TWI836179B - 纖維強化複合材料用環氧樹脂組成物、預浸體及纖維強化複合材料 - Google Patents
纖維強化複合材料用環氧樹脂組成物、預浸體及纖維強化複合材料 Download PDFInfo
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- TWI836179B TWI836179B TW110101396A TW110101396A TWI836179B TW I836179 B TWI836179 B TW I836179B TW 110101396 A TW110101396 A TW 110101396A TW 110101396 A TW110101396 A TW 110101396A TW I836179 B TWI836179 B TW I836179B
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- Prior art keywords
- epoxy resin
- aforementioned
- fiber
- reinforced composite
- resin composition
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- -1 aromatic diamine compounds Chemical class 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 9
- 230000001588 bifunctional effect Effects 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 2
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 claims description 2
- PUNIDMUCDALJAS-UHFFFAOYSA-N C(C1=CC=C(C=C1)N(C(=O)NC)C)C1=CC=C(C=C1)N(C(=O)NC)C Chemical compound C(C1=CC=C(C=C1)N(C(=O)NC)C)C1=CC=C(C=C1)N(C(=O)NC)C PUNIDMUCDALJAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000011342 resin composition Substances 0.000 description 15
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- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 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
- 238000000034 method Methods 0.000 description 7
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 150000003672 ureas Chemical class 0.000 description 4
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 3
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 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
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-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
- 238000009730 filament winding Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
