JP4986627B2 - 耐熱複合材料 - Google Patents
耐熱複合材料 Download PDFInfo
- Publication number
- JP4986627B2 JP4986627B2 JP2006543153A JP2006543153A JP4986627B2 JP 4986627 B2 JP4986627 B2 JP 4986627B2 JP 2006543153 A JP2006543153 A JP 2006543153A JP 2006543153 A JP2006543153 A JP 2006543153A JP 4986627 B2 JP4986627 B2 JP 4986627B2
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- JP
- Japan
- Prior art keywords
- composite material
- heat
- resistant composite
- epoxy compound
- epoxy
- 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.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000004593 Epoxy Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 24
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 5
- 239000004917 carbon fiber Substances 0.000 claims abstract description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 39
- 239000003822 epoxy resin Substances 0.000 claims description 37
- -1 alkali metal salt Chemical class 0.000 claims description 29
- 229910052783 alkali metal Inorganic materials 0.000 claims description 26
- 230000001588 bifunctional effect Effects 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 18
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 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 17
- 238000000034 method Methods 0.000 description 14
- 238000012423 maintenance Methods 0.000 description 13
- 125000003700 epoxy group Chemical group 0.000 description 12
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 229920006015 heat resistant resin Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000011825 aerospace material Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000009787 hand lay-up Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 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 1
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- PEHXKUVLLWGBJS-UHFFFAOYSA-N 2-[1-(2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=CC=C(O)C=1C(C)C1=CC=CC=C1O PEHXKUVLLWGBJS-UHFFFAOYSA-N 0.000 description 1
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 1
- NKANYVMWDXJHLE-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1OCC1CO1 NKANYVMWDXJHLE-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- RESFZFUAOCMIOD-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxy)-2,5-di(propan-2-yl)phenoxy]methyl]oxirane Chemical compound CC(C)C=1C=C(OCC2OC2)C(C(C)C)=CC=1OCC1CO1 RESFZFUAOCMIOD-UHFFFAOYSA-N 0.000 description 1
- FSYPIGPPWAJCJG-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1OCC1CO1 FSYPIGPPWAJCJG-UHFFFAOYSA-N 0.000 description 1
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- KBRQWCWVFNLHPU-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-2,3,5,6-tetramethylphenol Chemical compound CC1=C(O)C(C)=C(C)C(CC=2C=CC(O)=CC=2)=C1C KBRQWCWVFNLHPU-UHFFFAOYSA-N 0.000 description 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- YTZQPKSLNZRAPQ-UHFFFAOYSA-N C1(CCCCC1)OC(CC)=O.[K] Chemical compound C1(CCCCC1)OC(CC)=O.[K] YTZQPKSLNZRAPQ-UHFFFAOYSA-N 0.000 description 1
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 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
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000011074 autoclave method Methods 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
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 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
