TWI791513B - 片材捲繞(sheet winding)成形法 - Google Patents
片材捲繞(sheet winding)成形法 Download PDFInfo
- Publication number
- TWI791513B TWI791513B TW107113665A TW107113665A TWI791513B TW I791513 B TWI791513 B TW I791513B TW 107113665 A TW107113665 A TW 107113665A TW 107113665 A TW107113665 A TW 107113665A TW I791513 B TWI791513 B TW I791513B
- Authority
- TW
- Taiwan
- Prior art keywords
- prepreg
- meth
- acrylate
- thermosetting
- sheet winding
- Prior art date
Links
- 238000004804 winding Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 17
- 239000011229 interlayer Substances 0.000 abstract description 11
- 230000000704 physical effect Effects 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- 239000003822 epoxy resin Substances 0.000 description 24
- 229920000647 polyepoxide Polymers 0.000 description 24
- -1 glycidyl ester Chemical class 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000005056 polyisocyanate Substances 0.000 description 12
- 229920001228 polyisocyanate Polymers 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 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 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- 239000004917 carbon fiber Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 description 7
- 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 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012783 reinforcing fiber Substances 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229920006389 polyphenyl polymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000285023 Formosa Species 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- DSSYKIVIOFKYAU-UHFFFAOYSA-N camphor Chemical compound C1CC2(C)C(=O)CC1C2(C)C DSSYKIVIOFKYAU-UHFFFAOYSA-N 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000006178 methyl benzyl group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- IMYCVFRTNVMHAD-UHFFFAOYSA-N 1,1-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CCCCC1 IMYCVFRTNVMHAD-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 description 1