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- VXGWAWGQKJMAMN-UHFFFAOYSA-N (carbamoylamino) acetate Chemical compound CC(=O)ONC(N)=O VXGWAWGQKJMAMN-UHFFFAOYSA-N 0.000 description 1
- COSWCAGTKRUTQV-UHFFFAOYSA-N 1,1,3-trimethylurea Chemical compound CNC(=O)N(C)C COSWCAGTKRUTQV-UHFFFAOYSA-N 0.000 description 1
- TUMNHQRORINJKE-UHFFFAOYSA-N 1,1-diethylurea Chemical compound CCN(CC)C(N)=O TUMNHQRORINJKE-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
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- QCQBUZVEQZFGQV-UHFFFAOYSA-N 2-octadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCCC1=NC=CN1 QCQBUZVEQZFGQV-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-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
- BQAOFOTUFBAIQA-UHFFFAOYSA-N 4-[1-(4-aminophenyl)ethenyl]aniline Chemical group C1=CC(N)=CC=C1C(=C)C1=CC=C(N)C=C1 BQAOFOTUFBAIQA-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- HLPKYOCVWVMBMR-UHFFFAOYSA-N azane benzylbenzene Chemical compound N.N.C=1C=CC=CC=1CC1=CC=CC=C1 HLPKYOCVWVMBMR-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
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- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- YBSLUBPQYDULIZ-UHFFFAOYSA-N oxalic acid;urea Chemical compound NC(N)=O.OC(=O)C(O)=O YBSLUBPQYDULIZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
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- 238000012552 review Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- 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
-
- 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
- C08G59/22—Di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
-
- 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
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Abstract