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- HJZLEGIHUQOJBA-UHFFFAOYSA-N cyclohexane propionic acid Chemical compound OC(=O)CCC1CCCCC1 HJZLEGIHUQOJBA-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WDWQCZSGSFCYTP-UHFFFAOYSA-L dipotassium;2-undecylpropanedioate Chemical compound [K+].[K+].CCCCCCCCCCCC(C([O-])=O)C([O-])=O WDWQCZSGSFCYTP-UHFFFAOYSA-L 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
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
-
- 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
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- 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
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- 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
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- C08G59/68—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 catalysts used
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明の他の態様においては、上記エポキシ化合物は、2官能のエポキシ化合物と3官能以上のエポキシ化合物とからなる。
本発明はまた、上記耐熱複合材料からなる車両部材又は建築部材でもある。
(1)カルボン酸のアルカリ金属塩を用いて2官能以上のエポキシ化合物を高い反応速度で重合させることにより、停止反応、連鎖移動が起こりにくく、エポキシ化合物の高い重合度を実現した重合体をマトリックスとすることができる。
(2)本発明におけるアニオン重合開始剤は、吸湿性が比較的低く、本発明の複合材料は空気中で作業することが可能である。
(3)2官能以上のエポキシ化合物を重合することにより、損失正接の極大値として観測しうるTgを事実上持たず、高温でも高い弾性率維持率を有する高耐熱性樹脂をマトリックスとする複合材料を製造することができる。
(4)2官能のエポキシ化合物と3官能のエポキシ化合物とを併用することにより、極めて高い弾性率維持率を有する高耐熱性樹脂をマトリックスとする複合材料を製造することができる。
(5)本発明の複合材料は、複合材料としての高温弾性率の維持率が極めて高く、従来の複合材料における高温弾性率の維持率をはるかに凌ぐ高い値を示す。
Butadiene Acrylonitrile Copolymer、宇部興産社製)等を挙げることができる。
Ec=k[EfVf+Em(1−Vf)]
ここで、Ecは複合材料の弾性率、Efは強化繊維の弾性率、Emはマトリックス樹脂の弾性率、Vfは強化繊維の体積含有率である。また、kは、繊維の形態、不整配向や空隙等の影響を考慮した修正係数で通常0.5〜1.0程度の値をとる。上述のように、300℃近い高温では、マトリックス樹脂の弾性率の低下が激しく、強化繊維が複合材料内で形状保持をすることができないため、この式では、本発明のような300℃近い高温での複合材料の弾性率を推定することはできない。換言すれば、この式はあくまでも、強化繊維が複合材料内でマトリックス樹脂により支持され、束ねられている場合での静的な弾性率を推定する式である。その結果、従来は高温での複合材料の弾性率を推定することができず、高温での複合材料設計が極めて困難であった。
Ec=0.5×[74×0.4+5×(1−0.4)]=16.3GPa (25℃)
Ec=0.5×[74×0.4+2×(1−0.4)]=15.4GPa (300℃)
AER260:旭化成エポキシ社製、ビスフェノールA型液状エポキシ樹脂、エポキシ当量190g/eq)
EPIKOTE1032H60:ジャパンエポキシレジン社製、3官能エポキシ樹脂、エポキシ当量168g/eq
EPIKOTE828:ジャパンエポキシレジン社製、2官能エポキシ樹脂、エポキシ当量190g/eq
リカシッドMT−500TZ:新日本理化社製、メチルテトラヒドロフタル酸無水物
S−CURE−661:化薬アクゾ社製、硬化促進剤
CHPK:シクロヘキシルプロピオン酸カリウム
DDK:ドデカンジカルボン酸ジカリウム
WE181:ガラス繊維織物(日東紡績社製)
複合材料の製作
表1に示す使用原料のうちガラス繊維織物WF181以外の原料を表1記載の重量部混合し、混合体を得た。なお、得られた混合体は、混合体作成時及び室温に保管している状態では重合反応を生じなかった。
ついで、この混合体をマトリックス樹脂とし、強化材にはガラス繊維織物WF181(日東紡績社製)を表1記載の体積%で用いてガラス繊維強化プラスチック(GFRP)の製作を行った。具体的には、液状の混合体を60℃に予備加熱し、ハンド・レイ・アップ法にて、各強化繊維織物に所定枚数(6Ply)を含浸積層させた。その後、設定厚みのスペーサーを準備して液状の混合体と一緒に層間の気泡を押し出してプリプレグを作成した。そして、平板形状の金型を使用し、120℃×2時間+180℃×4時間の硬化条件にて、成形圧力1.0MPaで加熱プレス成形を行った。
得られた複合材料の耐熱性を評価するために、動的粘弾性試験を実施した。以下の方法で貯蔵弾性率と損失正接(tanδ)を求めた。
測定方法
セイコーインスツルメンツ社製粘弾性測定装置DMS6100を用いて、両持ち曲げモードで1Hzの正弦波を印加し、0〜300℃の温度範囲で、昇温速度2℃/分で行った。結果を図1に示した。
また、25℃における弾性率と300℃における弾性率の値から、弾性率維持率を求めた。弾性率維持率は以下の式による。
弾性率維持率=(300℃における弾性率の値)/(25℃における弾性率の値)×100(%)
得られた複合材料の静的な強度と弾性率を確認するために、JIS K 7198に準じて3点曲げ試験を行った(万能試験機インスロン(インスロン社製)を使用して測定した。クロスヘッドスピード5.3mm/分)。試験片形状は、高さ2mm、幅15mm、長さ80mmで、曲げスパンは60mmとした。測定は25℃、170℃、200℃及び230℃で行った。結果を表1に示した。
更に、図1から、貯蔵弾性率の300℃までの高温維持率は81%にも達したことが判明した。このように、本発明の複合材料が従来の複合材料と異なり、300℃のような高温でも非常に高い弾性率の維持率を示すのは、次のような理由によるものであると考えられる:
(1)本発明に使用した樹脂が、300℃での弾性率の維持率が30〜40%程度であること、(2)複合化した強化繊維が非常に高い弾性率を有しており、300℃までの弾性率の低下がないこと、及び、(3)本発明に使用した樹脂が、ガラス繊維やカーボン繊維との密着性に優れていること。
また、実施例1の複合材料ではtanδのピークが現れず、Tgが存在しないことも確認された。弾性率が300℃に至るまでほぼ一定の値を維持していることからも、実施例1の複合材料は高い耐熱性を有することが明らかであった。
Claims (8)
