JPH01217032A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH01217032A JPH01217032A JP4378088A JP4378088A JPH01217032A JP H01217032 A JPH01217032 A JP H01217032A JP 4378088 A JP4378088 A JP 4378088A JP 4378088 A JP4378088 A JP 4378088A JP H01217032 A JPH01217032 A JP H01217032A
- Authority
- JP
- Japan
- Prior art keywords
- tables
- formulas
- component
- resin composition
- polyglycidyl
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 title claims description 27
- 229920000647 polyepoxide Polymers 0.000 title claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- -1 aminophenol compound Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 7
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 7
- INWVTRVMRQMCCM-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 INWVTRVMRQMCCM-UHFFFAOYSA-N 0.000 claims abstract 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000011342 resin composition Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 abstract description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 abstract description 3
- 238000013035 low temperature curing Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 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 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000013016 damping Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000012779 reinforcing material Substances 0.000 description 8
- 102100040287 GTP cyclohydrolase 1 feedback regulatory protein Human genes 0.000 description 7
- 101710185324 GTP cyclohydrolase 1 feedback regulatory protein Proteins 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- FEDLEBCVFZMHBP-UHFFFAOYSA-N 2-amino-3-methylphenol Chemical compound CC1=CC=CC(O)=C1N FEDLEBCVFZMHBP-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 238000009730 filament winding Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- HCPJEHJGFKWRFM-UHFFFAOYSA-N 2-amino-5-methylphenol Chemical compound CC1=CC=C(N)C(O)=C1 HCPJEHJGFKWRFM-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- ZVPQMESWKIQHGS-UHFFFAOYSA-N 3-(2,3-dichlorophenyl)-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=CC(Cl)=C1Cl ZVPQMESWKIQHGS-UHFFFAOYSA-N 0.000 description 1
- ZDBWYUOUYNQZBM-UHFFFAOYSA-N 3-(aminomethyl)aniline Chemical compound NCC1=CC=CC(N)=C1 ZDBWYUOUYNQZBM-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- ZWKXEALJTBALGD-UHFFFAOYSA-N 4-amino-2-ethylphenol Chemical compound CCC1=CC(N)=CC=C1O ZWKXEALJTBALGD-UHFFFAOYSA-N 0.000 description 1
- ZZENTDXPBYLGKF-UHFFFAOYSA-N 4-amino-3-ethylphenol Chemical compound CCC1=CC(O)=CC=C1N ZZENTDXPBYLGKF-UHFFFAOYSA-N 0.000 description 1
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 description 1
- JOJAEBZHFWYZAY-UHFFFAOYSA-N 4-methoxy-6-methylbenzene-1,3-diamine Chemical compound COC1=CC(C)=C(N)C=C1N JOJAEBZHFWYZAY-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- BNDNAARXJVXTED-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 4-methyl-7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1OC(=O)C1(C)CC2OC2CC1 BNDNAARXJVXTED-UHFFFAOYSA-N 0.000 description 1
- XGHVRCGLUWBALZ-UHFFFAOYSA-N C(C1CO1)C(C1=CC(=CC=C1N)O)(CC1CO1)CC1CO1 Chemical compound C(C1CO1)C(C1=CC(=CC=C1N)O)(CC1CO1)CC1CO1 XGHVRCGLUWBALZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 241000447394 Desmos Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006376 polybenzimidazole fiber Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は優れたコンポジット物性を有する繊維強化プラ
スチック（以下ＦＲＰと略称）を製造、特にフィラメン
トワインディング法によりＦＲＰを製造するのに適する
低粘度エポキシ樹脂組成物に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention is a low-viscosity epoxy suitable for producing fiber-reinforced plastics (hereinafter abbreviated as FRP) having excellent composite physical properties, particularly for producing FRP by a filament winding method. The present invention relates to a resin composition.
−ｍにパイプやタンクなどの製造は補強材に液状樹脂を
含浸させながら、マンドレルに巻きつけて形成する、い
わゆるフィラメントワインディング法（以下ＦＷ法と略
称する）が広く採用されている。この方法は補強材の分
布と配列の均一性が高いため、重量当りの強度が高く、
寸法精度が高い複雑な形状のものが作れ、また製造の自
動化が図れる等の利点があるため、ＦＲＰ製造分野では
重要な成形方法となっている。すなわち、一般にＦＲＰ
産業においては補強材にガラス繊維を使用し、マトリッ
クス樹脂に不飽和ポリエステル樹脂を使用するのが主流
であり、ＦＷ法が広く採用されている。In manufacturing pipes, tanks, etc., the so-called filament winding method (hereinafter abbreviated as FW method), in which reinforcing material is impregnated with liquid resin and wound around a mandrel, is widely used. This method has high strength per weight due to the high uniformity of the distribution and arrangement of the reinforcement.
This method has become an important molding method in the field of FRP manufacturing because it has the advantages of being able to manufacture complex shapes with high dimensional accuracy and automating manufacturing. That is, generally FRP
In industry, it is mainstream to use glass fiber as a reinforcing material and unsaturated polyester resin as a matrix resin, and the FW method is widely adopted.
一方、補強材に炭素繊維、アラミド繊維などを使用する
場合には、これらの繊維との接着性の優れているエポキ
シ樹脂がマトリックス樹脂として使用され、特にプリプ
レグ法等で物性的に優れた繊維強化プラスチックが得ら
れている。On the other hand, when carbon fibers, aramid fibers, etc. are used as reinforcing materials, epoxy resins that have excellent adhesion with these fibers are used as matrix resins, and fiber reinforcement with excellent physical properties is used, especially by prepreg methods. plastic is obtained.