本發明課題為提供一種纖維強化複合材料用環氧樹脂組成物,其係可藉由低溫低壓來成形,具有實用上充足的耐熱性及機械特性,且可大幅降低製造成本。
解決手段為一種纖維強化複合材料用環氧樹脂組成物,其係將(a)一種或兩種以上的環氧樹脂、(b)芳香族二胺化合物、(c)二氰二胺、(d)脲化合物及(e)胺加成化合物依照以下比例摻合而成。前述(b)成分的摻合比例,相對於前述(a)成分為0.2~0.6當量;前述(c)成分的摻合比例,相對於前述(a)~(e)成分全體為0.5~4.0質量%;前述(d)成分的摻合比例,相對於前述(a)~(e)成分全體為0.5~2.0質量%;前述(e)成分的摻合比例,相對於前述(a)~(e)成分全體為0~3.0質量%。
Description
本發明關於一種纖維強化複合材料用環氧樹脂組成物、預浸體及纖維強化複合材料。
適用於飛機等的碳纖維或玻璃纖維強化複合材料(FRP)用的基材樹脂,過去以來是以環氧樹脂為主流,可適用於大多數的機體構造。例如專利文獻1揭示了一種環氧樹脂組成物,含有作為基材的環氧樹脂、用來調整黏度的熱塑性樹脂、填料、及硬化劑,另外還揭示了使該組成物與強化纖維複合所得到的預浸體。
飛機的耐熱要求會依照部位來決定,可大致區別為例如約95℃(以上)與約70℃。對應於這些要求的環氧樹脂組成物配方,可分類成180℃硬化型配方與120℃硬化型配方,依照其各自的硬化溫度可得到180℃硬化物與120℃硬化物。
另一方面,FRP被指出會有耗費製造成本的缺點。尤其預浸體經過機械或手工積層,藉由高壓滅菌釜硬化成形的步驟中,使用於硬化前的封袋的許多次級產物的費用,以及高壓滅菌釜設備管理費用、能量費用很高,被認為是拉高製造成本的主要原因。因此,長絲纏繞(FW)或樹脂轉移成形(RTM)法等的預浸體,或不使用高壓滅菌釜的FRP的製造方法的檢討和開發正在盛行。但是,從製造零件的品質再現性、信賴性的觀點看來,無法得到與前述預浸體的手工積層-高壓滅菌釜成形法同等以上的水準。在使用高壓滅菌釜的情況,製造成本會和硬化溫度、壓力、時間成正比,因此只要能夠適用一些可在低溫且低壓下硬化的預浸體材料,即可降低現況中信賴性最高的利用高壓滅菌釜的方法的製造成本。例如只要能夠將現在被分成120℃硬化、180℃硬化的程序統一成為低溫側的120℃硬化,即可謀求利用高壓滅菌釜進行硬化的效率化,對降低製造成本非常有幫助。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2011-99094號公報
[發明所欲解決的課題]
所以本發明之目的,在於提供一種能夠藉由低溫低壓來成形,具有實用上充足的耐熱性及機械特性,且可大幅降低製造成本之纖維強化複合材料用環氧樹脂組成物、預浸體及纖維強化複合材料。
[用於解決課題的手段]
本發明人等反覆鑽研結果發現,藉由將(a)一種或兩種以上的環氧樹脂、(b)芳香族二胺化合物、(c)二氰二胺、(d)脲化合物及(e)胺加成化合物以特定量摻合而成的樹脂組成物可解決上述課題,而完成了本發明。
亦即本發明提供一種纖維強化複合材料用環氧樹脂組成物,其特徵為:將(a)一種或兩種以上的環氧樹脂、(b)芳香族二胺化合物、(c)二氰二胺、(d)脲化合物及(e)胺加成化合物依照下述摻合比例摻合而成。
前述(b)芳香族二胺化合物的摻合比例,相對於前述(a)環氧樹脂為0.2~0.6當量;
前述(c)二氰二胺的摻合比例,相對於前述(a)~(e)成分全體為0.5~4.0質量%;
前述(d)脲化合物的摻合比例,相對於前述(a)~(e)成分全體為0.5~2.0質量%;及
前述(e)胺加成化合物的摻合比例,相對於前述(a)~(e)成分全體為0~3.0質量%。
[發明之效果]
本發明之纖維強化複合材料用環氧樹脂組成物(以下會有簡稱為樹脂組成物的情形),是將(a)一種或兩種以上的環氧樹脂、(b)芳香族二胺化合物、(c)二氰二胺、(d)脲化合物及(e)胺加成化合物以特定量摻合而成,因此能夠藉由低溫低壓來成形,具有實用上充足的耐熱性及機械特性,且可大幅降低製造成本。
