WO2018003691A1 - エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 - Google Patents
エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 Download PDFInfo
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- WO2018003691A1 WO2018003691A1 PCT/JP2017/023190 JP2017023190W WO2018003691A1 WO 2018003691 A1 WO2018003691 A1 WO 2018003691A1 JP 2017023190 W JP2017023190 W JP 2017023190W WO 2018003691 A1 WO2018003691 A1 WO 2018003691A1
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- Prior art keywords
- epoxy resin
- mass
- parts
- resin composition
- component
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 277
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 277
- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 239000000463 material Substances 0.000 title claims abstract description 59
- -1 prepreg Substances 0.000 title claims abstract description 38
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 32
- 239000004593 Epoxy Substances 0.000 claims abstract description 44
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 30
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 8
- 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 description 35
- 239000011342 resin composition Substances 0.000 claims description 18
- 239000012783 reinforcing fiber Substances 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002759 woven fabric Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 32
- 239000011347 resin Substances 0.000 abstract description 32
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000004327 boric acid Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 44
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- 239000000047 product Substances 0.000 description 29
- 238000003860 storage Methods 0.000 description 27
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- 239000000126 substance Substances 0.000 description 16
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- 239000004753 textile Substances 0.000 description 14
- 235000013877 carbamide Nutrition 0.000 description 11
- 238000004040 coloring Methods 0.000 description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
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- ZWOULFZCQXICLZ-UHFFFAOYSA-N 1,3-dimethyl-1-phenylurea Chemical compound CNC(=O)N(C)C1=CC=CC=C1 ZWOULFZCQXICLZ-UHFFFAOYSA-N 0.000 description 2
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
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- KBQNNOCVJFDHSC-UHFFFAOYSA-N (3-methylphenoxy)boronic acid Chemical compound CC1=CC=CC(OB(O)O)=C1 KBQNNOCVJFDHSC-UHFFFAOYSA-N 0.000 description 1
- DQVXWCCLFKMJTQ-UHFFFAOYSA-N (4-methylphenoxy)boronic acid Chemical compound CC1=CC=C(OB(O)O)C=C1 DQVXWCCLFKMJTQ-UHFFFAOYSA-N 0.000 description 1
- OQZDJLFNMXRJHZ-UHFFFAOYSA-N 1-benzyl-2-ethylimidazole Chemical compound CCC1=NC=CN1CC1=CC=CC=C1 OQZDJLFNMXRJHZ-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
- STHCTMWQPJVCGN-UHFFFAOYSA-N 2-[[2-[1,1,2-tris[2-(oxiran-2-ylmethoxy)phenyl]ethyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1CC(C=1C(=CC=CC=1)OCC1OC1)(C=1C(=CC=CC=1)OCC1OC1)C1=CC=CC=C1OCC1CO1 STHCTMWQPJVCGN-UHFFFAOYSA-N 0.000 description 1
- UJWXADOOYOEBCW-UHFFFAOYSA-N 2-[[2-[bis[2-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C(C=1C(=CC=CC=1)OCC1OC1)C1=CC=CC=C1OCC1CO1 UJWXADOOYOEBCW-UHFFFAOYSA-N 0.000 description 1
- PULOARGYCVHSDH-UHFFFAOYSA-N 2-amino-3,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1OC1CC1=C(CC2OC2)C(N)=C(O)C=C1CC1CO1 PULOARGYCVHSDH-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
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- QBJKMPPBWQMKGY-UHFFFAOYSA-N 3-(2-phenyl-1h-imidazol-5-yl)propanenitrile Chemical compound N1C(CCC#N)=CN=C1C1=CC=CC=C1 QBJKMPPBWQMKGY-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
- QXMQBCRKITYLGR-UHFFFAOYSA-N 4,4,6-trimethyl-2-[2-methyl-4-[(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)oxy]pentan-2-yl]oxy-1,3,2-dioxaborinane Chemical compound O1C(C)CC(C)(C)OB1OC(C)CC(C)(C)OB1OC(C)CC(C)(C)O1 QXMQBCRKITYLGR-UHFFFAOYSA-N 0.000 description 1
- NWZGJOMHAHVXMA-UHFFFAOYSA-N 4,6-bis(oxiran-2-ylmethyl)benzene-1,3-diol Chemical compound C(C1CO1)C1=CC(=C(C=C1O)O)CC1CO1 NWZGJOMHAHVXMA-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
- 229920003319 Araldite® Polymers 0.000 description 1
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- 208000001692 Esotropia Diseases 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 241000665112 Zonitoides nitidus Species 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 1
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- 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
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- BOOITXALNJLNMB-UHFFFAOYSA-N tricyclohexyl borate Chemical compound C1CCCCC1OB(OC1CCCCC1)OC1CCCCC1 BOOITXALNJLNMB-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- DTBRTYHFHGNZFX-UHFFFAOYSA-N trioctyl borate Chemical compound CCCCCCCCOB(OCCCCCCCC)OCCCCCCCC DTBRTYHFHGNZFX-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G59/3236—Heterocylic compounds
- C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
-
- 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
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- 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
- 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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- 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
- C08G59/68—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/06—Triglycidylisocyanurates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to an epoxy resin composition preferably used as a matrix resin of a fiber reinforced composite material suitable for sports applications and general industrial applications, and a prepreg and a fiber reinforced composite material using the epoxy resin composition as a matrix resin.
- Epoxy resins take advantage of their excellent mechanical properties and are widely used in various industrial fields such as paints, adhesives, electrical and electronic information materials, and advanced composite materials.
- epoxy resins are frequently used in fiber-reinforced composite materials composed of matrix fibers and reinforcing fibers such as carbon fibers, glass fibers, and aramid fibers.