- CBCZOJHFXBBSDW-UHFFFAOYSA-N 2-ethyl-2-hexylperoxyhexanoic acid Chemical compound CCCCCCOOC(CC)(C(O)=O)CCCC CBCZOJHFXBBSDW-UHFFFAOYSA-N 0.000 description 1
- RMABUXQQULSJON-UHFFFAOYSA-N 2-hexylperoxypropan-2-yl hydrogen carbonate Chemical group CCCCCCOOC(C)(C)OC(O)=O RMABUXQQULSJON-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
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- GRWFFFOEIHGUBG-UHFFFAOYSA-N 3,4-Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo-hexanecarboxylate Chemical compound C1C2OC2CC(C)C1C(=O)OCC1CC2OC2CC1C GRWFFFOEIHGUBG-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CYSVFVRNOKYFPD-UHFFFAOYSA-N 4-butylperoxycarbonylbenzoic acid Chemical group CCCCOOC(=O)C1=CC=C(C=C1)C(=O)O CYSVFVRNOKYFPD-UHFFFAOYSA-N 0.000 description 1
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- RZJKZTPKSRPUFJ-UHFFFAOYSA-N 5,5-dimethyl-1,3-bis(oxiran-2-ylmethyl)imidazolidine-2,4-dione Chemical compound O=C1N(CC2OC2)C(=O)C(C)(C)N1CC1CO1 RZJKZTPKSRPUFJ-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- FRBAZRWGNOJHRO-UHFFFAOYSA-N 6-tert-butylperoxycarbonyloxyhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CC(C)(C)OOC(=O)OCCCCCCOC(=O)OOC(C)(C)C FRBAZRWGNOJHRO-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- SPUMEPMDCWIOPZ-UHFFFAOYSA-N C1OC1CC1=C(CC2OC2)C(N)=CC=C1CC1CO1 Chemical compound C1OC1CC1=C(CC2OC2)C(N)=CC=C1CC1CO1 SPUMEPMDCWIOPZ-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ADYVCZCQSVYNPQ-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 ADYVCZCQSVYNPQ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 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
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 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
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000006187 phenyl benzyl group Chemical group 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- KXYJPVZMZBJJBZ-UHFFFAOYSA-N tert-butyl 2-ethylbutaneperoxoate Chemical compound CCC(CC)C(=O)OOC(C)(C)C KXYJPVZMZBJJBZ-UHFFFAOYSA-N 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/80—Component parts, details or accessories; Auxiliary operations