尤其本發明之樹脂組成物可將現在被分成120℃硬化、180℃硬化的程序統一成為在低溫側的120℃硬化。例如在藉由高壓滅菌釜以低溫低壓條件(例如120℃、90分鐘、0.31MPa)使本發明中的預浸體硬化的情況,可得到具有與先前技術的120℃硬化物同等的耐熱性及機械特性的FRP。另外,藉由對此硬化物實施後硬化(例如180℃、2小時、大氣壓),可得到具有與先前技術的180℃硬化物同等的耐熱性及機械特性的FRP。前述後硬化沒有必要使用高壓滅菌釜來加壓,例如僅使用空氣循環式烘箱等來加熱即可。所以,在製造180℃硬化物的情況,也不需要藉由高壓滅菌釜進行180℃硬化時所必要的次級產物,可降低使用高壓滅菌釜的情況的製造成本。另外,在後硬化時可將製品由層合夾具脫模而在獨立狀態下加熱,因此縮短了模具佔用的時間,可謀求生產性提升。此外,本發明中的預浸體也可使用高壓滅菌釜來製造180℃硬化物,此情況下也可得到具有與先前技術的180℃硬化物同等的成形品質、耐熱性、機械特性的硬化物。
此外,如上述所述般,依據本發明,無論是製造120℃硬化物的情況還是製造180℃硬化物的情況,首先只要製造出120℃硬化物即可,因此沒有必要如先前技術般因應各硬化物來準備材料,而且也沒有必要將各硬化物保存管理,而能夠降低製造成本。
由以上可知,依據本發明可提供一種能夠藉由低溫低壓來成形,具有實用上充足的耐熱性及機械特性,且可大幅降低製造成本之纖維強化複合材料用環氧樹脂組成物、預浸體及纖維強化複合材料。
以下進一步詳細說明本發明。
本發明之樹脂組成物,其特徵為:將(a)一種或兩種以上的環氧樹脂、(b)芳香族二胺化合物、(c)二氰二胺、(d)脲化合物及(e)胺加成化合物依照下述摻合比例摻合而成。
前述(b)芳香族二胺化合物的摻合比例,相對於前述(a)環氧樹脂為0.2~0.6當量;
前述(c)二氰二胺的摻合比例,相對於前述(a)~(e)成分全體為0.5~4.0質量%;
前述(d)脲化合物的摻合比例,相對於前述(a)~(e)成分全體為0.5~2.0質量%;及
前述(e)胺加成化合物的摻合比例,相對於前述(a)~(e)成分全體為0~3.0質量%。
(a)環氧樹脂
(a)環氧樹脂在合適的形態中,可全部皆由三官能以上的環氧樹脂所形成。此外,(a)環氧樹脂亦可併用二官能的環氧樹脂,此情況下,(a)環氧樹脂以由二官能的環氧樹脂0~80質量%及三官能以上的環氧樹脂20~100質量%所形成為佳。
三官能以上的環氧樹脂,可列舉例如像是苯酚酚醛型、鄰甲酚酚醛型、參羥苯基甲烷型、四羥苯基乙烷型般的多官能型縮水甘油醚型環氧樹脂、像是四縮水甘油基二胺基二苯基甲烷、四縮水甘油基間茬二胺、三縮水甘油基對胺基酚、三縮水甘油基間胺基酚般的縮水甘油基胺型環氧樹脂等。
三官能以上的環氧樹脂,從耐熱性較高、黏度較適當、操作性(例如對纖維基材的含浸性)優異的觀點看來,以液狀或半固體狀環氧樹脂為佳。
三官能以上的環氧樹脂分別可單獨使用或將兩種以上組合使用。
二官能的環氧樹脂,可列舉例如像是雙酚A型、雙酚F型、溴化雙酚A型、氫化雙酚A型、雙酚S型、雙酚AF型、聯苯型般具有雙苯基的環氧化合物、聚伸烷二醇型、伸烷二醇型環氧化合物、具有萘環的環氧化合物、具有芴基的環氧化合物等。
二官能的環氧樹脂分別可單獨使用或將兩種以上組合使用。
(b)芳香族二胺化合物
(b)芳香族二胺化合物具有使(a)環氧樹脂硬化的作用。本發明所使用的(b)芳香族二胺化合物只要具有上述作用,則不受特別限制,從提升本發明之效果的觀點看來,以選自由3,3'-二胺基二苯碸、4,4'-二胺基二苯碸、4,4'-亞甲基雙(2,6-二乙基苯胺)及4,4'-亞甲基雙(2-乙基-6-甲基)苯胺所構成的群中的一種以上為佳。
將這些合適的(b)芳香族二胺化合物的構造揭示於以下。
在本發明之樹脂組成物之中,(b)芳香族二胺化合物的摻合比例,相對於前述(a)環氧樹脂為0.2~0.6當量。若在此摻合比例的範圍外,則耐熱性會降低。(b)芳香族二胺化合物合適的摻合比例,相對於前述(a)環氧樹脂為0.3~0.5當量。
(c)二氰二胺
(c)二氰二胺具有使(a)環氧樹脂硬化的作用,並且具有下述構造。
在本發明之樹脂組成物之中,(c)二氰二胺的摻合比例,相對於(a)~(e)成分全體為0.5~4.0質量%。若在此範圍外,則耐熱性的降低或在120℃等低溫下的硬化性會降低。(c)二氰二胺合適的摻合比例,相對於(a)~(e)成分全體為1.0~3.0質量%。
