 1,6-hexanedithiol, - 1,3-dithio-3-methylbutane, - ethylcyclohexyldithiol (ECHDT), - methylcyclohexyldithiol, - methyl-substituted dimercaptodiethyl sulfide, - dimethyl-substituted dimercaptodiethyl sulfide, - 2,3-dimercapto-1-propanol, - bis-(4-mercaptomethylphenyl) ether, - 2,2'-thiodiethanethiol.
[0033] Thiol group-containing hardeners that are particularly preferred according to the present invention are:
- Capcure 3-800, Capcure 3830-81, and Capcure LOF (Cognis), - GPM 800, GPM 800 LO, GPM 830 CB, and GPM 888 (Gabriel Performance Products), - Mercaptized Soy Oil, PM 407, PM 358, and Mercaptized Castor Oil 805-C
(Chevron Phillips), - Thiocure ETTMP (ethoxylated trimethylpropane tris-3-mercaptopropionate (polymer); CAS 345352-19-4) (Bruno Bock), - 1,5-pentanedithiol, - 1,3-pentanedithiol, and - 1,6-hexanedithiol.
- Capcure 3-800, Capcure 3830-81, and Capcure LOF (Cognis), - GPM 800, GPM 800 LO, GPM 830 CB, and GPM 888 (Gabriel Performance Products), - Mercaptized Soy Oil, PM 407, PM 358, and Mercaptized Castor Oil 805-C
(Chevron Phillips), - Thiocure ETTMP (ethoxylated trimethylpropane tris-3-mercaptopropionate (polymer); CAS 345352-19-4) (Bruno Bock), - 1,5-pentanedithiol, - 1,3-pentanedithiol, and - 1,6-hexanedithiol.
[0034] It may be preferred according to the present invention if the second component of the composition contains less than 25 wt%, in particular less than 20 wt%, in particular less than 10 wt%, of one or more of the following compounds, the quantity indications being based on the entire composition of the second component:
- pentaerythritol tetrakis(3-mercaptobutylate) (CAS 31775-89-0), - dipentenedimercaptan (CAS 4802-20-4), - glycol dimercaptoacetate (CAS 123-81-9), - trimethylopropane tris-3-mercaptopropionate (CAS 33007-83-9), - pentaerythritol tetra-3-mercaptopropionate (CAS 7575-23-7), - DMDO (3,6-dioxa-1,8-octanedithiol), - 1,2-ethanedithiol, - 1,3-propanedithiol, - 1,4-butanedithiol, - 1,3-butanedithiol, - 2,3-butanedithiol, and - 2,3-dimercapto-1-propanol.
- pentaerythritol tetrakis(3-mercaptobutylate) (CAS 31775-89-0), - dipentenedimercaptan (CAS 4802-20-4), - glycol dimercaptoacetate (CAS 123-81-9), - trimethylopropane tris-3-mercaptopropionate (CAS 33007-83-9), - pentaerythritol tetra-3-mercaptopropionate (CAS 7575-23-7), - DMDO (3,6-dioxa-1,8-octanedithiol), - 1,2-ethanedithiol, - 1,3-propanedithiol, - 1,4-butanedithiol, - 1,3-butanedithiol, - 2,3-butanedithiol, and - 2,3-dimercapto-1-propanol.
[0035] The thiol group-containing hardeners are used by preference at a ratio of 1 thiol equivalent hardener per 1 to 2 epoxy equivalent. This means that the utilization mixture preferably comprises an excess of reactive epoxy groups with respect to the reactive thiol groups.
[0036] In a preferred embodiment of the present invention, the first component further contains at least 10 wt% of an epoxy group-containing reaction product of epichlorohydrin with bisphenol A which has an epoxy equivalent weight of at least 500 g/eq.
[0037] In this embodiment, compositions that contain, based on the mass of all epoxy resins, the following components:
- a) 10 to 60 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, - b) 15 to 85 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and - c) 0 to 70 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, are accordingly particularly preferred.
- a) 10 to 60 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, - b) 15 to 85 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and - c) 0 to 70 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, are accordingly particularly preferred.
[0038] Compositions that contain, based on the mass of all epoxy resins, the following components:
- a) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, - b) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and - c) 10 to 40 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, are particularly preferred according to the present invention.
- a) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, - b) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and - c) 10 to 40 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, are particularly preferred according to the present invention.