しかし、ＦＷ法による繊維強化プラスチックの製造にお
いては、補強材に連続的に樹脂を含浸させる必要がある
ため、低粘度の液状樹脂を使用しなければならないとい
う制約があり、ＦＷ法を実施する場合には、樹脂組成物
の選定が重要な課題となっている。特にエポキシ樹脂の
場合には、低粘度の樹脂組成物はごく限られているため
、要求性能を十分満足しうる樹脂組成物を選定すること
は非常にむずかしく、高耐熱性、低弾性率かつ高靭性を
同時に有する樹脂組成物はほとんど知られていないのが
現状である。加えてエポキシ樹脂は硬化反応もしくはそ
の後の冷却によって収縮する際に発生する内部応力かつ
、亀裂、ボイド、剥離の原因となると考えられており、
その内部応力の除去の為には、ガラス転移温度の低下、
弾性率の低下等が対策として考えられている。However, in the production of fiber-reinforced plastics using the FW method, it is necessary to continuously impregnate the reinforcing material with resin, so there is a constraint that a low-viscosity liquid resin must be used. The selection of resin compositions has become an important issue. Especially in the case of epoxy resins, there are only a limited number of low-viscosity resin compositions, so it is extremely difficult to select a resin composition that fully satisfies the required performance. At present, there are almost no known resin compositions that also have toughness. In addition, it is believed that the internal stress that occurs when epoxy resin shrinks during the curing reaction or subsequent cooling causes cracks, voids, and peeling.
In order to remove the internal stress, lowering the glass transition temperature,
Decreasing the elastic modulus is considered as a countermeasure.
しかしながら−船釣にガラス転移温度と弾性率には、比
例関係がある為、耐熱性の高い、即ちガラス転移温度の
高い樹脂組成物の場合、弾性率も高くなり従って内部応
力も高くなる傾向がある。However, since there is a proportional relationship between glass transition temperature and elastic modulus, a resin composition with high heat resistance, that is, a high glass transition temperature, tends to have a high elastic modulus and therefore internal stress. be.
弾性率を低くすることは、振動減衰性にも効果があるこ
とは広く知られている。It is widely known that lowering the elastic modulus also has an effect on vibration damping properties.
エポキシ樹脂は、不飽和ポリエステル樹脂に比べて樹脂
の粘度が高いことからＦＷ用樹脂としては極めて不利な
樹脂であるため、ＦＷ用に適した樹脂組成物は極めて少
ない、そのため、通常低粘度エポキシ樹脂に反応性希釈
剤を添加したり、硬化剤に低粘度の酸無水物を使うのが
一般的な方法とされている。しかしながら、反応性希釈
剤を添加すると耐熱性が低下するし、酸無水物硬化剤に
はＦＷ中に硬化剤の吸湿に起因する性能低下が起こるな
どの欠点を有している。しかし、他に適当な樹脂組成物
がないため、ＦＷ用エポキシ樹脂組成物としては通常低
粘度工°ビビス型のエポキシ型のエポキシ樹脂、例えば
スミエポキシ＠ＥＬＡ１２８ （住人化学工業■製）、
硬化剤としてメチルナジック酸などの酸無水物、硬化促
進剤として３級アミンなどが広く使われている。しかし
、この樹脂組成物は低温で硬化させることはできるが、
反応を完結させるためには高温で長時間硬化させる必要
がある。またこの様にして硬化させた樹脂組成物は耐熱
性が十分でなく、かつ脆いものであり、炭素繊維等の強
化繊維と複合化された場合も繊維の特徴を十分発揮する
ことができない。Epoxy resin has a higher viscosity than unsaturated polyester resin, making it extremely disadvantageous as a resin for FW, so there are very few resin compositions suitable for FW, so low viscosity epoxy resins are usually used. Common methods include adding a reactive diluent to the resin or using a low-viscosity acid anhydride as a hardening agent. However, addition of a reactive diluent reduces heat resistance, and acid anhydride curing agents have drawbacks such as performance deterioration due to moisture absorption of the curing agent during FW. However, since there are no other suitable resin compositions, epoxy resin compositions for FW are usually low-viscosity bivis-type epoxy resins, such as Sumiepoxy@ELA128 (manufactured by Sumien Kagaku Kogyo ■),
Acid anhydrides such as methylnadic acid are widely used as curing agents, and tertiary amines are widely used as curing accelerators. However, although this resin composition can be cured at low temperatures,
In order to complete the reaction, it is necessary to cure at high temperature for a long time. Further, the resin composition cured in this manner does not have sufficient heat resistance and is brittle, and even when composited with reinforcing fibers such as carbon fibers, the characteristics of the fibers cannot be fully exhibited.
本発明の目的は、低温硬化性に優れ、かつ高耐熱性、低
弾性率、高振動減衰製、高靭性を有する硬化物を与える
ＦＲＰ用途に適したエポキシ樹脂組成物を提供すること
にある。An object of the present invention is to provide an epoxy resin composition suitable for FRP applications that has excellent low-temperature curability and provides a cured product having high heat resistance, low elastic modulus, high vibration damping, and high toughness.
本発明は、（Ａ）芳香環に少な（とも１個のアルキル基
が置換したアミノフェノール化合物のポリグリシジル誘
導体、
（Ｂ）多価脂肪族系アルコールのポリグリシジル誘導体
、
（Ｃ）下記一般式で表わされるイソシアネートプレポリ
マー
ルメタンジイソシアネート ノ
および（Ｄ）多価芳香族アミンを必須成分として含むこ
とを特徴とするエポキシ樹脂組成物を提供する。The present invention relates to (A) a polyglycidyl derivative of an aminophenol compound in which the aromatic ring is substituted with at least one alkyl group, (B) a polyglycidyl derivative of a polyhydric aliphatic alcohol, (C) a polyglycidyl derivative of a polyhydric aliphatic alcohol; The present invention provides an epoxy resin composition comprising the following isocyanate prepolymer methane diisocyanate and (D) a polyvalent aromatic amine as essential components.