(d)脲化合物
(d)脲化合物具有促進(a)環氧樹脂的硬化反應的作用。本發明所使用的(d)脲化合物只要具有上述作用,則不受特別限制,從本發明之效果提升的觀點看來,以選自由3-(3,4'-二氯苯基)-1,1-二甲基脲、2,4-甲苯雙二甲基脲及4,4'-亞甲基雙(苯基二甲基脲)所構成的群中的一種以上為佳。
將這些合適的(d)脲化合物的構造揭示於以下。
在本發明之樹脂組成物之中,(d)脲化合物的摻合比例,相對於(a)~(e)成分全體為0.5~2.0質量%。若在此範圍外,則耐熱性或硬化性會降低。(d)脲化合物合適的摻合比例,相對於(a)~(e)成分全體為0.5~1.5質量%。
(e)胺加成化合物
(e)胺加成化合物具有促進(a)環氧樹脂的硬化反應的作用。(e)胺加成化合物為胺的加成體,可列舉例如胺與選自環氧樹脂、異氰酸酯化合物及脲化合物所構成的群中的至少一種化合物的加成體。
前述胺只要是例如一分子內具有一個以上可與環氧基或酚基、異氰酸酯基發生加成反應的活性氫,且一分子內具有一個以上選自由一級胺基、二級胺基及三級胺基所構成的群中的至少一種的胺即可。具體而言,可列舉例如2-甲基咪唑、N-甲基咪唑、2-乙基-4-甲基咪唑、N-甲基哌嗪、2,4,6-參(二甲基胺基甲基)酚、2-二甲基乙醇胺、2-十一烷基咪唑、2-苯基咪唑、2-十八烷基咪唑。
前述環氧樹脂並不受特別限制。可列舉例如使雙酚A、雙酚F、雙酚AD、兒茶酚、間苯二酚等的多價酚、甘油或聚乙二醇等的多元醇與表氯醇反應所得到的聚縮水甘油醚;使像是對羥基安息香酸、β-羥基萘甲酸般的羥基羧酸與表氯醇反應所得到的縮水甘油醚酯;使像是鄰苯二甲酸、對苯二甲酸般的多元羧酸與表氯醇反應所得到的聚縮水甘油基酯;環氧化苯酚酚醛樹脂、環氧化甲酚酚醛樹脂、環氧化聚烯烴、環式脂肪族環氧樹脂、胺甲酸乙酯變性環氧樹脂、由4,4二胺基二苯基甲烷或間胺基酚等所得到的縮水甘油基胺型環氧樹脂。
前述異氰酸酯化合物並不受特別限制。可列舉例如像是正丁基異氰酸酯、苯基異氰酸酯、六亞甲基二異氰酸酯般的單官能異氰酸酯化合物;像是六亞甲基二異氰酸酯、甲伸苯基二異氰酸酯、1,5-萘二異氰酸酯、異佛酮二異氰酸酯、二甲苯二異氰酸酯、1,3,6-六亞甲基三異氰酸酯等般的多官能化合物。
前述脲化合物只要是具有選自脲鍵、伸脲鍵及NH-CO-N所構成的群中的至少一種的化合物,則不受特別限制。可列舉例如尿素、磷酸脲、草酸脲、醋酸脲、二乙醯基脲、二苯甲醯基脲、三甲基脲。
在本發明之樹脂組成物之中,(e)胺加成化合物的摻合比例,相對於(a)~(e)成分全體為0~3.0質量%。若(e)胺加成化合物的摻合比例超過3.0質量%,則樹脂硬化性的平衡會被破壞,在120℃下的低溫硬化性會惡化或硬化物的耐熱性會降低。(e)胺加成化合物合適的摻合比例,相對於(a)~(e)成分全體為0~2質量%。
在本發明之樹脂組成物中,在不脫離本發明目的的範圍內可再添加因應用途的添加劑。可添加的成分可列舉例如阻燃劑類、或用來提升硬化樹脂韌性的熱塑性樹脂類或橡膠類、用來控制硬化時的樹脂流動性或提升樹脂剛性的無機粒子類等。
本發明之樹脂組成物具有優異的硬化性。例如在120℃、1.5小時的硬化條件下可硬化至可由模具脫模的狀態。另外,所得到的硬化物的玻璃轉移溫度為110℃以上,而具有高耐熱性。本發明之樹脂組成物,藉由昇溫速度10℃/分鐘的示差掃描式熱量分析(DSC分析)所測得的反應起始溫度(放熱峰起始溫度)會在90℃以上120℃以下,因此120℃的硬化會確實進行。
另外,本發明中所謂的玻璃轉移溫度,可藉由熱機械分析(TMA)來測定,具體的條件如以下所述。
使用機器:Bruker AXS公司製的TMA4000S型熱機械分析裝置
昇溫速度:10℃/分鐘
測定模式:膨脹模式
施加荷重:2g
測定氣體環境:空氣
另外,前述DSC分析的具體條件如以下所述。
使用機器:TA Instruments公司製DSC2500型示差掃描式熱量分析裝置
昇溫速度:10℃/分鐘
測定氣體環境:氮氣