[0039] Compositions that contain, based on the mass of all epoxy resins, the following components:
- a) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, - b) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq and an epoxy functionality of at least 3, and - c) 10 to 40 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, are furthermore particularly preferred according to the present invention.
- a) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, - b) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq and an epoxy functionality of at least 3, and - c) 10 to 40 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, are furthermore particularly preferred according to the present invention.
[0040] It has proven to be particularly advantageous according to the present invention if the composition according to the present invention contains 0 to 70 wt% of an epoxy group-containing reaction product of epichlorohydrin with bisphenol A which has an epoxy equivalent weight of at least 500 g/eq. A
quantity range from 10 to 40 wt% is especially preferred. The quantity indications refer in each case to the mixture of all epoxy resins, without the further formulation constituents.
quantity range from 10 to 40 wt% is especially preferred. The quantity indications refer in each case to the mixture of all epoxy resins, without the further formulation constituents.
[0041] In the context of the work on which this invention is based, it was possible to show that epoxy group-containing reaction products of epichlorohydrin with bisphenol A having an epoxy equivalent weight of at least 560 g/eq exhibit particularly advantageous properties.
[0042] Epoxy group-containing reaction products of epichlorohydrin with bisphenol A which have an epoxy equivalent weight of at least 500 g/eq that are particularly preferred according to the present invention are the epoxy resins marketed under the commercial designations:
- Epikote 1002 (EEW 575 to 700 g/eq; epoxy functionality 2; Hexion), - DER 662E (EEW 590 to 630 g/eq; epoxy functionality 2), - Epon 1002F (EEW 600 to 700 g/eq; epoxy functionality 2), - DER 662UH (EEW 675 to 750 g/eq; epoxy functionality 2), - DER 663U (EEW 730 to 820 g/eq; epoxy functionality 2), - DER 664U (EEW 875 to 955 g/eq; epoxy functionality 2), - Epon 1009F (EEW 2300 to 3800 g/eq; epoxy functionality 2; Hexion), - Epon 1007F (EEW 1700 to 2300 g/eq; epoxy functionality 2; Hexion), - Epon 1004F (EEW 800 to 950 g/eq; epoxy functionality 2; Hexion), - DER 692H (EEW 660 to 720 g/eq; epoxy functionality 2; Dow), - DER 692 (EEW 660 to 720 g/eq; epoxy functionality 2; Dow).
The products marketed under the commercial designations Epikote 1002, DER 662E, and Epon 1002F are very particularly preferred according to the present invention. Epon 1002F is very particularly preferred according to the present invention.
- Epikote 1002 (EEW 575 to 700 g/eq; epoxy functionality 2; Hexion), - DER 662E (EEW 590 to 630 g/eq; epoxy functionality 2), - Epon 1002F (EEW 600 to 700 g/eq; epoxy functionality 2), - DER 662UH (EEW 675 to 750 g/eq; epoxy functionality 2), - DER 663U (EEW 730 to 820 g/eq; epoxy functionality 2), - DER 664U (EEW 875 to 955 g/eq; epoxy functionality 2), - Epon 1009F (EEW 2300 to 3800 g/eq; epoxy functionality 2; Hexion), - Epon 1007F (EEW 1700 to 2300 g/eq; epoxy functionality 2; Hexion), - Epon 1004F (EEW 800 to 950 g/eq; epoxy functionality 2; Hexion), - DER 692H (EEW 660 to 720 g/eq; epoxy functionality 2; Dow), - DER 692 (EEW 660 to 720 g/eq; epoxy functionality 2; Dow).
The products marketed under the commercial designations Epikote 1002, DER 662E, and Epon 1002F are very particularly preferred according to the present invention. Epon 1002F is very particularly preferred according to the present invention.
[0043] It is particularly advantageous according to the present invention if corresponding epoxy group-containing reaction products of epichlorohydrin with bisphenol A which have an epoxy equivalent weight below 500 g/eq are contained in the compositions at a proportion of at most 3 wt%, in particular at a proportion of at most 1 wt%, based in each case on the first component made up of a mixture of reactive epoxy resins and optionally further formulation constituents.
[0044] Especially in toxicological terms, it has proven to be advantageous if the compositions according to the present invention contain, in addition to the aforesaid epoxy group-containing reaction products a), b), and c) that are essential to the invention, less than 3 wt%, in particular less than 1 wt%, of further epoxy group-containing reaction products, based in each case on the first component made up of the mixture of reactive epoxy resins and optionally further formulation constituents.