- a prepreg in which a carbon fiber base material is impregnated with an epoxy resin in advance is generally used.
- the prepreg is heated after being laminated or preformed to cure the epoxy resin, thereby giving a molded product.
- the handleability decreases. Therefore, high storage stability is required for epoxy resins for prepreg use, and dicyandiamide, which is a curing agent with excellent latent curability, is widely used.
- Carbon fiber composite materials are used in a wide range of fields, from sports and leisure applications to industrial applications such as automobiles and aircraft, taking advantage of their light weight, high strength, and high rigidity.
- the epoxy resin used as the matrix resin has been given importance to the low colorability of the cured product and the appearance of the molded product, in addition to the excellent heat resistance and mechanical properties of the cured product.
- dicyandiamide is used as a curing agent, there is a problem that a white precipitate is formed on the surface of the molded product and the appearance is impaired.
- Patent Document 1 uses a masterbatch using dicyandiamide having a small particle size to dissolve or compatibilize dicyandiamide and an epoxy resin when impregnating the base material. Discloses a technique for suppressing white precipitates in a prepreg.
- Patent Document 2 discloses a technique using a polythiol and a urea compound as a curing agent
- Patent Document 3 discloses a technique using an acid anhydride as a curing agent. Yes.
- Patent Document 2 since dicyandiamide is not used, white precipitates are not generated on the surface of the molded product, but the heat resistance and mechanical properties of the cured resin product may be insufficient.
- the present invention improves the drawbacks of the prior art, and provides a cured epoxy resin product having both high heat resistance, elastic modulus and low colorability, and the surface of a molded article when used as a matrix resin for a fiber-reinforced composite material.
- An epoxy resin composition having an excellent appearance without producing white precipitates, and a prepreg using the epoxy resin composition, and an excellent appearance without causing white precipitates on the surface formed by curing the prepreg It is providing the fiber reinforced composite material which has this.
- the present inventors have found an epoxy resin composition having the following constitution, and have completed the present invention. That is, the epoxy resin composition of this invention consists of the following structures.
- Component [A] includes an epoxy resin
- component [B] includes [B1] aromatic urea and / or [B2] imidazole compound
- component [C] includes a borate ester compound
- the content of dicyandiamide is 100% of all epoxy resins.
- the epoxy resin composition which is 0.5 mass part or less with respect to a mass part, and satisfy
- ⁇ I> The following conditions (a), (b), and (c) are satisfied.
- ⁇ Ii> The following condition (d) and condition (e) are satisfied.
- the prepreg of the present invention is a prepreg composed of the above epoxy resin composition and reinforcing fibers.
- the fiber reinforced composite material of the present invention is a fiber reinforced composite material obtained by curing the prepreg.
- a cured epoxy resin product having high heat resistance and excellent mechanical properties is obtained, and a white precipitate is formed on the surface of a molded product when used as a matrix resin of a fiber reinforced composite material.
- An epoxy resin composition that does not occur and has an excellent appearance can be provided.
- the epoxy resin composition of the present invention contains an epoxy resin as component [A], [B1] aromatic urea and / or [B2] imidazole compound as component [B], and borate ester compound as component [C], It is necessary that the content of dicyandiamide is 0.5 parts by mass or less with respect to 100 parts by mass of the total epoxy resin and satisfies the following ⁇ i> or ⁇ ii>.
- ⁇ I> The following conditions (a), (b), and (c) are satisfied.
- ⁇ Ii> The following condition (d) and condition (e) are satisfied.
- Component [A] in the present invention is an epoxy resin.
- an epoxy resin for example, bisphenol-type epoxy resin, biphenyl-type epoxy resin, naphthalene-type epoxy resin, novolak-type epoxy resin, epoxy resin having a fluorene skeleton, epoxy resin made from a copolymer of a phenol compound and dicyclopentadiene, diglycidyl resorcinol, Glycidyl ether type epoxy resin such as tetrakis (glycidyloxyphenyl) ethane, tris (glycidyloxyphenyl) methane, glycidyl ether type epoxy resin, tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylenediamine Resin etc. are mentioned.
- the lower limit is 15 parts by mass or more
- the upper limit is 30 parts by mass or less. It is preferable that By containing [A1] within this range, the resin cured product is less colored and the balance between the elastic modulus and the heat resistance is improved.
- [A1] Commercially available products of [A1] include “TEPIC (registered trademark)” -S, -L, -PAS B22 (manufactured by Nissan Chemical Industries, Ltd.), “Araldite (registered trademark)” PT9810 (Huntsman Advanced) Materials, Inc.) can be used.
- [A2] includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, epoxy resin obtained by glycidyl etherification of bisphenol compounds including bisphenol S type epoxy resin.
- bisphenol A type epoxy resins include “jER (registered trademark)” 825, 828, 834, 1001, 1002, 1003, 1003F, 1004, 1004AF, 1005F, 1006FS, 1007, 1009, 1010 (and above, Mitsubishi Chemical) Etc.).
- bisphenol F type epoxy resins include “jER (registered trademark)” 806, 807, 4002P, 4004P, 4007P, 4009P, 4010P (above, manufactured by Mitsubishi Chemical Corporation), “Epototo (registered trademark)” YDF2001. YDF2004 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), “EPICRON (registered trademark)” 830, 830-S, 835 (manufactured by DIC Corporation), and the like.
- Examples of commercially available bisphenol S-type epoxy resins include “EPICRON (registered trademark)” EXA-1514 (manufactured by DIC Corporation).