另外,在本發明中,藉由對前述硬化物實施後硬化(例如180℃、2小時、大氣壓),可成為具有與先前技術的180℃硬化物同等的耐熱性及機械特性的硬化物。前述後硬化沒有必要使用高壓滅菌釜加壓,例如僅使用空氣循環式烘箱等來加熱即可。所以,也不需要藉由高壓滅菌釜180℃硬化時所必要的次級產物,可降低使用高壓滅菌釜的情況的製造成本。另外,在後硬化時可將製品由層合夾具脫模而在獨立狀態下加熱,因此縮短了模具佔用的時間,可謀求生產性提升。
然後,硬化後的硬化物的玻璃轉移溫度會在180℃以上,而具有高耐熱性。
本發明之預浸體是使用本發明之樹脂組成物與纖維基材所得到。
具體而言,本發明之預浸體是藉由使本發明之樹脂組成物含浸於纖維基材所得到。
本發明之預浸體所使用的纖維基材並未受到特別限制,以例如玻璃纖維、石英纖維、芳香族聚醯胺纖維或碳纖維之任一者為佳。纖維基材的形態,可列舉例如織物、粗紗、不織布、針織物、薄紗等。
本發明中的預浸體之製造方法並不受特別限制。可列舉例如使用溶劑的浸漬法、無溶劑法的熱熔法。
本發明之纖維強化複合材料是本發明之預浸體的硬化物。本發明之纖維強化複合材料的用途並不受特別限制,可列舉例如雷達罩、整流罩、襟翼、機翼前緣、機艙地板、螺旋槳、機身等的飛機零件;機車車架、車頭罩、擋泥板等的兩輪車零件;車門、引擎蓋、尾板、側擋泥板、側圍板、擋泥板、能量吸收構件、行李廂蓋、敞篷車硬頂、後視鏡蓋、擾流板、擴散器、滑雪屐座、汽缸蓋、引擎罩、底盤、空氣擾流板、推進軸等的汽車零件;列車車頭、車頂、車身側牆、車門、轉向架蓋板、側裙板等的列車用外板;行李架、座椅等的鐵路列車零件;內裝、鷗翼貨車的翼上的內板、外板、車頂、地板等、安裝於汽車或單車的側裙板等的空力套件;筆記型電腦、行動電話等的框體用途;X光片匣、頂板等的醫學用途;平板揚聲器面板、揚聲器紙盆等的音響製品用途;高爾夫球桿頭及打擊面板、滑雪單板、衝浪板、護具等的運動用品用途;如板簧、風力發電機葉片、電梯(梯廂操作面板、門)般的一般產業用途。
[實施例]
以下藉由實施例及比較例進一步說明本發明,然而本發明不受下述例子限制。
實施例1~4及比較例1~8
在實施例及比較例中使用了以下的材料。
(a)環氧樹脂
・三官能以上的環氧樹脂(日鐵Chemical & Material股份有限公司製的YH-404,環氧當量=115)
・三官能以上的環氧樹脂(Huntsman Advanced Material公司製的MY-0510,環氧當量=101)
・三官能以上的環氧樹脂(Printec股份有限公司製的VG3101L,環氧當量=210)
・二官能的環氧樹脂(日鐵Chemical & Material股份有限公司製的YD-128,環氧當量=191)
・二官能的環氧樹脂(DIC股份有限公司製的HP-4032SS,環氧當量=143)
・二官能的環氧樹脂(Printec股份有限公司製的Epox MKSR35K,環氧當量=962)
(b)芳香族二胺
・4,4'-二胺基二苯碸(和歌山精化工業股份有限公司製)
(c)二氰二胺
・二氰二胺(三菱化學股份有限公司製的Dicy15)
(d)脲化合物
・4,4'-亞甲基雙(苯基二甲基脲)(CVC Thermoset Specialities公司製的Omicure U-24M)
(e)胺加成化合物
・胺-環氧加成化合物(味之素Fine-Techno股份有限公司製的PN-40J)
依照下述表1所示的摻合比例(質量份),使用捏合機將各材料混練,調製出樹脂組成物。
接下來,將所調製出的樹脂組成物倒進尺寸為200mm×200mm×3mm的金屬模具,然後以120℃、1.5小時的條件進行加熱,嘗試製造出120℃硬化物。表1揭示了硬化可否、所得到的硬化物的外觀、玻璃轉移溫度。另外,玻璃轉移溫度是將樹脂硬化物的一部分切成約3mm見方,並藉由上述方法作測定。
接下來,對於前述120℃硬化物實施180℃、3小時的後硬化,製造出180℃硬化物。另外,該後硬化是在不使用金屬模具的獨立狀態下,使用空氣循環式烘箱在大氣壓下將樹脂硬化物加熱來進行。調查所得到的硬化物的外觀、玻璃轉移溫度。
分別將結果揭示於表1。
另外,對於前述所得到的120℃硬化物及180℃硬化物測定以下的機械特性。
・拉伸強度(依據ASTM D638作測定)
・拉伸彈性率(依據ASTM D638作測定)
・拉伸伸度(依據ASTM D638作測定)
・彎曲強度(依據ASTM D790作測定)
・彎曲彈性率(依據ASTM D790作測定)