[0045] In a particularly preferred embodiment of this subject, the mixture of the epoxy resins is made up of - a) 10 to 60 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, - b) 15 to 85 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and - c) 0 to 70 wt% of an epoxy group-containing reaction product of epichiorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, the quantities of constituents a), b), and c) adding up to 100 wt%.
[0046] In a very particularly preferred embodiment of this subject, the mixture of the epoxy resins is made up of - a) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, - b) 30 to 45 wt% of an epoxy group-containing reaction product of epichiorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and - c) 10 to 40 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, the quantities of constituents a), b), and c) adding up to 100 wt%.
[0047] In a further very particularly preferred embodiment of this subject, the mixture of the epoxy resins is made up of a) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, b) 30 to 45 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq and an epoxy functionality of at least 3, and c) 10 to 40 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq, the quantities of constituents a), b), and c) adding up to 100 wt%.
[0048] It has furthermore proven to be advantageous, in an embodiment of the present invention, if the second component of the two-component composition according to the present invention contains, in addition to the thiol group-containing hardener, an amine group-containing hardener for epoxy resins.
[0049] These amine group-containing hardeners for epoxy resins can be selected, for example, from the following compounds: cyclic tertiary amines such as, for example, 1,5-diazabicyclo[4.3.]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), aromatic amines, and/or mixtures thereof. The hardeners can be incorporated stoichiometrically into the hardening reaction, but they can also be catalytically active.
[0050] Adducts of amino compounds with epoxy resins are furthermore suitable as accelerating additives. Suitable amino compounds are tertiary aliphatic, aromatic, or cyclic amines. Suitable epoxy compounds are, for example, polyepoxides based on glycidyl ethers of bisphenol A or F, or of resorcinol. Concrete examples of such adducts are adducts of tertiary amines such as 2-dimethylaminoethanol, N-substituted piperazines, N-substituted homopiperazines, N-substituted aminophenols with di- or polyglycidyl ethers of bisphenol A or F or of resorcinol.
[0051] Suitable for this, for example, are the di- or trifunctional aminoterminated polyalkylene glycols known as "JeffamineTM D" or "JeffamineTM T," especially based on ethylene oxide and/or propylene oxide.
Further examples are polyaminoamides (preferably various grades of VersamidTM, AradurTM, or AncamideTM), polyamines (preferably diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, pentaethylenehexamine, AradurTM, AncaminTM, LaurominTM), cycloaliphatic polyamines (preferably AncamineTM, LauromineTM), polyaminoimidazoline (preferably VersamidTM), aralkylamines (preferably MXDA), aromatic amines (preferably 4,4'-diaminodiphenyl sulfone, MDA), tertiary amines (preferably Versamine EH-30, Versamine EH-50).
Further examples are polyaminoamides (preferably various grades of VersamidTM, AradurTM, or AncamideTM), polyamines (preferably diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, pentaethylenehexamine, AradurTM, AncaminTM, LaurominTM), cycloaliphatic polyamines (preferably AncamineTM, LauromineTM), polyaminoimidazoline (preferably VersamidTM), aralkylamines (preferably MXDA), aromatic amines (preferably 4,4'-diaminodiphenyl sulfone, MDA), tertiary amines (preferably Versamine EH-30, Versamine EH-50).
[0052] The amino group-containing hardener or hardeners for epoxy resins are contained in the agents according to the present invention by preference in quantities from 0 to 20 wt%, based on the second component made up of hardeners and optionally further formulation constituents.
[0053] In a preferred embodiment, the tertiary amines in particular have proven to be particularly advantageous. They are contained in the agents according to the present invention by preference in a quantity from 0 to 20 wt%, in particular in quantities from 0.1 to 18 wt%, very particularly preferably in quantities from 5 to 15 wt%, based in each case on the second component made up of hardeners and optionally further formulation constituents.
[0054] Compositions whose second component contains or represents a hardener for epoxy resins that is effective in a temperature range from 0 to 60 C, in particular from 0 to 25 C, are particularly preferred according to the present invention.