- the average epoxy equivalent of [A2] of the epoxy resin composition is 220 to 500 g / eq from the viewpoint of the balance between heat resistance and coloring of the cured epoxy resin.
- the lower limit is preferably 300 g / eq or more, and the upper limit is preferably 400 g / eq or less.
- the average epoxy equivalent of [A2] is less than 220 g / eq, the heat resistance of the cured resin is lowered and the coloring becomes strong, so that the appearance of the fiber-reinforced composite material is deteriorated.
- the average epoxy equivalent of [A2] is larger than 500 g / eq, although there is little coloring, the heat resistance of resin cured material falls.
- the average epoxy equivalent of [A2] of the epoxy resin composition is calculated by the following method.
- [A3] includes phenol novolac epoxy resins and cresol novolac epoxy resins.
- phenol novolac epoxy resins examples include “jER (registered trademark)” 152, 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
- cresol novolac epoxy resins examples include “EPICRON (registered trademark)” N-660, N-665, N-670, N-673, N-680, N-690, N-695 (above, DIC ( EOCN-102S, EOCN-103S, EOCN-104S (above, Nippon Kayaku Co., Ltd.) and the like.
- the average epoxy equivalent of all epoxy resins in the epoxy resin composition is 165 to 265 g / eq from the viewpoint of the balance between heat resistance and coloring of the cured epoxy resin. It is necessary that the lower limit is 180 g / eq or more, and the upper limit is 250 g / eq or less.
- the average epoxy equivalent of all the epoxy resins is less than 165 g / eq, the heat resistance of the cured resin is lowered and the coloring becomes strong, so that the appearance of the fiber-reinforced composite material is deteriorated.
- the average epoxy equivalent of all the epoxy resins is larger than 265 g / eq, although there is little coloring, the heat resistance of a resin cured material falls.
- the average epoxy equivalent of all epoxy resins in the epoxy resin composition is calculated by the following method.
- Component [B] in the present invention is [B1] aromatic urea and / or [B2] imidazole compound.
- the component [B] serves as a curing agent that promotes self-polymerization of the epoxy resin of the component [A].
- component [B] it is possible to obtain a cured epoxy resin that is less colored and has a good balance with heat resistance as compared with other self-polymerizing curing agents.
- the content of [B1] and [B2] has a preferable range from the viewpoint of the balance between heat resistance and coloring of the cured epoxy resin.
- component [B] contains substantially only [B1]
- the lower limit is 3 parts by mass or more
- the upper limit is more preferably 7 parts by mass or less.
- [B1] and [B2] are included as component [B]
- the total content of [B1] and [B2] is preferably 2.5 to 7.5 parts by mass.
- the lower limit of [B1] is preferably 1 part by mass or more, and the upper limit is more preferably 4 parts by mass or less, and the lower limit of [B2] is 1 part by mass or more. Is more preferably 4 parts by mass or less, and the total content of [B1] and [B2] is more preferably 3 parts by mass or more and 7 parts by mass or less.
- Aromatic ureas include 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, phenyldimethylurea, toluenebisdimethylurea, etc. Is mentioned. Moreover, as a commercial item of aromatic urea, DCMU99 (made by Hodogaya Chemical Industry Co., Ltd.), “Omicure (registered trademark)” 24 (made by PTI Japan Co., Ltd.) and the like can be used. .
- Imidazole compounds include 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, And cyanoethyl-2-phenylimidazole.
- An imidazole compound may be used independently or may be used in combination of multiple types.
- R 4 , R 5 , R 6 and R 7 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a phenyl group, and X represents a single bond, an alkylene group or an alkylidene group
- the compound represented by the general formula (II) is an adduct obtained by the reaction of an imidazole compound and an epoxy compound.
- Commercial products of such an adduct include “Cure Duct (registered trademark)” P-0505 (Shikoku Kasei Kogyo Co., Ltd.) and “JER Cure (registered trademark)” P200H50 (Mitsubishi Chemical Corporation).
- dicyandiamide when contained as a curing agent, white precipitates are formed on the surface of the molded product and the appearance may be impaired. 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, and most preferably not containing dicyandiamide.
- the epoxy resin composition of the present invention needs to contain a borate ester compound as component [C].
- the borate ester compound of component [C] serves as a stabilizer for the aromatic urea and / or imidazole compound of component [B]. It is preferable to contain a boric acid ester compound because the storage stability of the epoxy resin composition and the prepreg is improved.
- boric acid ester compounds include trimethyl borate, triethyl borate, tributyl borate, tri n-octyl borate, tri (triethylene glycol methyl ether) borate ester, alkyl borate esters such as tricyclohexyl borate and trimenthyl borate, tri o- Aromatic borate esters such as cresyl borate, tri m-cresyl borate, tri p-cresyl borate, triphenyl borate, tri (1,3-butanediol) biborate, tri (2-methyl-2,4- Pentanediol) biborate, trioctylene glycol diborate and the like.
- a cyclic borate compound having a cyclic structure in the molecule can also be used.
- the cyclic borate compound include tris-o-phenylene bisborate, bis-o-phenylene pyroborate, bis-2,3-dimethylethylene pyroborate, bis-2,2-dimethyltrimethylene pyroborate, and the like. .
- boric acid ester compounds examples include “Cureduct (registered trademark)” L-01B and L-07N (above, Shikoku Kasei Kogyo Co., Ltd.).
- a kneader, a planetary mixer, a three-roll extruder and a twin-screw extruder may be used for kneading. If uniform kneading is possible, a beaker and Use a spatula or the like and mix by hand.
- Preferred methods for preparing include the following methods. That is, the component [A] is put into a container, and the temperature is raised to an arbitrary temperature of 130 ° C. to 180 ° C. while stirring to dissolve the epoxy resin uniformly. Thereafter, with stirring, the temperature is preferably lowered to 100 ° C.