また本発明は（Ａ）芳香環に少なくとも一個のアルキル
基が置換したアミノフェノール化合物のポリグリシジル
誘導体、
（Ｂ）多価脂肪族系アルコールのポリグリシジル誘導体
、
（Ｃ）下記一般弐で表わされるイソシアネートプレポリ
マー
［七；！′ニアじ井にｔ“ｊ
および（Ｄ）多価芳香族アミンを必須成分とするエポキ
シ樹脂組成物を提供する。The present invention also provides (A) a polyglycidyl derivative of an aminophenol compound having an aromatic ring substituted with at least one alkyl group, (B) a polyglycidyl derivative of a polyhydric aliphatic alcohol, and (C) an isocyanate represented by the following general 2. Prepolymer [7;! An epoxy resin composition is provided which contains t"j and (D) a polyvalent aromatic amine as essential components.
本発明は低温で硬化可能でかつ靭性、耐熱性にすぐれ、
低弾性率で振動減衰性が大きい、ＦＷ用エポキシ樹脂組
成物に関して鋭意検討した結果、上記エポキシ樹脂組成
物が低温硬化性に優れ、かつ耐熱性が高く、曲げ弾性率
が低く、振動減衰性が大きく、特に高靭性（破断歪みの
大きい〕の硬化物を見い出したものである。The present invention can be cured at low temperatures and has excellent toughness and heat resistance.
As a result of intensive studies on epoxy resin compositions for FW that have low elastic modulus and high vibration damping properties, we found that the above epoxy resin compositions have excellent low-temperature curability, high heat resistance, low flexural modulus, and vibration damping properties. We have discovered a cured product that is large in size and particularly has high toughness (large strain at break).
以下本発明について詳述する。The present invention will be explained in detail below.
本発明において用いられるポリグリシジル誘導体（Ａ）
（以下（Ａ）成分と称す）は芳香環に少なくとも１個の
アルキル基が置換したアミノフェノールのポリグリシジ
ル誘導体である。この（Ａ）成分はアルキル基が無置換
のアミノフェノールのポリグリシジル誘導体と比較して
低い粘度を有するため成形性が優れており、また層間剪
断強度、耐熱性、耐水性の優れた繊維強化複合材料を得
ることができる。特に成形性の面から好ましくは２５゛
ｃの粘度が１５００センチボイズ以下の（Ａ）成分であ
る。Polyglycidyl derivative (A) used in the present invention
(hereinafter referred to as component (A)) is a polyglycidyl derivative of aminophenol having an aromatic ring substituted with at least one alkyl group. This component (A) has a lower viscosity than polyglycidyl derivatives of aminophenol with unsubstituted alkyl groups, so it has excellent moldability, and is a fiber-reinforced composite with excellent interlaminar shear strength, heat resistance, and water resistance. materials can be obtained. In particular, from the viewpoint of moldability, component (A) is preferably one having a viscosity of 1,500 centivoise or less at 25°C.
（＾）成分を製造する方法については特に限定されない
が、−例を述べればアルキル基置換アミノフェノールを
過剰（例えば５倍モル、好ましくは１０倍モル以上）の
エピハロヒドリン（例えばエピクロルヒドリン）中で１
００”Ｃ以下の温度でアミノ基ヘエピハロμドリンを付
加反応させた後、４０〜１００℃の温度で減圧下に苛性
アルカリの水溶液を満下し、同時に反応系内の水を共沸
で留去しながらエポキシ化反応させる方法が挙げられる
。上記の反応においては既存のエポキシ化反応と違って
エポキシ化反応以外の副反応が極めて抑制されているの
が特徴である。このためエポキシ基含有量の高い低分子
量の（＾）成分が得られる。特に好ましくはエピハロヒ
ドリンを約１５モル倍以上使用することにより２５°Ｃ
で１５ボイズないしそれ以下の粘度のポリグリシジル誘
導体が得られる。これは３官能性のポリグリシジル誘導
体としては極めて低い値である。(^) There are no particular limitations on the method for producing the component, but to give an example, an alkyl group-substituted aminophenol is added to an excess (e.g., 5 times the mole, preferably 10 times or more) of epihalohydrin (e.g., epichlorohydrin).
After the addition reaction of epihalo-μ-drin to the amino group at a temperature of 00"C or less, an aqueous solution of caustic alkali is added under reduced pressure at a temperature of 40 to 100C, and at the same time water in the reaction system is distilled off azeotropically. The above reaction is characterized by extremely suppressing side reactions other than the epoxidation reaction, unlike existing epoxidation reactions.For this reason, the epoxy group content can be reduced. A component with a high low molecular weight (^) can be obtained. Particularly preferably, by using about 15 moles or more of epihalohydrin, the temperature at 25°C
A polyglycidyl derivative having a viscosity of 15 voids or less is obtained. This is an extremely low value for a trifunctional polyglycidyl derivative.
本発明で用いられる（Ａ）成分は、好ましくは１個の芳
香環に３個程度のグリシジル基が結合しており、さらに
既存のポリグリシジル誘導体と比較してエポキシ基含有
量が高いので、その硬化物は架橋密度が高くなり、高度
の耐熱性を発現すると考えられる。Component (A) used in the present invention preferably has about three glycidyl groups bonded to one aromatic ring, and has a higher epoxy group content than existing polyglycidyl derivatives. It is thought that the cured product has a high crosslinking density and exhibits a high degree of heat resistance.
本発明で用いられる（Ａ）成分の原料であるアルキル基
置換のアミノフェノール化合物のアルキル基の炭素数は
１〜５のもので１個のアルキル基置換のものが好ましく
、具体的には４−アミノ−ｍ−クレゾール、４−アミノ
−０−クレゾール、６−アミノ−ｍ−クレゾール、５−
アミノ−ｍ−クレゾール、３−エチル−４−アミノフェ
ノール、２−エチル−４−アミノフェノール等の１種ま
たは２種以上が例示される。特に好ましくは４−アミノ
−ｍ−クレゾール、４−アミノ−０−クレゾールである
。The alkyl group of the alkyl group-substituted aminophenol compound that is the raw material for component (A) used in the present invention is one having 1 to 5 carbon atoms, and preferably one having one alkyl group substitution. Amino-m-cresol, 4-amino-0-cresol, 6-amino-m-cresol, 5-
Examples include one or more of amino-m-cresol, 3-ethyl-4-aminophenol, and 2-ethyl-4-aminophenol. Particularly preferred are 4-amino-m-cresol and 4-amino-0-cresol.