[0055] In order to improve fracture behavior, in particular at temperatures below 0 C, the preparations according to the present invention can contain one or more different so-called toughness improvers or "tougheners." Such tougheners are known to those skilled in the art of epoxy adhesives. They can be selected, for example, from: thermoplastic isocyanates or polyurethanes, rubber particles, in particular those having a core-shell structure, and block copolymers, in particular those that contain a first polymer block having a glass transition temperature of less than 15 C and a second polymer block having a glass transition temperature of more than 25 C. Such block copolymers are by preference selected from those in which a first polymer block is selected from a polybutadiene or polyisoprene block, and a second polymer block is selected from a polystyrene or polymethyl methacrylate block. Specific examples thereof are block copolymers having the following block structure: styrene-butadiene-(meth)acrylate, styrene-butadiene-(meth)acrylic acid esters, ethylene-(meth)acrylic acid ester-glycidyl (meth)acrylic acid ester, ethylene-(meth)acrylic acid ester-maleic acid anhydride, methyl methacrylate-butyl acrylate-methyl methacrylate.
[0056] It has furthermore proven advantageous according to the present invention if the first component of the compositions according to the present invention contains, in addition to the mixture of epoxy resins, at least one inorganic and/or organic filler.
[0057] In a further embodiment, it has proven advantageous if the second component of the composition according to the present invention contains, in addition to the hardeners that are essential to the invention, at least one inorganic and/or inorganic filler.
[0058] Fillers preferred according to the present invention are, for example, the various ground or precipitated chalks, carbon black, calcium-magnesium carbonates, talc, barite, and in particular silicate fillers of the aluminum-magnesium-calcium silicate type, for example wollastonite, chlorite. It may furthermore be preferred to use calcium sulfate as a filler.
[0059] For weight reduction, the preparation can also contain, in addition to the aforesaid "normal" fillers, so-called lightweight fillers. These can be selected from the group of the hollow metal spheres such as, for example, hollow steel spheres, hollow glass spheres, fly ash (fillite), hollow plastic spheres based on phenol resins, epoxy resins, or polyesters, expanded hollow microspheres having a wall material made of (meth)acrylic acid ester copolymers, polystyrene, styrene/(meth)acrylate copolymers, and in particular of polyvinylidene chloride as well as copolymers of vinylidene chloride with acrylonitrile and/or (meth)acrylic acid esters, ceramic hollow spheres, or organic lightweight fillers of natural origin such as ground nut shells, for example the shells of cashew nuts, coconuts, or peanuts, as well as cork flour or coke powder. Particularly preferred in this context are those lightweight fillers, based on hollow microspheres, that ensure high compressive strength in the cured preparation.
[0060] The formulations according to the present invention can in principle be formulated to be free of fillers. In the context of this embodiment, the term "free of is to be understood as a filler content of less than 0.5 wt%, by preference less than 0.1 wt%, based in each case on all formulation constituents of the respective component.
[0061] In the case of formulations that are liquid at room temperature, a filler content from 0 to 65 wt%, by preference from 20 to 40 wt%, based in each case on all formulation constituents of the respective component, has proven particularly advantageous.
[0062] In the case of formulations that are solid at room temperature, a filler content from 25 to 95 wt%, by preference from 40 to 75 wt%, based in each case on all formulation constituents of the respective component, has proven particularly advantageous.
[0063] In addition, the curable preparations according to the present invention can contain further usual adjuvants and additives such as, for example, plasticizers, rheology adjuvants, wetting agents, adhesion promoters, aging protection agents, stabilizers, and/or color pigments.
[0064] The two-component adhesives according to the present invention can be used as adhesives, or as a matrix for a composite, a further embodiment of the present invention being constituted thereby. The adhesive can be utilized in particular for joining and repairing parts in shipbuilding, aircraft construction, and vehicle construction. It is notable for good processability and high strength on the one hand, and particularly low health risk on the other. Further areas of application for the systems according to the present invention are the do-it-yourself sector, as well as the maintenance, repair, and overhaul sector for vehicles, machines, and aviation, but areas of application in other sectors of general industry are also encompassed according to the present invention.
[0065] The agents according to the present invention are made up of two components. These must be stored separately from one another until immediately before utilization.
[0066] This can preferably be done by packaging in separate containers.
Removal of the preparation can then be accomplished immediately before utilization. This can be accomplished by manually measuring out the requisite quantities from storage vessels, for example drums.
Removal of the preparation can then be accomplished immediately before utilization. This can be accomplished by manually measuring out the requisite quantities from storage vessels, for example drums.