- a fiber reinforced composite material containing the cured product of the epoxy resin composition of the present invention as a matrix resin can be obtained by compositely integrating the epoxy resin composition of the present invention with reinforcing fibers and then curing.
- the reinforcing fiber used in the present invention is not particularly limited, and glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like are used. Two or more of these fibers may be mixed and used. Among these, it is preferable to use carbon fibers because a lightweight and high-rigidity fiber-reinforced composite material can be obtained, and a molded product having black luster and high design properties can be obtained.
- a white precipitate generated on the surface of a molded article when dicyandiamide is used as a curing agent, which is a problem in the present invention, is that the dicyandiamide is smeared with fibers when impregnated with an epoxy resin composition, or a resin being molded It is thought that this occurs due to segregation of dicyandiamide in the vicinity of the fiber along with the flow of.
- white precipitates are likely to occur in fibers having a small single fiber diameter, and therefore the effect of the present invention is significant when the single fiber diameter of the reinforcing fibers used in the fiber-reinforced composite material is small. Demonstrated.
- the single fiber diameter of the reinforcing fiber is preferably 3 to 20 ⁇ m, and more preferably 3 to 10 ⁇ m. By making the single fiber diameter within this range, the effect of the present invention is greatly exhibited.
- ⁇ Prepreg> In obtaining a fiber-reinforced composite material, it is preferable to prepare a prepreg composed of an epoxy resin composition and reinforcing fibers in advance because it is easy to store and has excellent handleability.
- the prepreg can be obtained by impregnating the reinforcing fiber base material with the epoxy resin composition of the present invention. Examples of the impregnation method include a hot melt method (dry method).
- the hot melt method is a method in which a reinforcing fiber is directly impregnated with an epoxy resin composition whose viscosity has been reduced by heating. Specifically, a film in which an epoxy resin composition is coated on a release paper or the like is prepared, and then the film is applied from both sides or one side of a reinforced fiber fabric (cloth). This is a method of impregnating a reinforcing fiber with a resin by repeatedly applying heat and pressure.
- the form of the reinforcing fiber used for the prepreg is not particularly limited, it is preferably a woven fabric because it has a beautiful texture and a high design when formed into a molded product.
- dicyandiamide is used as a curing agent
- a prepreg using a woven fabric is molded, white precipitates are often generated in the vicinity of the intersection (eyes) of the fibers.
- the effect of the present invention is particularly greatly exhibited.
- the reinforcing fiber used for the prepreg is not particularly limited, and various fibers listed in the description of the fiber-reinforced composite material can be used. Among them, it is preferable to use carbon fiber because a lightweight and highly rigid fiber-reinforced composite material can be obtained, and a molded product having black gloss and high design properties can be obtained.
- ⁇ Prepreg molding method> As a method for applying heat and pressure, a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, or the like can be used as appropriate.
- the cured product of the epoxy resin composition of the present invention and a fiber-reinforced composite material containing reinforcing fibers are preferably used for sports applications, general industrial applications, and aerospace applications. More specifically, in sports applications, it is preferably used for golf shafts, fishing rods, tennis and badminton rackets, hockey sticks, ski poles, and the like. Furthermore, in general industrial applications, structural materials and interior materials for moving objects such as automobiles, motorcycles, bicycles, ships and railway vehicles, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, paper rollers, roofing materials, cables And preferably used for repair and reinforcement materials.
- each epoxy resin composition The materials used for preparing each epoxy resin composition are as shown below.
- Epoxy resin represented by general formula (I) [A3] -1 “jER (registered trademark)” 154 (phenol novolac type epoxy resin, epoxy equivalent: 175, in general formula (I), R 1 , R 2 , a compound in which R 3 is hydrogen, manufactured by Mitsubishi Chemical Corporation.
- Aromatic urea and / or imidazole compound Aromatic urea
- Aromatic urea [B1] -1 DCMU99 (3- (3,4-dichlorophenyl) -1,1-dimethylurea, Hodogaya Chemical Co., Ltd.) Made) [B1] -2 “Omicure (registered trademark)” 24 (4,4′-methylenebis (phenyldimethylurea, manufactured by PTI Japan).
- ⁇ Method for preparing epoxy resin composition (1) Preparation of curing agent master 10 parts by mass (all components [A2] -1, [A2] -2, and [A3] -1 included in the resin composition) of liquid epoxy resin 10 parts by mass for 100 parts by mass of epoxy resin).
- aromatic urea and / or imidazole compound of component [B] [B ′] other curing agent, and the boric acid ester compound of component [C]
- those contained in the resin composition are added, and a kneader is used. And kneaded at room temperature.
- a curing agent master was prepared by passing the mixture through three rolls twice.
- woven CFRP ⁇ Method for producing woven carbon fiber composite material (hereinafter referred to as woven CFRP)>
- the epoxy resin composition prepared according to the above ⁇ Preparation Method of Epoxy Resin Composition> was applied onto release paper using a film coater to prepare a resin film having a basis weight of 66 g / m 2 .
- the resin content of the prepreg was 40% by mass.
- ⁇ Physical property evaluation method> Storage stability of epoxy resin composition
- the storage stability of an epoxy resin composition was evaluated by the amount of Tg change obtained by the following method. 2 g of the epoxy resin composition prepared in accordance with the above ⁇ Method for preparing epoxy resin composition> is placed in a container having a circular bottom surface with a diameter of 4 cm and kept in an environment of temperature 25 ° C. and relative humidity 50% RH. Stored for 7 days. Weigh 3 mg of each resin before and after storage in a sample pan and use a differential scanning calorimeter (Q-2000: manufactured by TA Instruments) to raise the temperature from -50 ° C to 100 ° C at a constant rate of 10 ° C / min.