- B29C53/84—Heating or cooling
- B29C53/845—Heating or cooling especially adapted for winding and joining
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
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Abstract
本發明提供一種片材捲繞成形法,其係將熱固性預浸漬物一邊加熱一邊捲繞在基體上之片材捲繞成形法,其特徵為:到將下一個熱固性預浸漬物對已捲繞之熱固性預浸漬物進行積層為止的時間,要比已捲繞之熱固性預浸漬物的溫度下之凝膠時間還短。此片材捲繞成形法係可獲得生產性優異、層間剪斷強度等各種物性優異之成形品。
Description
本發明係關於生產性優異之片材捲繞(sheet winding)成形法。
以碳纖維、玻璃纖維等強化纖維所強化過之纖維強化樹脂複合材料,其輕量且耐熱性、機械強度優異的特徵受到矚目,以汽車、飛機之殼體或者各種構材為首,而在各種構造體用途的利用正在擴大。就此纖維強化樹脂複合材料之成形法而言,係使用例如:使用使強化纖維含浸了熱固性樹脂之被稱為預浸漬物的中間材料,而藉由加壓鍋成形、壓製成形、捲繞成形來使其硬化、成形的方法。尤其是為了要獲得筒狀成形物,係施行捲繞成形。
就預浸漬物用之樹脂而言,通常需要兼具有安定性與藉由加熱等之硬化性的樹脂,故一般來說常採用以環氧樹脂組成物為首之熱固性樹脂(參照例如專利文獻1)。
然而,採用了此環氧樹脂組成物之預浸漬物,係有為了要使其具有安定性而硬化緩慢的問題。又,在採用了環氧樹脂之預浸漬物的捲繞成形上,係有以下之課題:於捲繞後以高溫使其硬化時,黏度會降低,且 藉由因捲繞而會發生之殘存張力的張力緩和,而纖維會紊亂且強化降低。
於是,要求可獲得生產性優異、層間剪斷強度等各種物性優異的成形品之成形法。
專利文獻1 日本特開2015-127386號公報
本發明所欲解決之課題,係提供可獲得生產性優異、層間剪斷強度等各種物性優異的成形品之片材捲繞成形法。
本發明人等發現一種特徵為將熱固性預浸漬物以特定條件捲繞於基體上之片材捲繞成形法,係生產性優異,且可獲得層間剪斷強度等各種物性優異之成形品,而完成了本發明。
亦即,關於一種片材捲繞成形法,其係將熱固性預浸漬物一邊加熱一邊捲繞在基體上之片材捲繞成形法,其特徵為:到將下一個熱固性預浸漬物對已捲繞之熱固性預浸漬物進行積層為止的時間,要比已捲繞之熱固性預浸漬物的溫度下之凝膠時間還短。
利用本發明之片材捲繞成形法可得到之成形品,係因為層間剪斷強度等優異,而適合使用於汽車構件、鐵路車輛構件、航空宇宙機構件、船舶構件、住宅設備構件、體育用構件、輕車輛構件、建築土木構件、OA機器等之殼體等。
本發明之片材捲繞成形法,係將熱固性預浸漬物一邊加熱一邊捲繞在基體上之片材捲繞成形法,其到將下一個熱固性預浸漬物對已捲繞之熱固性預浸漬物進行積層為止的時間,要比已捲繞之熱固性預浸漬物的溫度下之凝膠時間還短。
本發明之成形法,由於藉由將硬化性優異之熱固性預浸漬物一邊加熱一邊捲繞於基體,而硬化會與捲繞並行地進行,所以不需要捲繞結束後之硬化步驟,生產性優異。又,可抑制因張力緩和所致之纖維的紊亂,可獲得層間剪斷強度優異之成形品。
又,由於到將下一個熱固性預浸漬物對已捲繞之熱固性預浸漬物進行積層為止的時間(以下,簡稱為「預浸漬物之積層時間」),要比已捲繞之熱固性預浸漬物之凝膠時間還短,所以可獲得層間密接性優異、層間剪斷強度優異之成形品。
前述熱固性預浸漬物含有熱固性樹脂組成物及強化纖維,但就熱固性樹脂組成物而言,因硬化性及成形品之層間剪斷強度會更為提升,而較佳為含有自由基聚合性樹脂及聚合起始劑。
就前述自由基聚合性樹脂而言,可列舉例如環氧(甲基)丙烯酸酯、胺基甲酸酯改性環氧(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、不飽和聚酯等,但因硬化性及成形品之層間剪斷強度會更為提升,而較佳為胺基甲酸酯改性環氧(甲基)丙烯酸酯或胺基甲酸酯(甲基)丙烯酸酯。該等自由基聚合性樹脂,係可單獨使用也可併用2種以上。
就前述胺基甲酸酯改性環氧(甲基)丙烯酸酯而言,因作業性及成形品之層間剪斷強度會更為提升,而較佳為藉由每1分子的平均羥基數1.8~2.6之環氧(甲基)丙烯酸酯與每1分子之平均異氰酸酯基數2~3之聚異氰酸酯的反應所得到者。