[0067] In addition to purely manual measuring, dispensing can also be accomplished using simple manual dispensing units or even fully automated systems. Such systems are marketed, for example, by the Loctite company.
Examples of such automated systems are volumetric double gear pumps, double precision piston dispensers, double screw pump dispensers, or drum pump systems.
Examples of such automated systems are volumetric double gear pumps, double precision piston dispensers, double screw pump dispensers, or drum pump systems.
[0068] In a particularly preferred embodiment of the present invention, the preparation according to the present invention are offered in corresponding cartridges having a volume ratio of I : 1, 1 : 2, or 1 : 10 (component having epoxy resin mixture : component having thiol group-containing hardeners). The selection of such double cartridges is intended, according to the present invention, to ensure consistent dispensing and thus a constant mixing ratio between the two components. The cartridges according to the present invention can be emptied, upon utilization, with the aid of simple manual dispensing units, but also using pneumatic and/or completely automated systems.
[0069] A second subject of the present invention is therefore a dispensing system that comprises two separate containers which, separately from one another, contain the first and the second component of the compositions according to the present invention, as well as a dispensing apparatus.
[0070] In another packaging form, the two components of the composition according to the present invention can be coextruded and accordingly manufactured so as to be present directly next to one another until utilization.
The two components must then be thoroughly mixed with one another at the time of utilization. This can be accomplished, for example, by kneading the coextrudates.
The two components must then be thoroughly mixed with one another at the time of utilization. This can be accomplished, for example, by kneading the coextrudates.
[0071] A third subject of the present invention is therefore a composition according to one of Claims 1 to 9 that is presented as a coextrudate.
[0072] In the context of this embodiment, it has proven to be advantageous if one or both components of the coextrudate have small quantities of a dye added to them. The different coloring of the components of the coextrudate makes it possible to track the degree of intermixing of the two components of the coextrudate.
[0073] A fourth subject of the present invention is a method for joining and/or repairing parts, in which method, in a first step, the two components of the compositions according to the present invention are mixed with one another, the resulting utilization mixture is applied onto the overlapping surfaces of the parts to be joined, the parts are then brought into contact with one another, and the utilization mixture then cures.
[0074] The curing time depends, in this context, on the exact composition of the system, the quantity applied, and the layer thickness, and can be between a few minutes and several days.
EXEMPLIFYING EMBODIMENTS
I Resin mixtures 1.1 Producing the resin mixtures
EXEMPLIFYING EMBODIMENTS
I Resin mixtures 1.1 Producing the resin mixtures
[0075] The following resin mixtures were produced by mixing the individual components and stirring vigorously at 70 to 100 C for 1 hour.
1.2 Measuring viscosities
1.2 Measuring viscosities
[0076] Viscosities were measured on an ARES unit of the TA Instruments company, New Castle, DE 19720, USA, at a temperature of 25 C, and evaluated using TA Orchestrator software. At a viscosity < 0.25 Pa*s, measurement was performed using a cone and plate (0.04 /25 mm) at a shear rate of 0 to 100/s. Viscosities > 0.25 Pa*s and < 10,000 Pa*s were measured using parallel plates (25 mm/25 mm) at a shear rate of 0 to 100/s. Viscosities >
10,000 Pa*s were measured using parallel plates (25 mm/25 mm) and at an angular frequency of 100 rad/s.
10,000 Pa*s were measured using parallel plates (25 mm/25 mm) and at an angular frequency of 100 rad/s.
[0077] 1.3 Compositions and results DER 732 DEN 439 Epikote Viscosity EEW*
[g] [g] 1002 [Pa*s] [g/eq]
[g]
N1 20 0 80 20,000 532 N2 15 0 85 75,000 555 N3 85 0 15 0.375 345
[g] [g] 1002 [Pa*s] [g/eq]
[g]
N1 20 0 80 20,000 532 N2 15 0 85 75,000 555 N3 85 0 15 0.375 345
[0078] The EEW* value indicated in the last column was calculated from the weighted EEW values of the individual components. As compared with resin mixtures H1 to H5 according to the present invention, resin mixtures N1 and N2 not according to the present invention exhibit viscosities that are much too high. Optimum utilization is not possible at such viscosities.