- Q-2000 differential scanning calorimeter
- Tg glass transition temperature
- Tg of cured epoxy resin A test piece having a width of 10 mm, a length of 40 mm, and a thickness of 2 mm was cut out from the cured epoxy resin prepared according to the above ⁇ Method for preparing cured epoxy resin>, and a dynamic viscoelasticity measuring apparatus (DMA-Q800: TA instrument) was obtained.
- the deformation mode was cantilevered, the span was 18 mm, the strain was 20 ⁇ m, the frequency was 1 Hz, and the temperature was measured from 40 ° C. to 200 ° C. at a constant rate of temperature increase of 5 ° C./min.
- the onset temperature of the storage elastic modulus in the obtained storage elastic modulus-temperature curve was defined as Tg.
- Example 1 As an epoxy resin of component [A], “TEPIC (registered trademark)”-L 20 parts by mass, “jER (registered trademark)” 828 25 parts by mass, “Epototo (registered trademark)” YDF2001 55 parts by mass, [B1] aromatic Using 4 parts by mass of “Omicure (registered trademark)” 24 as urea and 3 parts by mass of “Cureduct (registered trademark)” L-07N as a mixture containing the boric acid ester compound of component [C], the above ⁇ Epoxy resin composition
- the epoxy resin composition was prepared according to the following preparation method.
- the Tg variation of this epoxy resin composition was measured and found to be + 4 ° C., and the storage stability was good.
- a cured epoxy resin was prepared according to ⁇ Method for preparing cured epoxy resin>.
- the epoxy resin cured product was measured for Tg, flexural modulus, and yellowness. As a result, the Tg was 136 ° C., the flexural modulus was 3.5 GPa, and the yellowness was 52. The physical properties of the cured resin were good.
- fabric CFRP was produced from the obtained epoxy resin composition and the external appearance was evaluated, the white deposit was not recognized.
- Example 2 to 23 An epoxy resin composition, a cured epoxy resin, and a woven CFRP were produced in the same manner as in Example 1 except that the resin composition was changed as shown in Tables 1, 2, and 3, respectively.
- the storage stability of the epoxy resin composition, the Tg of the cured epoxy resin, the elastic modulus, the yellowness, and the appearance of the woven CFRP are as shown in Tables 1, 2 and 3, and all were good. It was.
- Example 1 About the resin composition shown in Table 4, the epoxy resin composition, the epoxy resin hardened
- FIG. The physical property evaluation results are also shown in Table 4.
- the content of [A2] in 100 parts by mass of the total epoxy resin is less than 40 parts by mass and does not satisfy the condition (b) that is close to the composition that satisfies ⁇ i>, the yellowness of the cured epoxy resin is implemented. Compared to Example 1, it was poor.
- Example 2 About the resin composition shown in Table 4, the epoxy resin composition, the epoxy resin hardened
- FIG. The physical property evaluation results are also shown in Table 4.
- the Tg, elastic modulus, and CFRP appearance of the cured epoxy resin were good, but the storage stability of the epoxy resin composition was lower than that of Comparative Example 1.
- the content of [A2] in 100 parts by mass of all epoxy resins is less than 40 parts by mass and does not satisfy the condition (b) that is close to the composition that satisfies ⁇ i>. Compared to Example 1, it was poor.
- Example 3 About the resin composition shown in Table 4, the epoxy resin composition, the epoxy resin hardened
- FIG. The physical property evaluation results are also shown in Table 4.
- the content of [A1] in 100 parts by mass of the total epoxy resin is less than 10 parts by mass and does not satisfy the condition (a) of the composition close to satisfying ⁇ i>, the elastic modulus of the cured epoxy resin is implemented. Compared to Example 1, it was lower.
- Example 4 About the resin composition shown in Table 4, the epoxy resin composition, the epoxy resin hardened
- FIG. The physical property evaluation results are also shown in Table 4.
- the content of [A1] in 100 parts by mass of the total epoxy resin is less than 10 parts by mass and does not satisfy the condition (a) of the composition close to satisfying ⁇ i>, the elastic modulus of the cured epoxy resin is implemented. Compared to Example 1, it was lower.
- Example 5 About the resin composition shown in Table 4, the epoxy resin composition, the epoxy resin hardened
- FIG. The physical property evaluation results are also shown in Table 4.
- the content of [A1] in 100 parts by mass of all epoxy resins is less than 10 parts by mass and does not satisfy the condition (a) of the composition close to satisfying ⁇ i>, the elastic modulus of the cured epoxy resin is implemented. Compared to Example 1, it was lower.
- Example 10 About the resin composition shown in Table 5, the epoxy resin composition, the epoxy resin hardened
- FIG. The physical property evaluation results are also shown in Table 5.
- the average epoxy equivalent of all the epoxy resins is less than 165 g / eq, and does not satisfy the condition (e) of the composition close to satisfying ⁇ ii>. Therefore, the Tg and yellowness of the cured epoxy resin are compared with those in Example 3. It was bad.
- the epoxy resin composition of the present invention provides a cured epoxy resin that has both high heat resistance / elastic modulus and low colorability
- the fiber reinforced composite material using this as a matrix resin has excellent heat resistance / mechanical properties. Has characteristics and low colorability.
- a white precipitate is not produced on the surface of the molded article of the fiber reinforced composite material, it has excellent design properties in combination with its low colorability.
- the epoxy resin composition, prepreg, and fiber reinforced composite material of the present invention are preferably used for sports applications and general industrial applications.