- 2官能以上のエポキシ化合物とアニオン重合開始剤とからなり、前記アニオン重合開始剤は、1官能カルボン酸のアルカリ金属塩からなり、かつ、前記エポキシ化合物をアニオン重合して硬化エポキシ樹脂とするものである、アニオン重合性組成物を強化用繊維に含浸させ、硬化してなる硬化エポキシ樹脂をマトリックスとする、繊維強化耐熱複合材料。
- 前記1官能カルボン酸のアルカリ金属塩は、Na又はKの塩である請求項1記載の耐熱複合材料。
- 前記エポキシ化合物は、2官能のエポキシ化合物と3官能以上のエポキシ化合物とからなる請求項1又は2記載の耐熱複合材料。
- 前記強化用繊維は、カーボン繊維及びガラス繊維からなる群から選択される少なくとも1種である請求項1〜3のいずれか記載の耐熱複合材料。
- 前記強化用繊維の配合量は、複合材料中に20〜60体積%である請求項1〜4のいずれか記載の耐熱複合材料。
- 前記強化用繊維は、織物である請求項1〜5のいずれか記載の耐熱複合材料。
- 請求項1〜6のいずれか記載の耐熱複合材料からなる車両部材。
- 請求項1〜6のいずれか記載の耐熱複合材料からなる建築部材。
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JP4912834B2 (ja) * | 2006-10-24 | 2012-04-11 | ナガセケムテックス株式会社 | 炭素繊維強化複合材の製造方法 |
DE102009001855A1 (de) * | 2009-03-25 | 2010-09-30 | Henkel Ag & Co. Kgaa | Verfahren zur Herstellung eines faserhaltigen Verbundwerkstoffs |
US9527250B2 (en) * | 2011-12-19 | 2016-12-27 | Toyota Motor Engineering & Manufacturing North America, Inc. | Methods, apparatus and systems for reducing warpage in polymers with continuous fibers |
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JPS6270415A (ja) * | 1985-07-31 | 1987-03-31 | ザ ダウ ケミカル カンパニ− | エポキシ樹脂組成物 |
JP2004204186A (ja) * | 2002-12-26 | 2004-07-22 | Nagase Chemtex Corp | エポキシ樹脂組成物 |
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DE1900541C3 (de) * | 1969-01-07 | 1982-05-27 | Bayer Ag, 5090 Leverkusen | Verfahren zur kontinuierlichen Herstellung von homogenen faserverstärkten Polyamidformmassen |
DE3424700A1 (de) * | 1984-07-05 | 1986-02-06 | Basf Ag, 6700 Ludwigshafen | Faserverbundwerkstoffe auf basis von epoxidharzen |
US4804427A (en) * | 1986-11-05 | 1989-02-14 | Allied-Signal Inc. | Composites via in-situ polymerization of composite matrices using a polymerization initiator bound to a fiber coating |
US5212261A (en) * | 1990-12-17 | 1993-05-18 | Henkel Research Corporation | Latent, heat-curable epoxy resin compositions containing metal carboxylate curing systems |
JPH08134238A (ja) * | 1994-11-10 | 1996-05-28 | Hitachi Chem Co Ltd | エポキシ樹脂プリプレグの製造方法 |
EP0712899B1 (en) | 1994-11-19 | 1999-06-02 | General Electric Company | Hydrolytic stable glass fiber reinforced polyester resins |
JP3637987B2 (ja) * | 1995-11-20 | 2005-04-13 | ジャパンエポキシレジン株式会社 | 注型用エポキシ樹脂及びエポキシ樹脂組成物 |
JP2000273224A (ja) * | 1999-03-29 | 2000-10-03 | Toho Rayon Co Ltd | プリプレグ及びその成形物 |
JP2002020459A (ja) * | 2000-07-13 | 2002-01-23 | Yokohama Rubber Co Ltd:The | エポキシ樹脂組成物 |
US6838529B2 (en) * | 2000-11-22 | 2005-01-04 | Toray Industries, Inc. | Polyester composition and connector |
WO2003002661A1 (en) | 2001-06-28 | 2003-01-09 | Toray Industries, Inc. | Epoxy resin composition excellent in weather resistance and fiber-reinforced composite materials |
JP2004353141A (ja) * | 2003-05-30 | 2004-12-16 | Toray Ind Inc | 強化繊維束ならびにそれを用いた成形用材料および成形品 |
US7592067B2 (en) * | 2003-09-22 | 2009-09-22 | Hexion Specialty Chemicals, Inc. | Epoxy resin compositions, processes utilizing same and articles made therefrom |
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JPS6270415A (ja) * | 1985-07-31 | 1987-03-31 | ザ ダウ ケミカル カンパニ− | エポキシ樹脂組成物 |
JP2004204186A (ja) * | 2002-12-26 | 2004-07-22 | Nagase Chemtex Corp | エポキシ樹脂組成物 |
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US8530053B2 (en) | 2013-09-10 |
US20080139698A1 (en) | 2008-06-12 |
DE602005014500D1 (de) | 2009-06-25 |
WO2006046534A1 (ja) | 2006-05-04 |
ATE431371T1 (de) | 2009-05-15 |
JPWO2006046534A1 (ja) | 2008-08-07 |
EP1806376B1 (en) | 2009-05-13 |
EP1806376A1 (en) | 2007-07-11 |
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