2 Determining tensile shear strengths
2 Determining tensile shear strengths
[0079] To determine the tensile shear strengths, components I and II as indicated in Table 2 were thoroughly mixed with one another. Immediately thereafter, two sandblasted, cold-rolled steel specimens with an overlap area of 2.5 cm2 were wetted with the resulting adhesive at a layer thickness of 0.2 mm, and bonded. The specimens were then cured for 7 days at room temperature.
[0080] After that time, the tensile shear strength of the adhesive was tested in accordance with DIN EN 1465 at a speed of 15 mm/min.
[0081] Table 2:
Component I Component II Eq Cl/ LSS
Resin Fillers Hardener Catalyst Eq CII [N/mm2]
2.09 g Luzenac 2; 3.13 g 4.48 g H1 0.30 g Cabosil TS- Capcure 3830--- 1.6 15 (0.0159 Eq) 720 81 (0.0100 Eq) 1.56 g Omyacarb 3.0 g 4.94 g H1 4HD; 0.13 g Capcure 3-800 0.37 g 1.6 12 (0.0176 Eq) Versamine EH-30 Cabosil TS-720 (0.0108 Eq) 5.9 g 10.0 g H5 3-800 0.74 g 1.6 12 (0.0340 Eq) Capcure Versamine EH-30 (0.0212 Eq) 3.67 g 5.96 g H1 3-800 0.37 g 1.6 16 (0.0212 Eq) Capcure Versamine EH-30 (0.0132 Eq) 10.0 g H3 -- 5.0 g 0.64 g 1.6 15 (0.0287 Eq) Capcure 3-800 Versamine EH-30 (0.0180 Eq) 5.6 g 10.0 g H2 3-800 0.70 g 1.6 12 (0.0322 Eq) Capcure Versamine EH-30 (0.0201 Eq) 4.4 g 10.0 g H4 3-800 0.55 g 1.6 16 (0.0253 Eq) Capcure Versamine EH-30 (0.0158 Eq) 2.34 g 7.42 g N2 3-800 0.23 g 1.6 <0. 1 (0.0138 Eq) Capcure Versamine EH-30 (0.0084 Eq) 3.23 g 6.45 g N3 3-800 0.32 g 1.6 2 (0.0187 Eq) Capcure Versamine EH-30 (0.0116 Eq) 7.42gN1 2.41 g 0.24 g (0. Capcure 3-800 Versamine EH-30 1.6 <0.1 0139 Eq) (0.0087 Eq) 4.90 g DER 4.54 g 0.56 g 331 -- Capcure 3-800 1.6 11 Versamine EH-30 (0.0262 Eq) (0.0163 Eq)
Component I Component II Eq Cl/ LSS
Resin Fillers Hardener Catalyst Eq CII [N/mm2]
2.09 g Luzenac 2; 3.13 g 4.48 g H1 0.30 g Cabosil TS- Capcure 3830--- 1.6 15 (0.0159 Eq) 720 81 (0.0100 Eq) 1.56 g Omyacarb 3.0 g 4.94 g H1 4HD; 0.13 g Capcure 3-800 0.37 g 1.6 12 (0.0176 Eq) Versamine EH-30 Cabosil TS-720 (0.0108 Eq) 5.9 g 10.0 g H5 3-800 0.74 g 1.6 12 (0.0340 Eq) Capcure Versamine EH-30 (0.0212 Eq) 3.67 g 5.96 g H1 3-800 0.37 g 1.6 16 (0.0212 Eq) Capcure Versamine EH-30 (0.0132 Eq) 10.0 g H3 -- 5.0 g 0.64 g 1.6 15 (0.0287 Eq) Capcure 3-800 Versamine EH-30 (0.0180 Eq) 5.6 g 10.0 g H2 3-800 0.70 g 1.6 12 (0.0322 Eq) Capcure Versamine EH-30 (0.0201 Eq) 4.4 g 10.0 g H4 3-800 0.55 g 1.6 16 (0.0253 Eq) Capcure Versamine EH-30 (0.0158 Eq) 2.34 g 7.42 g N2 3-800 0.23 g 1.6 <0. 1 (0.0138 Eq) Capcure Versamine EH-30 (0.0084 Eq) 3.23 g 6.45 g N3 3-800 0.32 g 1.6 2 (0.0187 Eq) Capcure Versamine EH-30 (0.0116 Eq) 7.42gN1 2.41 g 0.24 g (0. Capcure 3-800 Versamine EH-30 1.6 <0.1 0139 Eq) (0.0087 Eq) 4.90 g DER 4.54 g 0.56 g 331 -- Capcure 3-800 1.6 11 Versamine EH-30 (0.0262 Eq) (0.0163 Eq)
[0082] In determining the quantities of raw materials caused to react with one another, care was taken to maintain a constant ratio between reactive epoxy components and reactive thiol groups in the utilization mixture. The respective equivalents used, and their ratios, are likewise evident from Table 2.