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Abstract
Description
<i>以下の条件(a)、条件(b)および条件(c)を満たす。
<ii>以下の条件(d)および条件(e)を満たす。
(a):成分[A]として[A1]イソシアヌル酸型エポキシ樹脂を、全エポキシ樹脂100質量部中10~40質量部含む。
(b):成分[A]として[A2]ビスフェノール型エポキシ樹脂を、全エポキシ樹脂100質量部中40~90質量部含む。
(c):[A2]の平均エポキシ当量が、220~500g/eqである。
(d):成分[A]として[A3]一般式(I)で示されるエポキシ樹脂を、全エポキシ樹脂100質量部中50~100質量部含む。
(e):全エポキシ樹脂の平均エポキシ当量が、165~265g/eqである。
<i>以下の条件(a)、条件(b)および条件(c)を満たす。
<ii>以下の条件(d)および条件(e)を満たす。
(a):成分[A]として[A1]イソシアヌル酸型エポキシ樹脂を、全エポキシ樹脂100質量部中10~40質量部含む。
(b):成分[A]として[A2]ビスフェノール型エポキシ樹脂を、全エポキシ樹脂100質量部中40~90質量部含む。
(c):[A2]の平均エポキシ当量が、220~500g/eqである。
(d):成分[A]として[A3]一般式(I)で示されるエポキシ樹脂を、全エポキシ樹脂100質量部中50~100質量部含む。
(e):全エポキシ樹脂の平均エポキシ当量が、165~265g/eqである。
本発明における成分[A]はエポキシ樹脂である。例えば、ビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ノボラック型エポキシ樹脂、フルオレン骨格を有するエポキシ樹脂、フェノール化合物とジシクロペンタジエンの共重合体を原料とするエポキシ樹脂、ジグリシジルレゾルシノール、テトラキス(グリシジルオキシフェニル)エタン、トリス(グリシジルオキシフェニル)メタンのようなグリシジルエーテル型エポキシ樹脂、テトラグリシジルジアミノジフェニルメタン、トリグリシジルアミノフェノール、トリグリシジルアミノクレゾール、テトラグリシジルキシレンジアミンのようなグリシジルアミン型エポキシ樹脂などが挙げられる。
本発明において<i>を満たすためには、成分[A]として[A1]イソシアヌル酸型エポキシ樹脂を含む必要がある。[A1]を含むことにより、樹脂硬化物の弾性率が高くなり、耐熱性も向上するため、優れた機械特性と耐熱性を有する繊維強化複合材料が得られる。
n種類の[A2]のエポキシ樹脂を併用し、[A2]のエポキシ樹脂の総質量部がG’であり、エポキシ当量がEx(g/eq)の[A2]のエポキシ樹脂XがWx質量部含有されているエポキシ樹脂組成物の[A2]の平均エポキシ当量(g/eq)は、以下の数式(I)によって算出できる(ここで、x=1、2、3、・・・、nである。)
本発明において<ii>を満たすためには、成分[A]として[A3]一般式(I)で示されるエポキシ樹脂を含む必要がある。
[A3]を含むことにより、樹脂硬化物の弾性率が高くなり、耐熱性も向上するため、優れた機械特性と耐熱性を有する繊維強化複合材料が得られる。
n種類の成分[A]のエポキシ樹脂を併用し、全エポキシ樹脂の総質量部がGであり、エポキシ当量がEy(g/eq)のエポキシ樹脂YがWy質量部含有されているエポキシ樹脂組成物の全エポキシ樹脂の平均エポキシ当量(g/eq)は、以下の数式(II)によって算出できる(ここで、y=1、2、3、・・・、nである。)
本発明における成分[B]は[B1]芳香族ウレアおよび/または[B2]イミダゾール化合物である。本発明において成分[B]は成分[A]のエポキシ樹脂の自己重合を進める硬化剤として働く。成分[B]を用いることで、他の自己重合型硬化剤と比較して、着色が少なく耐熱性とのバランスが良いエポキシ樹脂硬化物を得ることができる。
本発明のエポキシ樹脂組成物には、成分[C]としてホウ酸エステル化合物を含有する必要がある。本発明において成分[C]のホウ酸エステル化合物は成分[B]の芳香族ウレアおよび/またはイミダゾール化合物の安定化剤としてはたらく。ホウ酸エステル化合物を含有することにより、エポキシ樹脂組成物およびプリプレグの保管安定性が向上するため好ましい。
本発明のエポキシ樹脂組成物の調製には、例えばニーダー、プラネタリーミキサー、3本ロールおよび2軸押出機といった機械を用いて混練しても良いし、均一な混練が可能であれば、ビーカーとスパチュラなどを用い、手で混ぜても良い。好ましい調製方法としては、以下の方法があげられる。すなわち、容器に成分[A]を投入し、攪拌しながら温度を130℃~180℃の任意の温度まで上昇させ、エポキシ樹脂を均一に溶解させる。その後、攪拌しながら、好ましくは100℃以下、より好ましくは80℃以下、さらに好ましくは60℃以下の温度まで下げ、成分[B]ならびに成分[C]を投入し、混練する。このとき、成分[B]ならびに成分[C]を均一に混合するために、あらかじめ成分[A]の一部を用い、硬化剤マスターを作製しておくことがより好ましい。
次に、繊維強化複合材料について説明する。本発明のエポキシ樹脂組成物を、強化繊維と複合一体化した後、硬化させることにより、本発明のエポキシ樹脂組成物の硬化物をマトリックス樹脂として含む繊維強化複合材料を得ることができる。
繊維強化複合材料を得るにあたり、あらかじめエポキシ樹脂組成物と強化繊維からなるプリプレグとしておくことは、保管が容易となる上、取り扱い性に優れるため好ましいものである。プリプレグは、本発明のエポキシ樹脂組成物を強化繊維基材に含浸させて得ることができる。含浸させる方法としては、ホットメルト法(ドライ法)などを挙げることができる。