本発明においては、上記（＾）成分は目的に応じ既存の
エポキシ樹脂との併用も可能である。In the present invention, the above component (^) can be used in combination with existing epoxy resins depending on the purpose.
これらエポキシ樹脂としてはビスフェノールＡ１ビスフ
エノールＦ、ビスフェノールＡＤ、ハイドロキノン、レ
ゾルシン、フロログリシン、トリス−（４−ヒドロキシ
フェニル）メタン、１．１．２．２−テトラキス（４−
ヒドロキシフェニル）エタン等の２価あるいは３価以上
のフェノール類またはテトラブロムビスフェノールＡ等
のハロゲン化ビスフェノール類から誘導されるグリシジ
ルエーテル化合物、フェノール、０−クレゾール等のフ
ェノール類とホルムアルデヒドの反応生成物であるノボ
ラック系エポキシ樹脂、アニリン、ｐ−アミノフェノー
ル、ｍ−アミンフェノール、４．４’ −ジアミノジフ
ェニルメタン、３．３′−ジアミノジフェニルメタン、
４．４’−ジアミノジフェニルエーテル、３．４’ −
ジアミノジフェニルエーテル、１．４−ビス（４−アミ
ノフェノキシ）ベンゼン、１．４−ビス（３−アミノフ
ェノキシ）ベンゼン、１．３−ビス（４−アミノフェノ
キシ）ベンゼン、１．３−ビス（３−アミノフェノキシ
）ベンゼン、２．２−ビス（４−アミノフェノキシフェ
ニル）プロパン、ｐ−フェニレンジアミン、ｍ−フェニ
レンジアミン、２．４−トルエンジアミン、２．６−
）ルエンジアミン、ｐ−キシリレンジアミン、ｍ−キシ
リレンジアミン、１．４−シクロヘキサン−ビス（メチ
ルアミン） 、１．３−シクロヘキサン−ビス（メチル
アミン）、５−アミノ−１−（４−アミノフェニル）
−１，３，３−トリメチルインダン、６−アミノ−１−
（４’−アミノフェニル） −１，３゜３−トリメチル
インダン系から誘導されるアミン系エポキシ樹脂、Ｐ−
オキシ安息香酸、テレフタル酸、イソフタル酸等の芳香
族カルボン酸から誘導されるグリシジルエステル系化合
物、５．５−ジメチル・ヒダントイン等から誘導される
ヒダントイン系エポキシ樹脂、２．２′−ビス（３，４
−エポキシシクロヘキシル）プロパン、２．２ ’−ビ
ス〔４−（２，３−エポキシプロピル）シクロヘキシル
〕プロパン、ビニルシクロヘキセンジオキサイド、３．
４−エポキシシクロヘキシルメチル−３，４−エポキシ
シクロヘキサンカルボキシレート等の脂環式エポキシ樹
脂、その他、トリグリシジルイソシアヌレート、２，４
．６−１−リグリシドキシーｓ−）リアジン等の１種ま
たは２種以上を挙げることができる。These epoxy resins include bisphenol A1 bisphenol F, bisphenol AD, hydroquinone, resorcinol, phloroglycin, tris-(4-hydroxyphenyl)methane, 1.1.2.2-tetrakis(4-
Glycidyl ether compounds derived from divalent or trivalent or higher valent phenols such as hydroxyphenyl)ethane or halogenated bisphenols such as tetrabromobisphenol A, reaction products of phenols such as phenol, 0-cresol, and formaldehyde. Certain novolak epoxy resins, aniline, p-aminophenol, m-aminephenol, 4.4'-diaminodiphenylmethane, 3.3'-diaminodiphenylmethane,
4.4'-diaminodiphenyl ether, 3.4'-
Diaminodiphenyl ether, 1.4-bis(4-aminophenoxy)benzene, 1.4-bis(3-aminophenoxy)benzene, 1.3-bis(4-aminophenoxy)benzene, 1.3-bis(3- aminophenoxy)benzene, 2.2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2.4-toluenediamine, 2.6-
) Luene diamine, p-xylylene diamine, m-xylylene diamine, 1,4-cyclohexane-bis(methylamine), 1,3-cyclohexane-bis(methylamine), 5-amino-1-(4-aminophenyl )
-1,3,3-trimethylindane, 6-amino-1-
(4'-aminophenyl)-1,3゜Amine-based epoxy resin derived from 3-trimethylindane, P-
Glycidyl ester compounds derived from aromatic carboxylic acids such as oxybenzoic acid, terephthalic acid, and isophthalic acid, hydantoin epoxy resins derived from 5,5-dimethyl hydantoin, etc., 2,2'-bis(3, 4
-epoxycyclohexyl)propane, 2.2'-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3.
Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, others, triglycidyl isocyanurate, 2,4
．． One or more types of 6-1-liglycidoxy s-) lyazine can be mentioned.
芳香環に少なくとも１個のアルキル基が置換したアミン
フェノールの（＾）成分と他のエポキシ樹脂を混合して
使用する場合、上記の（Ａ）成分が、エポキシ樹脂に対
し、好ましくは１０重量％以上、特に好ましくは３０重
量％以上含有されていることが望ましい。When using a mixture of the (^) component of amine phenol whose aromatic ring is substituted with at least one alkyl group and another epoxy resin, the above component (A) is preferably 10% by weight based on the epoxy resin. As mentioned above, it is particularly desirable that the content be 30% by weight or more.