前述環氧(甲基)丙烯酸酯,係可使環氧樹脂與(甲基)丙烯酸及/或(甲基)丙烯酸酐進行反應而得到。就用以使成為每1分子之平均羥基數1.8~2.6之手法的例子而言,係藉由環氧樹脂之平均環氧基數與平均羥基數、與(甲基)丙烯酸及/或(甲基)丙烯酸酐之反應時之莫耳數的設定而可進行控制。
就前述環氧樹脂而言,可列舉例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚茀型環氧樹脂、雙甲酚茀型等之雙酚型環氧樹脂、酚酚醛清漆型環氧樹 脂、甲酚酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂、唑啶酮改性環氧樹脂、該等樹脂之溴化環氧樹脂等之酚之縮水甘油基醚、二丙二醇二縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、雙酚A之環氧烷類加成物之二縮水甘油基醚、氫化雙酚A之二縮水甘油基醚等之多元醇之縮水甘油基醚、3,4-環氧-6-甲基環己基甲基-3,4-環氧-6-甲基環己烷羧酸酯、1-環氧乙基-3,4-環氧環己烷等之脂環式環氧樹脂、酞酸二縮水甘油酯、四氫酞酸二縮水甘油酯、二縮水甘油基對氧基安息香酸、二聚酸縮水甘油酯等之縮水甘油酯、四縮水甘油基二胺基二苯基甲烷、四縮水甘油基間二甲苯二胺、三縮水甘油基間對胺基苯、N,N-二縮水甘油基苯胺等之縮水甘油基胺、1,3-二縮水甘油基-5,5-二甲基乙內醯脲、三縮水甘油基三聚異氰酸酯等之雜環式環氧樹脂等。該等之中,又因可獲得機械強度及耐熱性更優異的成形品,而更佳為雙酚型環氧樹脂、酚醛清漆型環氧樹脂或唑啶酮改性環氧樹脂,進一步因可獲得層間剪斷強度與機械強度之平衡優異的硬化物,而更佳為雙酚型環氧樹脂或唑啶酮改性環氧樹脂。就環氧樹脂之環氧當量而言,自150起到400為止係從耐熱性、硬化性的觀點來看為較佳。另外,該等環氧樹脂,係可單獨使用也可併用2種以上。
前述環氧樹脂與(甲基)丙烯酸之反應,係較佳為在60~140℃下使用酯化觸媒來進行。又,也可以使用聚合抑制劑等。
就在前述胺基甲酸酯改性環氧(甲基)丙烯酸酯之製造所使用的聚異氰酸酯而言,較佳為每1分子之平均異氰酸酯基數為2~3者,但可使用例如二苯基甲烷二異氰酸酯(4,4’-體、2,4’-體或2,2’-體、或其混合物)、二苯基甲烷二異氰酸酯之碳二亞胺改性體、Nurate改性體、Buretta改性體、胺基甲酸酯亞胺改性體、以二乙二醇或丙二醇等之數量平均分子量1000以下之聚醇進行改性之聚醇改性體等之二苯基甲烷二異氰酸酯改性體、甲伸苯基二異氰酸酯、聯甲苯胺二異氰酸酯、多亞甲基多苯基聚異氰酸酯、伸茬基二異氰酸酯、1,5-萘二異氰酸酯、四甲基伸茬基二異氰酸酯等之芳香族聚異氰酸酯;異佛爾酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化伸茬基二異氰酸酯、降莰烯二異氰酸酯等之脂環式聚異氰酸酯;六亞甲基二異氰酸酯、六亞甲基二異氰酸酯、之Nurate改性體、Buretta改性體、加成體、二聚酸二異氰酸酯等之脂肪族聚異氰酸酯等。又,該等聚異氰酸酯,係可單獨使用也可併用2種以上。
前述胺基甲酸酯改性環氧(甲基)丙烯酸酯之製造中的聚異氰酸酯之異氰酸酯基(NCO)與前述環氧(甲基)丙烯酸酯之羥基(OH)的莫耳比(NCO/OH),因藉由鏈伸長反應之高分子量化所致作業性(黏性)與樹脂的流動性之平衡會更為優異,而較佳為0.6~1.1之範圍為佳,更佳為0.7~1.0之範圍。
就前述胺基甲酸酯(甲基)丙烯酸酯而言,因可獲得作業性及成形性優異、層間剪斷強度、耐熱性等 各種物性優異之成形品,而較佳為以多亞甲基多苯基聚異氰酸酯為必要原料的聚異氰酸酯化合物、與以具有羥基及(甲基)丙烯醯基之化合物為必要原料的具有羥基之化合物的反應物之胺基甲酸酯(甲基)丙烯酸酯。
前述多亞甲基多苯基聚異氰酸酯,係以如下通式(1)所示者。
(式中,n為1以上的整數。)
就前述胺基甲酸酯之具有羥基及(甲基)丙烯醯基之化合物而言,可列舉例如羥基烷基(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。另外,該等具有羥基及(甲基)丙烯醯基之化合物,係可單獨使用也可併用2種以上。
會成為前述胺基甲酸酯(甲基)丙烯酸酯(A)之原料的異氰酸酯化合物之異氰酸酯基(NCO)與具有羥基之化合物(a2)之羥基(OH)的莫耳比(NCO/OH),較佳為0.1~1.5,更佳為0.3~1.2。