プリプレグ積層成形法において、熱および圧力を付与する方法としては、プレス成形法、オートクレーブ成形法、バッギング成形法、ラッピングテープ法、内圧成形法などを適宜使用することができる。
成分[A]:エポキシ樹脂
・[A1]イソシアヌル酸型エポキシ樹脂
[A1]-1 “TEPIC(登録商標)”-S(エポキシ当量:100、日産化学工業(株)製)
[A1]-2 “TEPIC(登録商標)”-L(エポキシ当量:101、日産化学工業(株)製)
[A1]-3 “TEPIC(登録商標)”-PAS B22(エポキシ当量:190、日産化学工業(株)製)。
[A2]-1 “EPICLON(商標登録)”830(ビスフェノールF型エポキシ樹脂、エポキシ当量:172、大日本インキ化学工業(株)製)
[A2]-2 “jER(商標登録)”828(ビスフェノールA型エポキシ樹脂、エポキシ当量:189、三菱化学(株)製)
[A2]-3 “エポトート(登録商標)”YDF-2001(ビスフェノールF型エポキシ樹脂、エポキシ当量:475、東都化成(株)製)
[A2]-4 “jER(商標登録)”1001(ビスフェノールA型エポキシ樹脂、エポキシ当量:470、三菱化学(株)製)
[A2]-5 “jER(商標登録)”4004P(ビスフェノールF型エポキシ樹脂、エポキシ当量:910、三菱化学(株)製)
[A2]-6 “jER(商標登録)”1007(ビスフェノールA型エポキシ樹脂、エポキシ当量:910、三菱化学(株)製)。
[A3]-1 “jER(商標登録)”154(フェノールノボラック型エポキシ樹脂、エポキシ当量:175、一般式(I)において、R1、R2、R3が水素である化合物、三菱化学(株)製)。
[A4]-1 “スミエポキシ(登録商標)”ELM434(ジアミノジフェニルメタン型エポキシ樹脂、エポキシ当量:120、住友化学工業(株)製)。
・[B1]芳香族ウレア
[B1]-1 DCMU99(3-(3,4-ジクロロフェニル)-1,1-ジメチルウレア、保土ヶ谷化学工業(株)製)
[B1]-2 “Omicure(登録商標)”24(4,4’-メチレンビス(フェニルジメチルウレア、ピィ・ティ・アイ・ジャパン(株)製)。
[B2]-1 “キュアゾール(登録商標)”2PZ(イミダゾール当量:144、2-フェニルイミダゾール、四国化成工業(株)製)
[B2]-2 “キュアダクト(登録商標)”P-0505(イミダゾール当量:280、一般式(II)において、R4およびR5がエチル基、R6およびR7がメチル基、Xがイソプロピリデン基である化合物、四国化成工業(株)製)。
[B’]-1 “jERキュア(登録商標)”DICY7(ジシアンジアミド、三菱化学(株)製)。
・成分[C]のホウ酸エステル化合物 を含む混合物
[C]-1 “キュアダクト(登録商標)”L-07N(酸性化合物としてホウ酸エステル化合物を5質量部含む混合物、四国化成工業(株)製)。
(1)エポキシ樹脂組成物の[A2]の平均エポキシ当量の算出方法
n種類の[A2]のエポキシ樹脂を併用し、[A2]のエポキシ樹脂の総質量部がG’であり、エポキシ当量がEx(g/eq)の[A2]のエポキシ樹脂XがWx質量部含有されているエポキシ樹脂組成物の[A2]の平均エポキシ当量(g/eq)を、以下の数式(I)によって算出した(ここで、x=1、2、3、・・・、nである。)
n種類の成分[A]のエポキシ樹脂を併用し、全エポキシ樹脂の総質量部がGであり、エポキシ当量がEy(g/eq)のエポキシ樹脂YがWy質量部含有されているエポキシ樹脂組成物の全エポキシ樹脂の平均エポキシ当量(g/eq)を、以下の数式(II)によって算出した(ここで、y=1、2、3、・・・、nである。)
(1)硬化剤マスターの調製
液状のエポキシ樹脂([A2]-1、[A2]-2、[A3]-1のうち、樹脂組成に含まれるもの)を10質量部(全ての成分[A]のエポキシ樹脂100質量部に対して10質量部)用意した。ここに成分[B]の芳香族ウレアおよび/またはイミダゾール化合物、[B’]その他の硬化剤、成分[C]のホウ酸エステル化合物のうち、樹脂組成に含まれるものを添加し、ニーダーを用いて室温で混練した。混合物を三本ロールに2回通すことで、硬化剤マスターを調製した。
ニーダー中に、前記(1)で使用した液状のエポキシ樹脂10質量部を除いた成分[A]のエポキシ樹脂90質量部を投入した。混練しながら、150℃まで昇温した後、同温度で1時間保持することで、透明な粘調液を得た。混練を続けながら60℃まで降温した後、前記(1)で調製した硬化剤マスターを投入し、同温度で30分間混練することで、エポキシ樹脂組成物を得た。表1~5に各実施例および比較例のエポキシ樹脂組成物の組成を示した。
上記<エポキシ樹脂組成物の調製方法>に従い調製したエポキシ樹脂組成物を真空中で脱泡した後、2mm厚の“テフロン(登録商標)”製スペーサーにより厚み2mmになるように設定したモールド中で、130℃の温度で90分間硬化させ、厚さ2mmの板状のエポキシ樹脂硬化物を得た。
上記<エポキシ樹脂組成物の調製方法>に従い調製したエポキシ樹脂組成物を、フィルムコーターを用いて離型紙上に塗布し、目付66g/m2の樹脂フィルムを作製した。炭素繊維“トレカ(登録商標)”T300(東レ(株)製)を用いた二方向クロス(2/2綾織、目付198g/m2)を用意し、これに2枚の樹脂フィルムを両面に貼り合わせた後、これをプリプレグ化装置で両面から加熱加圧含浸し織物プリプレグを得た。プリプレグの樹脂含有率は40質量%であった。
(1)エポキシ樹脂組成物の保管安定性