一方、本発明に用いられる多価脂肪族系アルコールのポ
リグリシジル誘導体（Ｂ）（以下（Ｂ）成分と称す）は
樹脂組成物の粘度を低粘度化するのと同時に硬化物の靭
性を向上させる働きを有する。On the other hand, the polyglycidyl derivative (B) of polyhydric aliphatic alcohol used in the present invention (hereinafter referred to as component (B)) lowers the viscosity of the resin composition and simultaneously improves the toughness of the cured product. It has a function.
一般に樹脂組成物の粘度を低下させるために希釈剤、反
応性希釈剤等が用いられるが、非反応性希釈剤や１官能
反応性希釈剤の場合、これらを添加することにより粘度
を低くすることは可能であるが、他の機械物性や耐熱性
、耐水性を大きく低下させてしまう。Diluents, reactive diluents, etc. are generally used to lower the viscosity of resin compositions, but in the case of non-reactive diluents and monofunctional reactive diluents, the viscosity can be lowered by adding them. Although this is possible, other mechanical properties, heat resistance, and water resistance will be greatly reduced.
一方、多官能反応性希釈剤として芳香環、脂環を有する
ものを使用した場合、これらを添加することにより低粘
度化は達成されるが、本発明の目的とする高靭性化を達
成することができない。On the other hand, when a polyfunctional reactive diluent having an aromatic ring or an alicyclic ring is used, the viscosity can be lowered by adding these, but the toughness which is the objective of the present invention cannot be achieved. I can't.
本発明に好適な（Ｂ）成分はポリプロピレングリコール
ジグリシジルエーテル、ネオペンチルグリコールジグリ
シジルエーテル、グリセリントリグリシジルエーテル、
トリメチロールプロパントリグリシジルエーテル、ブタ
ンジオールジグリシジルエーテル、１．６−ヘキサンシ
オールジグリシジルエーテル等であるが、特に好ましく
はネオペンチルグリコールジグリシジルエーテルである
。Component (B) suitable for the present invention is polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin triglycidyl ether,
Examples include trimethylolpropane triglycidyl ether, butanediol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, and neopentyl glycol diglycidyl ether is particularly preferred.
（Ｂ）成分の添加量は、 （＾）成分、（Ｂ）成分およ
び（Ｃ）下記一般式で表わされるイソシアネートプレポ
リマー
（以下（Ｃ）成分と称する）あるいは（Ｃ）下記一般式
で表わされるイソシアネートプレポリマー（以下前記同
様に（Ｃ）成分と称する）の全体を１００重量％とした
場合１０重量％〜５０重量％が望ましい、さらに好まし
くは２０重量％〜４０重量％である。The amount of component (B) added is as follows: (^) component, (B) component, and (C) isocyanate prepolymer represented by the following general formula (hereinafter referred to as (C) component), or (C) represented by the following general formula. When the entire isocyanate prepolymer (hereinafter referred to as component (C) as described above) is taken as 100% by weight, it is preferably 10% to 50% by weight, more preferably 20% to 40% by weight.
添加量が１０重量％より少ない場合は組成物の粘度が低
くならないためにＦＷ成形が難しくかつ靭性付与の効果
が小さい、一方、添加量かつ５０重量％を超えると耐熱
性能が低下し、硬化物のガラス転移温度が低くなり、実
用的で、なくなる。If the amount added is less than 10% by weight, the viscosity of the composition will not become low, making FW molding difficult and the effect of imparting toughness will be small. On the other hand, if the amount added exceeds 50% by weight, the heat resistance performance will decrease and the cured product will deteriorate. The glass transition temperature of the glass becomes low, making it practical and disappearing.
更に本発明に用いられる（Ｃ）成分は硬化樹脂の耐熱性
を低下させることなく、弾性率を低下させ、かつ靭性を
向上させる働きを有する。（Ｃ）成分の添加量は、（Ａ
）成分、（Ｂ）成分および（Ｃ）成分の全体を１００ｆ
ｆｉ１％とした場合１０重量％〜４帽１％が望ましい、
さらに好ましくは１５重量％〜３０重量％である。添加
量が４０重量％より多い場合は組成物の粘度が高くなり
ＦＷ成形が困難になる。一方添加量が１０重量％より少
ない場合は硬化物の曲げ弾性率の低下は少なく、ガラス
転移温度の低下の方が大きくなる。Furthermore, the component (C) used in the present invention has the function of lowering the elastic modulus and improving the toughness without lowering the heat resistance of the cured resin. The amount of component (C) added is (A
) component, (B) component and (C) component as a whole at 100f.
When fi is 1%, 10% by weight to 1% by weight is desirable.
More preferably, it is 15% to 30% by weight. When the amount added is more than 40% by weight, the viscosity of the composition becomes high and FW molding becomes difficult. On the other hand, if the amount added is less than 10% by weight, the flexural modulus of the cured product will decrease less, but the glass transition temperature will decrease more.
本発明に好適な（Ｃ）成分は前記２つの一般式でそれぞ
れ表わされるインシアネートプレポリマーであるが、よ
り好ましくは両者ともＲ１がｍ＝７〜１１、前者のＲ′
がｎ−２〜４である。特に好ましくは住友バイエルウレ
タン■製のデスモカップｔｉを挙げることができる。Component (C) suitable for the present invention is an incyanate prepolymer represented by the above two general formulas, but more preferably both R1 is m=7 to 11, and R' of the former is
is n-2 to n-4. Particularly preferred is Desmocup ti manufactured by Sumitomo Bayer Urethane.