就前述熱固性樹脂組成物中所含有之該聚合起始劑而言,較佳為有機過氧化物,可列舉例如二醯基過氧化物化合物、過氧酯化合物、鹵素過氧化物化合物、酮過氧化物化合物、烷基過氧酯化合物、過碳酸酯化合物、過氧縮酮等,且因應成形條件而可適當選擇。該等聚合起始劑,係可單獨使用也可併用2種以上。
又,該等之中,又因預浸漬物在常溫下的壽命長,且藉由加熱而硬化會在短時間內進行,而較佳為用以獲得10小時半衰期之溫度為70℃以上100℃以下的聚合起始劑。可藉由使用該等聚合起始劑,而在短時間內得到具有優異之層間剪斷強度的成形品。就此類聚合起始劑而言,可列舉例如1,6-雙(第三丁基過氧羰基氧基)己烷、1,1-雙(第三丁基過氧)環己烷、1,1-雙(第三戊基過氧)環己烷、1,1-雙(第三丁基過氧)環己烷、第三丁基過氧二乙基醋酸酯、第三丁基過氧異丙基碳酸酯、第三戊基過氧異丙基碳酸酯、第三己基過氧異丙基碳酸酯、二第三丁基過氧氫對酞酸酯、第三戊基過氧三甲基己酸酯、第三己基過氧-2-乙基己酸酯等。
又,前述熱固性樹脂組成物中,因硬化性及成形品之層間剪斷強度會更為提升,而較佳為含有乙烯性不飽和單體者。
就前述乙烯性不飽和單體而言,可列舉例如苯乙烯、甲基苯乙烯、鹵化苯乙烯、二乙烯基苯等之苯乙烯化合物;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸甲基苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸甲基苯氧基乙酯、(甲基)丙烯酸啉酯、(甲基)丙烯酸苯基苯氧基乙酯、(甲基)丙烯酸苯基苄酯、甲基丙烯酸苯酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、甲基丙烯酸二環戊二 烯酯等之單官能基(甲基)丙烯酸酯化合物;(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯等之含羥基(甲基)丙烯酸酯化合物;乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚二(甲基)丙烯酸酯、1,4-環己烷二甲醇二(甲基)丙烯酸酯等之二(甲基)丙烯酸酯化合物等。該等係可單獨使用也可併用2種以上。
其中,又因作業環境時之臭氣及危險物的處理、成形體之機械強度及耐熱性,而較佳為分子量150~250之單官能(甲基)丙烯酸酯,更佳為(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸甲基苯氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸甲基苄酯,進一步較佳為(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苄酯。
就前述強化纖維而言,可列舉出碳纖維、玻璃纖維、碳化矽纖維、氧化鋁纖維、硼纖維、金屬纖維、聚芳醯胺纖維、維尼綸纖維、特龍綸纖維等,因可獲得更高強度、高彈性之成形品,而較佳為碳纖維或玻璃纖維,更佳為碳纖維。該等強化纖維,係可單獨使用也可併用2種以上。
就前述熱固性預浸漬物而言,可使用已將強化纖維絲束整理成單一方向之單向材料、已將單向材積層者,包含織製織物或已裁短之強化纖維的不織布等。就單向預浸漬物之積層構成而言,係可列舉出0°、(0°、90°)、(+45°/0°/-45°/90°)、(+60°/0°/-60°)等。
又,前述熱固性預浸漬物之厚度,係較佳為0.02~1mm之範圍,更佳為0.05~0.5mm。
前述熱固性預浸漬物之寬度,係較佳為100~2000mm之範圍,更佳為300~1500mm之範圍。
前述熱固性預浸漬物,因生產性及成形品之層間剪斷強度會更為提升,而較佳為150℃下之凝膠時間為10~90秒鐘之範圍,更佳為15~60秒鐘之範圍。
本發明之預浸漬物之凝膠時間及硬化時間,係以CURELASTOMETER7 TYPE P(JSR TRADING股份有限公司製)所測定者。
將熱固性預浸漬物捲繞在基體上之速度,重要的是以預浸漬物之積層時間比熱固性預浸漬物之凝膠時間還短的方式進行調整,但因生產性及成形品之層間剪斷強度會更為提升,而較佳為8~850mm/秒鐘之範圍,更佳為15~400mm/秒鐘之範圍。
前述預浸漬物之積層時間,因生產性及成形品之層間剪斷強度會更為提升,而較佳為1~90秒鐘之範圍,更佳為1~60秒鐘之範圍。
就前述已捲繞之熱固性預浸漬物之溫度而言,因生產性及成形品之層間剪斷強度會更為提升的觀點,而較佳為80~160℃之範圍,更佳為110~160℃之範圍,進一步較佳為120~150℃之範圍。
本發明之熱固性預浸漬物之溫度,係將預浸漬物的表面以熱電偶型溫度計進行了測定的溫度。
就熱固性預浸漬物之加熱方法而言,並未特別受到限定,但因可輕易加熱,而較佳為藉由與已加熱之基材的接觸、與加熱輥之接觸、與加熱板之接觸、紅外線加熱器、微波、鹵素加熱器的加熱。