[0083] The measured tensile shear strengths (LLS) clearly show that the two-component compositions according to the present invention having resins H1 to H3 are clearly superior to the two-component compositions not according to the present invention having resins N1 to N3. It was additionally possible to show by way of these measurements that the tensile shear strengths of the systems according to the present invention in fact turn out to be higher than the tensile shear strength of a conventional adhesive based on DER 331, which has a high sensitizing potential and is subject to labeling requirements.
[0084] In a further embodiment of the Examples, the fillers Luzenac 2, Cabosil TS-720, and Omyacarb 4HD associated with component I in the context of the Examples were also incorporated into components II.
3 List of raw materials used
3 List of raw materials used
[0085] Cabosil TS-720 Silicon dioxide, pyrogenic amorphous silicic acid;
manufacturer: Cabot Capcure 3-800 Mercaptan-terminated liquid polymer; mercaptan number at least 3.0 meq/g; mercaptans equivalent weight 278 g/eq.; manufacturer: Cognis Capcure 3830-81 Mixture of 8 parts by weight Capcure 3-800 and 1 part by weight Versamine EH-30; manufacturer: Cognis DEN 439 Reaction product of epichlorohydrin with a phenol/formaldehyde novolac; EEW 200g/eq; epoxy functionality 3.8; manufacturer: Dow DER 331 Reaction product of bisphenol A with epichlorohydrin;
EEW 187 g/eq; manufacturer: Dow DER 732 Reaction product of epichlorohydrin with polypropylene glycol; EEW 320 g/eq; manufacturer: Dow Epikote 1002 Reaction product of epichlorohydrin with bisphenol A;
EEW 638 g/eq; manufacturer: Hexion;
Luzenac 2 Natural association of talc, chlorite, and dolomite;
manufacturer: Luzenac Group Omyacarb 4HD Calcium carbonate (limestone flour; manufacturer: Omya GmbH
Versamine EH-30 2,4,6-Tris(dimethylaminomethyl)phenol; 100% active substance content; manufacturer: Cognis.
manufacturer: Cabot Capcure 3-800 Mercaptan-terminated liquid polymer; mercaptan number at least 3.0 meq/g; mercaptans equivalent weight 278 g/eq.; manufacturer: Cognis Capcure 3830-81 Mixture of 8 parts by weight Capcure 3-800 and 1 part by weight Versamine EH-30; manufacturer: Cognis DEN 439 Reaction product of epichlorohydrin with a phenol/formaldehyde novolac; EEW 200g/eq; epoxy functionality 3.8; manufacturer: Dow DER 331 Reaction product of bisphenol A with epichlorohydrin;
EEW 187 g/eq; manufacturer: Dow DER 732 Reaction product of epichlorohydrin with polypropylene glycol; EEW 320 g/eq; manufacturer: Dow Epikote 1002 Reaction product of epichlorohydrin with bisphenol A;
EEW 638 g/eq; manufacturer: Hexion;
Luzenac 2 Natural association of talc, chlorite, and dolomite;
manufacturer: Luzenac Group Omyacarb 4HD Calcium carbonate (limestone flour; manufacturer: Omya GmbH
Versamine EH-30 2,4,6-Tris(dimethylaminomethyl)phenol; 100% active substance content; manufacturer: Cognis.
Claims (12)
1. A two-component composition whose first component is a mixture of reactive epoxy resins and optionally further formulation constituents which contains, based on the mass of all epoxy resins, c) at least 10 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, and d) at least 10 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and whose second component contains at least one thiol group-containing hardener for epoxy resins.
2. The composition according to Claim 1, wherein the first component further contains at least 10 wt% of an epoxy group-containing reaction product of epichlorohydrin with bisphenol A which has an epoxy equivalent weight of at least 500 g/eq.
3. The composition according to one of Claims 1 or 2, wherein the second component additionally contains an amine group-containing hardener for epoxy resins.