また本発明では硬化剤として（０）多価芳香族アミン（
以下（Ｄ）成分と称す）を用いる。（Ｄ）成分を上記（
Ａ）および（Ｂ）および（Ｃ）成分と組合わせて用いる
ことにより耐熱性に優れ、かっ可撓性を有する硬化物が
得られる。（０）成分としてｍ−キシリレンジアミン、
ジアミノジフェニルメタン（ＤＤＭ） 、ジアミノジフ
ェニルエーテル、０−フェニレンジアミン、ｍ−フェニ
レンジアミン、ｐ−フェニレンジアミン、２．４−ジア
ミノアニソール、４゜４゛−メチレンジアニリン、ジア
ミノジフェニルスルホン、２．４−）ルエンジアミン、
４−メトキシ−６−メチル−ｍ−フェニレンジアミン、
ｍ−アミノベンジルアミン等が例示される。ＦＷ法に用
いるためには室温で液状のものがより好ましく、メタフ
ェニレンジアミン／ジアミノジフェニルメタン−６０／
４０ （重量比）の共融混合物、メタキシリレンジアミ
ン等や、個体状芳香族ポリアミンを変性し、液状化した
もの等が挙げられる。In addition, in the present invention, as a curing agent (0) polyvalent aromatic amine (
(hereinafter referred to as component (D)) is used. (D) Component above (
When used in combination with components A), (B), and (C), a cured product with excellent heat resistance and flexibility can be obtained. (0) m-xylylene diamine as a component,
Diaminodiphenylmethane (DDM), diaminodiphenyl ether, 0-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 4゜4゛-methylene dianiline, diaminodiphenylsulfone, 2.4-)luenediamine ,
4-methoxy-6-methyl-m-phenylenediamine,
Examples include m-aminobenzylamine. For use in the FW method, a liquid at room temperature is more preferable, and metaphenylenediamine/diaminodiphenylmethane-60/
40 (weight ratio), metaxylylene diamine, etc., and solid aromatic polyamines modified and liquefied.
また、本発明においては、さらに公知の硬化促進剤を併
用してもよい０例えばジクロロフェニル−１，１−ジメ
チルウレア、イミダゾール、イミダゾール誘導体等の硬
化促進剤が使用できる０周知のように、一般に多価アミ
ンを硬化剤として用いる場合には、硬化剤の添加量はエ
ポキシ基１当量当り、アミン１当量を用いるのが普通で
あり、本発明においても（Ｄ）成分をエポキシ基１当量
に対して１当量用いればよい、しかし、必要に応じてポ
ットライフや硬化時間の調節の目的で硬化剤の添加量を
増減しても差し支えないが、本発明を有効に実施するた
めには、（Ｄ）成分の添加量はエポキシ基１当量に対し
て０．８〜１．２当量の範囲が望ましい。In addition, in the present invention, a known curing accelerator may be used in combination.For example, curing accelerators such as dichlorophenyl-1,1-dimethylurea, imidazole, and imidazole derivatives may be used. When using a functional amine as a curing agent, the amount of curing agent added is usually 1 equivalent of amine per 1 equivalent of epoxy group, and in the present invention, component (D) is added per equivalent of epoxy group. However, if necessary, the amount of curing agent added may be increased or decreased for the purpose of adjusting pot life or curing time, but in order to effectively carry out the present invention, (D) The amount of the component added is preferably in the range of 0.8 to 1.2 equivalents per equivalent of epoxy group.
本発明のエポキシ樹脂組成物はそれ単独で硬化させて物
性の優れた成形体を得ることも可能であるが、特に繊維
を強化材とした複合材料のマトリックス材料として使用
するときに優れた効果を発揮する。Although the epoxy resin composition of the present invention can be cured alone to obtain a molded product with excellent physical properties, it exhibits particularly excellent effects when used as a matrix material for a composite material reinforced with fibers. Demonstrate.
複合材料の強化材として使用される繊維としては炭素繊
維、黒鉛繊維、ガラス繊維、炭化ケイ素繊維、アルミナ
繊維、チタニア繊維、窒素硼素繊維、芳香族ポリアミド
繊維、芳香族ポリエステル繊維、ポリベンツイミダゾー
ル繊維等、引張強度５０ｋｇ／ｍ”以上、ヤング率５，
０００ｋｇ／ａｓ”以上の無機質または有機質繊維を例
示することができる。Fibers used as reinforcing materials for composite materials include carbon fiber, graphite fiber, glass fiber, silicon carbide fiber, alumina fiber, titania fiber, nitrogen boron fiber, aromatic polyamide fiber, aromatic polyester fiber, polybenzimidazole fiber, etc. , tensile strength 50 kg/m" or more, Young's modulus 5,
Examples include inorganic or organic fibers with a weight of 1,000 kg/as'' or more.
これら繊維は連続トウ、織布、短繊維、ボイスカーなど
の形で用いることができる。These fibers can be used in the form of continuous tows, woven fabrics, short fibers, voice cars, and the like.
また、使用目的によっては２種以上の繊維、形状の異な
った繊維を併用することも可能である。Furthermore, depending on the purpose of use, it is also possible to use two or more types of fibers or fibers with different shapes.
さらに強化繊維の他にタルク、マイカ、炭酸カルシウム
、アルミナ水和物、炭化ケイ素、カーボンブラック、シ
リカ等の粒状物を混用することも樹脂組成物の粘性を改
良して複合材料の成形を容易にしたり、あるいは得られ
る複合材料の物性、例えば圧縮強度などを改良するため
にを効である。Furthermore, in addition to reinforcing fibers, mixing granular materials such as talc, mica, calcium carbonate, alumina hydrate, silicon carbide, carbon black, and silica improves the viscosity of the resin composition and makes it easier to mold the composite material. or to improve the physical properties of the resulting composite material, such as compressive strength.
さらに本発明による樹脂組成物はＦＷ用に適しているば
かりでなく、樹脂組成物が低粘度であることを活かして
キャスティング・モールディング、レジン・インジェク
ションモールディング用樹脂組成物としても適している
。Furthermore, the resin composition according to the present invention is not only suitable for FW, but also suitable as a resin composition for casting molding and resin injection molding, taking advantage of the low viscosity of the resin composition.
本発明のエポキシ樹脂組成物は成形性に優れ、かつ繊維
を強化材としたとき高い耐熱性を維持して高い靭性を有
しつつ、低曲げ弾性率および高振動減衰性を有する繊維
強化複合材料を与える。The epoxy resin composition of the present invention is a fiber-reinforced composite material that has excellent moldability, maintains high heat resistance and has high toughness when fiber is used as a reinforcing material, and has a low flexural modulus and high vibration damping properties. give.