・彎曲伸度(依據ASTM D790作測定)
・拉伸韌性(由拉伸測試中的荷重-應變曲線來計算)
・彎曲韌性(由彎曲測試中的荷重-應變曲線來計算)
將結果揭示於表2。
由表1及2的結果確認了在各實施例中,在120℃下會良好地硬化,而且所得到的硬化物的耐熱性及機械特性在實用上也是充足的。另外還確認了使120℃硬化物在180℃下後硬化而成的180℃硬化物,耐熱性及機械特性在實用上也是充足的。
相對於此,比較例1、2並未摻合本發明中的(c)二氰二胺及(d)脲化合物,因此雖然可確認在180℃下的硬化,然而在120℃下無法硬化。
比較例3的(c)成分摻合比例超過本發明所規定的上限,因此180℃硬化物的耐熱性惡化。
此外,比較例4~8只進行硬化度的確認,將其結果揭示於表1。
Claims (13)
- 一種纖維強化複合材料用環氧樹脂組成物,其特徵為:將(a)一種或兩種以上的環氧樹脂、(b)芳香族二胺化合物、(c)二氰二胺、(d)脲化合物、及(e)胺加成化合物依照下述摻合比例摻合而成,前述(b)芳香族二胺化合物的摻合比例,相對於前述(a)環氧樹脂為0.2~0.6當量;前述(c)二氰二胺的摻合比例,相對於前述(a)~(e)成分全體為0.5~4.0質量%;前述(d)脲化合物的摻合比例,相對於前述(a)~(e)成分全體為0.5~2.0質量%;及前述(e)胺加成化合物的摻合比例,相對於前述(a)~(e)成分全體為0.78~3.0質量%。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中以120℃、1.5小時的硬化條件硬化至可由模具脫模的狀態所得到的硬化物的玻璃轉移溫度為110℃以上。
- 如請求項2之纖維強化複合材料用環氧樹脂組成物,其中前述硬化物藉由180℃、2小時的後硬化而玻璃轉移溫度成為180℃以上。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中前述(a)環氧樹脂包含二官能的環氧樹脂0~80質量%及三官能以上的環氧樹脂20~100質量%。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中藉由昇溫速度10℃/分鐘的示差掃描式熱量分析(DSC分析)所得到的反應起始溫度(放熱峰起始溫度)為90℃以上120℃以下。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中前述(b)芳香族二胺化合物係選自由3,3'-二胺基二苯碸、4,4'-二胺基二苯碸、4,4'-亞甲基雙(2,6-二乙基苯胺)及4,4'-亞甲基雙(2-乙基-6-甲基)苯胺所構成的群中的一種以上。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中前述(d)脲化合物係選自由3-(3,4'-二氯苯基)-1,1-二甲基脲、2,4-甲苯雙二甲基脲及4,4'-亞甲基雙(苯基二甲基脲)所構成的群中的一種以上。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中前述(b)芳香族二胺化合物的摻合比例,相對於前述(a)環氧樹脂為0.3~0.5當量。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中前述(c)二氰二胺的摻合比例,相對於前述(a)~(e)成分全體為1.0~3.0質量%。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中前述(d)脲化合物的摻合比例,相對於 前述(a)~(e)成分全體為0.5~1.5質量%。
- 如請求項1之纖維強化複合材料用環氧樹脂組成物,其中前述(e)胺加成化合物的摻合比例,相對於前述(a)~(e)成分全體為0.78~2質量%。
- 一種預浸體,其係使如請求項1之纖維強化複合材料用環氧樹脂組成物含浸於玻璃纖維、石英纖維、芳香族聚醯胺纖維或碳纖維之任一者。
- 一種纖維強化複合材料,其係如請求項12之預浸體之硬化物。
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