4. The composition according to one of Claims 1 to 3, wherein component a) has an epoxy equivalent weight of at least 300 g/eq, and/or component b) has an epoxy equivalent weight of at least 190 g/eq.
5. The composition according to one or more of Claims 1 to 4, wherein component b) contains or represents a novolac resin having an epoxy functionality of at least 3.
6. The composition according to one of more of Claims 1 to 5, wherein component b) contains or represents a phenol-formaldehyde novolac resin and/or a cresol-formaldehyde novolac resin.
7. The composition according to one or more of Claims 1 to 5, wherein it contains, based on the mass of all epoxy resins, the following components:
a. 10 to 60 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, b. 15 to 85 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and c. 0 to 70 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq.
a. 10 to 60 wt% of an epoxy group-containing reaction product of epichlorohydrin with polypropylene glycol which has an epoxy equivalent weight of at least 250 g/eq, b. 15 to 85 wt% of an epoxy group-containing reaction product of epichlorohydrin with a novolac resin which has an epoxy equivalent weight of at least 175 g/eq, and c. 0 to 70 wt% of an epoxy group-containing reaction product of epichlorohydrin with at least one bisphenol which has an epoxy equivalent weight of at least 500 g/eq.
8. The composition according to one of Claims 1 to 7, wherein its second component contains or represents a hardener for epoxy resins that is effective in a temperature range from 0 to 60°C, in particular from 0 to 25°C.
9. The composition according to one of Claims 1 to 9, wherein the first components contains, in addition to the mixture of epoxy resins, at least one inorganic and/or organic filler.
10. A dispensing system that comprises two separate containers which, separately from one another, contain the first and the second component of the compositions according to one of Claims 1 to 9, as well as a dispensing apparatus.
11. The composition according to one of Claims 1 to 9, which is manufactured as a coextrudate.
12. A method for joining and/or repairing parts, in which in a first step the two components of a composition according to one of Claims 1 to 9 are mixed with one another, the resulting application mixture is applied onto the overlapping surfaces of the parts to be joined, the parts are then brought into contact with one another, and the application mixture then cures.
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US61/316,476 | 2010-03-23 | ||
PCT/EP2011/054332 WO2011117229A2 (en) | 2010-03-23 | 2011-03-22 | Epoxy resin composition with reduced toxicity |
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BR (1) | BR112012023821B1 (en) |
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US20140171552A1 (en) * | 2011-08-24 | 2014-06-19 | Henkel Ag & Co. Kgaa | Indicator for cure of two-component-epoxy adhesives |
US9790320B2 (en) | 2012-12-21 | 2017-10-17 | Dow Global Technologies Llc | Thiol-cured elastomeric epoxy resins |
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EP3510081A1 (en) * | 2016-09-12 | 2019-07-17 | Poly6 Technologies, Inc. | One-pot, high-performance recycling method for polymer waste using renewable polymer synthesis |
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US3630997A (en) * | 1970-05-04 | 1971-12-28 | Paul M Craven | Curable epoxy resin compositions and method of preparing same |
JPS51137731A (en) * | 1975-05-26 | 1976-11-27 | Hitachi Ltd | Paints for electric wires of self fusion bonding |
JP2706709B2 (en) * | 1989-02-01 | 1998-01-28 | 建設省関東地方建設局長 山口 甚郎 | Reactive repair material with long-term storage properties such as pavement |
CN1849360A (en) * | 2003-09-19 | 2006-10-18 | 陶氏环球技术公司 | Adhesive composition and using thereof |
US7470755B2 (en) * | 2005-11-29 | 2008-12-30 | Prc-Desoto International, Inc. | Polyepoxide, amine and mercaptan-terminated polyoxyalkylene |
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- 2011-03-22 EP EP11709144.7A patent/EP2550327B1/en active Active
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US20140171552A1 (en) * | 2011-08-24 | 2014-06-19 | Henkel Ag & Co. Kgaa | Indicator for cure of two-component-epoxy adhesives |
US9315698B2 (en) * | 2011-08-24 | 2016-04-19 | Henkel Ag & Co. Kgaa | Indicator for cure of two-component-epoxy adhesives |
US9790320B2 (en) | 2012-12-21 | 2017-10-17 | Dow Global Technologies Llc | Thiol-cured elastomeric epoxy resins |
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BR112012023821A2 (en) | 2016-08-02 |
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WO2011117229A3 (en) | 2011-12-22 |
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