実施例１〜７および比較例１〜８
（＾）成分としてトリグリシジル−４−アミノ−ｍ−ク
レゾール（住友化学工業■製スミエポキシ＠［！ＩＪＩ
−１００）、（Ｂ）成分としてネオペンチルグリコール
ジグリシジルエーテル（共栄社油脂化学工業■製１５０
ＯＮＰ）、（Ｃ）成分としてインシアネートプレポリマ
ー（住人バイエルウレタン■製デスモカップ１１）、（
Ｄ）成分としてｍ−フェニレンジアミン／ジアミノジフ
ェニルメタン−６０／４０ （重量）共融混合物（ユニ
・ロイヤル社Ｍｔｏｓｏｘ ＠６０／４０）あるいはフ
ェニレンジアミン系（日本化薬■製カヤボンド＠Ｃ−１
０００）および既存のエポキシ樹脂としてビスフェノー
ルＦ（大日本インキ化学工業■製エピクロン＠ ８３０
）を第１表に示すように種々の割合で混合し、室温にお
ける液の初期粘度を測定した。 次にガラス板の間にこ
れらの樹脂組成物を流し込み、恒温乾燥器中で１５０℃
で２時間硬化し、１００■角で厚み２■の樹脂硬化板を
作製した。Examples 1 to 7 and Comparative Examples 1 to 8 (^) As a component, triglycidyl-4-amino-m-cresol (Sumiepoxy manufactured by Sumitomo Chemical ■ [!IJI
-100), as component (B) neopentyl glycol diglycidyl ether (150 manufactured by Kyoeisha Yushi Kagaku Kogyo ■)
ONP), incyanate prepolymer (Desmo Cup 11 manufactured by Bayer Urethane ■) as component (C), (
D) Component m-phenylenediamine/diaminodiphenylmethane-60/40 (weight) eutectic mixture (Uni Royal Mtosox @60/40) or phenylenediamine type (Nippon Kayaku ■Kayabond @C-1)
000) and existing epoxy resins such as bisphenol F (Epiclon@830 manufactured by Dainippon Ink & Chemicals)
) were mixed in various proportions as shown in Table 1, and the initial viscosity of the liquid at room temperature was measured. Next, these resin compositions were poured between glass plates and heated at 150°C in a constant temperature dryer.
The resin was cured for 2 hours to produce a cured resin plate of 100 mm square and 2 mm thick.
これを巾ｌＯ■×長さ１０〇−厚み×２閣の短冊状のテ
ストピースとし３点曲げ試験を行った。試験条件はスパ
ン３０ｍクロスヘツド達度２鋪／分であった。This was used as a rectangular test piece measuring 10 mm in width x 10 mm in length and 2 mm in thickness, and a three-point bending test was conducted. The test conditions were a span of 30 m and a crosshead reach of 2 speeds/min.
その結果を第１表に示す。The results are shown in Table 1.
比較のため本発明で用いる（Ｃ）成分のかわりにウレタ
ン変性エポキシ樹脂（旭電化工業■製ＥＰＵ−１１）あ
るいはウレタン変性エポキシ樹脂（旭電化工業■製ＥＰ
υ−７３）を、 （０）成分のかわりにヘキサヒドロ無
水フタル酸（日立化成工業■ＨＮ３５００）あるいは２
．４．６− トリス（ジメチルアミノメチル）フェノー
ル（住友化学工業■製スミキュア＠Ｄ、ＤＭＰ３０）お
よびビスフェノールＡ（住人化学工業■製スミエポキシ
＠ＥＬＡ１２８）を第２表に示すように種々の割合で混
合し、上記と同様に室温における液の初期粘度を測定し
た。また上記実施例と同様に３点曲げ試験を行った。For comparison, instead of component (C) used in the present invention, urethane-modified epoxy resin (EPU-11 manufactured by Asahi Denka Kogyo) or urethane-modified epoxy resin (EP manufactured by Asahi Denka Kogyo) was used.
υ-73), hexahydrophthalic anhydride (Hitachi Chemical ■HN3500) or 2 instead of component (0).
．． 4.6- Tris(dimethylaminomethyl)phenol (Sumicure@D, DMP30 manufactured by Sumitomo Chemical ■) and bisphenol A (Sumiepoxy@ELA128 manufactured by Sumitomo Chemical ■) were mixed in various proportions as shown in Table 2. The initial viscosity of the liquid at room temperature was measured in the same manner as above. In addition, a three-point bending test was conducted in the same manner as in the above example.
その結果を第２表に示す。The results are shown in Table 2.
第１図は実施例、比較例の硬化樹脂のガラス転移温度と
曲げ弾性率の相関関係を示した図である。FIG. 1 is a diagram showing the correlation between the glass transition temperature and the flexural modulus of the cured resins of Examples and Comparative Examples.
次に２００ｍ角のアルミ板をマンドレルとしＦＷ法にて
実施例３、比較例４．６の樹脂組成物をマトリックとし
ガラス繊維を強化材として一方向に巻きつけた。この巻
付物をホットプレス中に入れ、繊維体積含有率が６０％
になるように圧を調節しながら１５０″Ｃで２時間硬化
し、切断して幅２５■、長さ１７０ａ＋＋ｅ、厚さ２ｍ
の一方向ガラス繊維強化樹脂（ＧＦＲＰ）板を得た。Next, a 200 m square aluminum plate was used as a mandrel, and the resin compositions of Example 3 and Comparative Examples 4 and 6 were used as a matrix and glass fiber was used as a reinforcing material and wound in one direction using the FW method. This rolled material is placed in a hot press and the fiber volume content is 60%.
Cured at 150"C for 2 hours while adjusting the pressure so that
A unidirectional glass fiber reinforced resin (GFRP) board was obtained.