就捲繞熱固性預浸漬物之基體而言,較佳為桶槽、管等筒狀的基體。
就前述該基體之周長而言,因捲繞速度的調整會更輕易,而較佳為30~3000mm之範圍。
因藉由本發明之片材捲繞成形法而得到之成形品的層間剪斷強度會更為提升,而較佳為在捲繞結束後,到熱固性預浸漬物之硬化時間經過為止,維持加熱。
藉由本發明之片材捲繞成形法所得到之成形品,因層間剪斷強度等優異,而可適當使用在汽車構件、鐵路車輛構件、航空宇宙機構件、船舶構件、住宅設備構件、體育用構件、輕車輛構件、建築土木構件、OA機器等之殼體等。
以下,列舉具體實施例來更詳盡地說明本發明。
在安裝有溫度計、氮氣及空氣導入管、攪拌機之1L燒瓶中,進料環氧樹脂(DIC股份有限公司製,「EPICLON 850-S」,雙酚A型環氧樹脂,環氧當量190)380質量份、甲基丙烯酸170質量份、第三丁基氫醌0.16質量份,在 以1比1混合了氮氣與空氣之氣體流通下,升溫至90℃。於此加入參二甲基胺基苯酚1.1質量份,升溫至110℃,使反應進行10小時,而因酸價成為4以下,而結束了反應。冷卻至60℃附近之後,從反應容器中取出,得到了環氧甲基丙烯酸酯(1)。
於預先混合了依上述所得之環氧甲基丙烯酸酯(1)75質量份與苯氧基乙基甲基丙烯酸酯25質量份的樹脂液100質量份中,混合了對苯醌0.02質量份、聚合起始劑(KAYAKU AKZO股份有限公司製「TRIGONOX 27」,有機過氧化物)1質量份之後,混合4,4’-二苯基甲烷二異氰酸酯28質量份,得到了熱固性樹脂組成物(1)。
採用預浸漬物製造裝置,使碳纖維(FORMOSA PLASTIC CORPORATION製「TC-36P」)含浸上述所得之熱固性樹脂組成物(1),使碳纖維之體積含有率成為60%,得到了熱固性預浸漬物(1)。此熱固性預浸漬物(1)之厚度為0.09mm,寬度為300mm。又,150℃下之凝膠時間為25秒鐘,146℃下之凝膠時間為29秒鐘,146℃下之硬化時間為49秒鐘。
將多亞甲基多苯基聚異氰酸酯與二苯基二異氰酸酯之混合物(TOSOH股份有限公司製「MILLIONATE MR-200」,多亞甲基多苯基聚異氰酸酯含量56%;以下簡稱為「POLYMERIC MDI混合物(1)」)100質量份與羥基乙基甲基丙烯酸酯75.5質量份、與季戊四醇多氧基伸 乙基醚(日本乳化劑股份有限公司製「PNT-40」)15質量份、與苯氧基乙基甲基丙烯酸酯21質量份、與聚合起始劑(KAYAKU AKZO股份有限公司製「TRIGONOX 27」,有機過氧化物)2質量份予以混合,得到了熱固性樹脂組成物(2)。
採用預浸漬物製造裝置,使碳纖維(FORMOSA PLASTIC CORPORATION製「TC-36P」)含浸依上述所得之熱固性樹脂組成物(2),使碳纖維之體積含有率成為60%,得到了熱固性預浸漬物(2)。此熱固性預浸漬物(2)之厚度為0.09mm,寬度為300mm。又,150℃下之凝膠時間為19秒鐘,146℃下之凝膠時間為21秒鐘,120℃下之凝膠時間為70秒鐘,116℃下之凝膠時間為76秒鐘,146℃下之硬化時間為43秒鐘,116℃下之硬化時間為105秒鐘。
一邊在即將要將依製造例1所得之300mm寬的熱固性預浸漬物(1)捲繞於基體之前,利用150℃之紅外線加熱器加熱預浸漬物的兩側,一邊對溫度150℃之直徑100mm、寬度500mm之管,以22mm/秒鐘(預浸漬物之積層時間:14秒鐘)之速度,以相同的捲繞寬度,進行捲繞30圈,其後,保持加熱90秒鐘,得到了成形品(1)。已捲繞之預浸漬物的溫度為146~150℃。此成形品(1)之層間剪斷強度為37MPa。
一邊在即將要將依製造例1所得之300mm寬的熱固性預浸漬物(1)捲繞於基體之前,利用150℃之紅外線加熱器加溫預浸漬物的兩側,一邊對溫度150℃之直徑100mm、寬度500mm之管,以67mm/秒鐘(預浸漬物之積層時間:5秒鐘)之速度,以相同的捲繞寬度,進行捲繞30圈,其後,保持加熱90秒鐘,得到了成形品(2)。已捲繞之預浸漬物的溫度為146~150℃。此成形品(2)之層間剪斷強度為52MPa。
一邊在即將要將依製造例1所得之300mm寬的熱固性預浸漬物(1)捲繞於基體之前,利用150℃之紅外線加熱器加溫預浸漬物的兩側,一邊對溫度150℃之直徑100mm、寬度500mm之管,以125mm/秒鐘(預浸漬物之積層時間:3秒鐘)之速度,以相同的捲繞寬度,進行捲繞30圈,其後,保持加熱90秒鐘,得到了成形品(3)。已捲繞之預浸漬物的溫度為146~150℃。此成形品(3)之層間剪斷強度為42MPa。