更に外径１４ｍのアルミ棒をマンドレルとしＦＷ法にて
実施例３、比較例Ｉ、４．６の樹脂組成物をマトリンク
スとしガラス繊維を強化材として一方向に巻きつけた。Further, an aluminum rod having an outer diameter of 14 m was used as a mandrel, and the resin compositions of Example 3, Comparative Example I, and 4.6 were used as a matrix and glass fiber was used as a reinforcing material and wound in one direction by the FW method.
この巻付物を乾燥器中に入れ、１５０°Ｃで２時間硬化
し、外径１６鑓、内径１４ＩＩＩ１１、長さ１８０ａＩ
のガラス繊維強化樹脂（ＧＦＲＰ）パイプを得た。This wrapped material was placed in a dryer and cured at 150°C for 2 hours, with an outer diameter of 16mm, an inner diameter of 14III11, and a length of 180aI.
A glass fiber reinforced resin (GFRP) pipe was obtained.
次に得られたＧＦＲＰ板及びＧＦＲＰバイブの振動減衰
比をメカニカルインピーダンス法にて測定した。Next, the vibration damping ratio of the obtained GFRP plate and GFRP vibe was measured using a mechanical impedance method.
その結果を第３表に示す。The results are shown in Table 3.
第２図は硬化樹脂の曲げ弾性率とＧＦＲＰ板およびＧＦ
ＲＰバイブの振動減衰比の相関関係を示した図である。Figure 2 shows the flexural modulus of cured resin, GFRP plate, and GF.
It is a figure showing the correlation of the vibration damping ratio of RP vibe.
第３表Table 3
第１図は硬化樹脂のガラス転移温度と曲げ弾性率の相関
関係を示した図であり、第２図は硬化樹脂の曲げ弾性率
とＧＦＲＰバイブおよびＧＦＲＰ板の振動減衰比の相関
関係を示した図である。
第１図
（１（ｇ／ｍｍ”）
ガラス転移温度 Ｔｇ （”Ｃ）Figure 1 shows the correlation between the glass transition temperature and flexural modulus of the cured resin, and Figure 2 shows the correlation between the flexural modulus of the cured resin and the vibration damping ratio of the GFRP vibe and GFRP board. It is a diagram. Figure 1 (1 (g/mm”) Glass transition temperature Tg (”C)
Claims (2)
換したアミノフェノール化合物のポリグリシジル誘導体
、 （Ｂ）多価脂肪族系アルコールのポリグリシジル誘導体
、 （Ｃ）下記一般式で表わされるイソシアネートプレポリ
マー ▲数式、化学式、表等があります▼ 式中Ｒ＿１：ＣｍＨ＿２＿ｍ＿＋＿１、ｍ＝１〜１６Ｒ
＿２：▲数式、化学式、表等があります▼、ｌ＝１〜４
０ このうちＲ’はＣｎＨ＿２＿ｎでｎ＝１〜８Ｒ＿３：▲
数式、化学式、表等があります▼で表わされるトリレン ジイソシアネートもしくは ▲数式、化学式、表等があります▼で 表わされるジメチルジフェニルメタンジイソシアネート および（Ｄ）多価芳香族アミンを必須成分とするエポキ
シ樹脂組成物。(1) (A) A polyglycidyl derivative of an aminophenol compound whose aromatic ring is substituted with at least one alkyl group, (B) A polyglycidyl derivative of a polyhydric aliphatic alcohol, (C) An isocyanate represented by the following general formula Prepolymer ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula R_1: CmH_2_m_+_1, m = 1 ~ 16R
＿２：▲There are mathematical formulas, chemical formulas, tables, etc.▼, l=1~4
0 Among these, R' is CnH_2_n, n=1~8R_3:▲
An epoxy resin composition containing tolylene diisocyanate represented by ▼, which has mathematical formulas, chemical formulas, tables, etc. or dimethyldiphenylmethane diisocyanate represented by ▼, which has mathematical formulas, chemical formulas, tables, etc., and (D) polyvalent aromatic amine as essential components. .
換したアミノフェノール化合物のポリグリシジル誘導体
、 （Ｂ）多価脂肪族系アルコールのポリグリシジル誘導体
、 （Ｃ）下記一般式で表わされるイソシアネートプレポリ
マー ▲数式、化学式、表等があります▼ 式中 Ｒ＿１：ＣｍＨ＿２＿ｍ＿＋＿１、ｍ＝１〜１６
Ｒ＿３：▲数式、化学式、表等があります▼で表わされ
るトリレンジイソシアネートもしくは ▲数式、化学式、表等があります▼で 表わされるジメチルジフェニルメタンジイソシアネート および（Ｄ）多価芳香族アミンを必須成分とするエポキ
シ樹脂組成物。(2) (A) A polyglycidyl derivative of an aminophenol compound whose aromatic ring is substituted with at least one alkyl group, (B) A polyglycidyl derivative of a polyhydric aliphatic alcohol, (C) An isocyanate represented by the following general formula Prepolymer ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula R_1: CmH_2_m_+_1, m = 1 to 16
R_3: Tolylene diisocyanate represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or dimethyl diphenylmethane diisocyanate represented by ▼ There are mathematical formulas, chemical formulas, tables, etc. ▼ Epoxy whose essential components are (D) polyvalent aromatic amine Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4378088A JPH01217032A (en) | 1988-02-25 | 1988-02-25 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4378088A JPH01217032A (en) | 1988-02-25 | 1988-02-25 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01217032A true JPH01217032A (en) | 1989-08-30 |
Family
ID=12673270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4378088A Pending JPH01217032A (en) | 1988-02-25 | 1988-02-25 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01217032A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009157295A1 (en) * | 2008-06-25 | 2009-12-30 | 東邦テナックス株式会社 | Epoxy resin composition and prepreg using same |
-
1988
- 1988-02-25 JP JP4378088A patent/JPH01217032A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009157295A1 (en) * | 2008-06-25 | 2009-12-30 | 東邦テナックス株式会社 | Epoxy resin composition and prepreg using same |
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