一邊在即將要將依製造例2所得之300mm寬的熱固性預浸漬物(2)捲繞於基體之前,利用150℃之紅外線加熱器加溫預浸漬物的兩側,一邊對溫度150℃之直徑100mm、寬度500mm之管,以125mm/秒鐘(預浸漬物之 積層時間:3秒鐘)之速度,以相同的捲繞寬度,進行捲繞30圈,其後,保持加熱90秒鐘,得到了成形品(4)。已捲繞之預浸漬物的溫度為146~150℃。此成形品(4)之層間剪斷強度為32MPa。
一邊在即將要將依製造例2所得之300mm寬的熱固性預浸漬物(2)捲繞於基體之前,利用120℃之紅外線加熱器加溫預浸漬物的兩側,一邊對溫度120℃之直徑100mm、寬度500mm之管,以67mm/秒鐘(預浸漬物之積層時間:5秒鐘)之速度,以相同的捲繞寬度,進行捲繞30圈,其後,保持加熱120秒鐘,得到了成形品(5)。已捲繞之預浸漬物的溫度為116~120℃。此成形品(5)之層間剪斷強度為38MPa。
一邊在即將要將依製造例1所得之300mm寬的熱固性預浸漬物(1)捲繞於基體之前,利用150℃之紅外線加熱器加溫預浸漬物的兩側,一邊對溫度150℃之直徑100mm、寬度500mm之管,以9mm/秒鐘(預浸漬物之積層時間:35秒鐘)之速度,以相同的捲繞寬度,進行捲繞30圈,其後,保持加熱90秒鐘,得到了成形品(R1)。已捲繞之預浸漬物的溫度為146~150℃。此成形品(R1)之層間剪斷強度為11MPa。
一邊在即將要將依製造例1所得之300mm寬的熱固性預浸漬物(1)捲繞於基體之前,利用150℃之紅外線加熱器加溫預浸漬物的兩側,一邊針對溫度150℃之直徑100mm、寬度500mm之管,以2mm/秒鐘(預浸漬物之積層時間:157秒鐘)之速度,以相同的捲繞寬度,進行捲繞30圈,其後,保持加熱90秒鐘,得到了成形品(R2)。已捲繞之預浸漬物的溫度為146~150℃。此成形品(R2)之層間剪斷強度為2MPa。
從依上述所得之成形品(1)切出寬10mm、長20mm的試驗片,針對此試驗片,依據JIS K7078,測定層間剪斷強度,依據下述基準進行了評價。
◎:50MPa以上
○:15MPa以上且小於50MPa
△:10MPa以上且小於15MPa
×:小於10MPa
將依上述所得之成形品(1)~(5)、及成形品(R1)~(R2)之評價結果呈示於表1。
藉由實施例1~5之本發明之片材捲繞成形法所得到之成形品,係已確認到層間剪斷強度優異。
另一方面,比較例1及2,係到將下一個熱固性預浸漬物對已捲繞之熱固性預浸漬物進行積層為止的時間,比已捲繞之熱固性預浸漬物的溫度下之凝膠時間還長的例子,但已確認到層間剪斷強度不佳。
Claims (3)
- 一種片材捲繞成形法,其係將熱固性預浸漬物一邊加熱一邊捲繞在基體上之片材捲繞成形法,其特徵為:到將下一個熱固性預浸漬物對已捲繞之熱固性預浸漬物進行積層為止的時間,要比已捲繞之熱固性預浸漬物的溫度下之凝膠時間還短,該熱固性預浸漬物的150℃下之凝膠時間為15秒鐘以上且小於60秒鐘之範圍。
- 如請求項1之片材捲繞成形法,其中該已捲繞之熱固性預浸漬物之溫度為80~160℃之範圍。
- 如請求項1或2之片材捲繞成形法,其中該熱固性預浸漬物含有自由基聚合性樹脂。
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Family Cites Families (12)
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---|---|---|---|---|
JPH0315521A (ja) * | 1990-05-30 | 1991-01-23 | Tenryu Kogyo Kk | 強化プラスチック製中空材 |
JP2003170513A (ja) * | 2001-12-04 | 2003-06-17 | Risho Kogyo Co Ltd | 熱硬化性樹脂積層管 |
US20070096371A1 (en) * | 2005-10-27 | 2007-05-03 | General Electric Company | Process of producing ceramic matrix composites |
JP5151095B2 (ja) * | 2006-08-31 | 2013-02-27 | 東レ株式会社 | プリプレグおよび繊維強化複合材料 |
JP4284705B2 (ja) * | 2006-12-11 | 2009-06-24 | トヨタ自動車株式会社 | 成形体の製造方法、成形体、並びにタンク |
JP5244840B2 (ja) * | 2009-04-09 | 2013-07-24 | ダンロップスポーツ株式会社 | 管状体及びその製造方法 |
US8123888B2 (en) * | 2009-04-28 | 2012-02-28 | Schlumberger Technology Corporation | Fiber reinforced polymer oilfield tubulars and method of constructing same |
WO2012000678A1 (en) * | 2010-07-02 | 2012-01-05 | Hexcel Holding Gmbh | Fibre reinforced composite moulding |
CN103363204B (zh) * | 2012-03-29 | 2017-02-22 | 上海杰事杰新材料(集团)股份有限公司 | 一种连续纤维增强热塑性树脂缠绕管材 |
KR102245594B1 (ko) * | 2013-11-26 | 2021-04-27 | 테이진 리미티드 | 열경화성 수지 조성물, 프리프레그 및 이것들을 사용하는 섬유 강화 복합 재료의 제조 방법 |
JP2015127386A (ja) | 2013-11-28 | 2015-07-09 | 三菱レイヨン株式会社 | トウプリプレグ、及び複合材料補強圧力容器とその製造方法 |
JP6593620B2 (ja) * | 2014-11-21 | 2019-10-23 | Dic株式会社 | エポキシ樹脂組成物、硬化物、繊維強化複合材料、繊維強化樹脂成形品、及び繊維強化樹脂成形品の製造方法 |
-
2018
- 2018-04-12 US US16/608,546 patent/US20200198221A1/en not_active Abandoned
- 2018-04-12 JP JP2018556952A patent/JP6493776B1/ja active Active
- 2018-04-12 KR KR1020197030973A patent/KR102183392B1/ko active IP Right Grant
- 2018-04-12 EP EP18791225.8A patent/EP3616888B1/en active Active
- 2018-04-12 WO PCT/JP2018/015359 patent/WO2018198795A1/ja unknown
- 2018-04-12 CN CN201880027779.2A patent/CN110573327A/zh active Pending
- 2018-04-23 TW TW107113665A patent/TWI791513B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02113927A (ja) * | 1988-10-24 | 1990-04-26 | Mazda Motor Corp | Frp成形体の製造方法 |
EP1191253A1 (en) * | 2000-09-11 | 2002-03-27 | Toray Composites (America), Inc. | High-speed manufacturing method for composite flywheels, flywheel and apparatus to manufacture flywheels |
JP2004099814A (ja) * | 2002-09-12 | 2004-04-02 | Toray Ind Inc | プリプレグおよび繊維強化複合材料 |
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KR20190126174A (ko) | 2019-11-08 |
US20200198221A1 (en) | 2020-06-25 |
EP3616888A4 (en) | 2020-11-11 |
TW201902719A (zh) | 2019-01-16 |
WO2018198795A1 (ja) | 2018-11-01 |
EP3616888B1 (en) | 2022-08-10 |
JP6493776B1 (ja) | 2019-04-03 |
JPWO2018198795A1 (ja) | 2019-06-27 |
EP3616888A1 (en) | 2020-03-04 |
KR102183392B1 (ko) | 2020-11-27 |
CN110573327A (zh) | 2019-12-13 |
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