エポキシ樹脂組成物の保管安定性は、以下の方法で得られたTg変化量によって評価した。直径4cmの円形の底面を持つ容器に、上記<エポキシ樹脂組成物の調製方法>に従い調製したエポキシ樹脂組成物を2g取り分け、温度25℃・相対湿度50%RHの環境に保った恒温恒湿槽内で7日間保管した。保管前後の樹脂それぞれ3mgをサンプルパンに量り取り、示差走査熱量分析計(Q-2000:TAインスツルメント社製)を用い、-50℃から100℃まで10℃/分の等速昇温条件で測定した。得られた熱量-温度曲線における変曲点の中点をガラス転移温度(以下、Tgと記す)とした。保管後のTgから保管前のTgを差し引いたものをTg変化量とした。Tg変化量が小さいほど、保管安定性は良好と判断される。
上記<エポキシ樹脂硬化物の作製方法>に従い作製したエポキシ樹脂硬化物から、幅10mm、長さ40mm、厚さ2mmの試験片を切り出し、動的粘弾性測定装置(DMA-Q800:TAインスツルメント社製)を用い、変形モードを片持ち曲げ、スパン間を18mm、歪みを20μm、周波数を1Hzとし、40℃から200℃まで5℃/分の等速昇温条件で測定した。得られた貯蔵弾性率-温度曲線における貯蔵弾性率のオンセット温度をTgとした。
上記<エポキシ樹脂硬化物の作製方法>に従い作製したエポキシ樹脂硬化物から、幅10mm、長さ60mmの試験片を切り出し、インストロン万能試験機(インストロン社製)を用い、スパンを32mm、クロスヘッドスピードを100mm/分とし、JIS K7171(1994)に従って3点曲げを実施し、弾性率を測定した。試験片数n=6で測定した値の平均値を弾性率とした。
上記<エポキシ樹脂硬化物の作製方法>に従い作製したエポキシ樹脂硬化物から3cm角、厚さ2mmの試験片を切り出した。この試験片について、分光測色計MSC-P(スガ試験機(株)製)を用い、JIS Z8722(2009)に従って透過物体色を測定し、三刺激値を求めた。イルミナントはD65、幾何条件e、測定方法は分光測色方法、有効波長幅は5nm、波長間隔は5nmとし、表色系はXYZ表色系とした。得られた三刺激値を基に、JIS K7373(2006)に従って黄色度を計算した。
上記<織物CFRPの作製方法>に従い作製した織物CFRPを40℃の水に7日間浸漬した。浸漬後の織物CFRPについて、織目部分の外観を目視で確認した。結果は、白色析出物が認められない場合をgood、認められる場合をpoorと表記した。
成分[A]のエポキシ樹脂として“TEPIC(登録商標)”-L 20質量部、“jER(商標登録)”828 25質量部、“エポトート(商標登録)”YDF2001 55質量部、[B1]芳香族ウレアとして“Omicure(登録商標)”24 4質量部、成分[C]のホウ酸エステル化合物 を含む混合物として“キュアダクト(登録商標)”L-07N 3質量部を用い、上記<エポキシ樹脂組成物の調製方法>に従ってエポキシ樹脂組成物を調製した。
樹脂組成をそれぞれ表1、2および3に示したように変更した以外は、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。
表4に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表4に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物のTg、弾性率、織物CFRPの外観は良好であった。しかし、全エポキシ樹脂100質量部中[A2]の含有量が40質量部に満たず、<i>を満たす組成に近いものの条件(b)を満たさないため、エポキシ樹脂硬化物の黄色度が実施例1に比べて不良であった。
表4に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表4に併せて示した。エポキシ樹脂硬化物のTg、弾性率、CFRPの外観は良好であったが、エポキシ樹脂組成物の保管安定性は比較例1に比べて低かった。また、全エポキシ樹脂100質量部中[A2]の含有量が40質量部に満たず、<i>を満たす組成に近いものの条件(b)を満たさないため、エポキシ樹脂硬化物の黄色度が実施例1に比べて不良であった。
表4に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表4に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物のTg、黄色度、織物CFRPの外観は良好であった。しかし、全エポキシ樹脂100質量部中[A1]の含有量が10質量部に満たず、<i>を満たす組成に近いものの条件(a)を満たさないため、エポキシ樹脂硬化物の弾性率が実施例1に比べて低かった。
表4に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表4に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物のTg、黄色度、織物CFRPの外観は良好であった。しかし、全エポキシ樹脂100質量部中[A1]の含有量が10質量部に満たず、<i>を満たす組成に近いものの条件(a)を満たさないため、エポキシ樹脂硬化物の弾性率が実施例1に比べて低かった。
表4に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表4に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物のTg、織物CFRPの外観は良好であったが、黄色度が不良であった。また、全エポキシ樹脂100質量部中[A1]の含有量が10質量部に満たず、<i>を満たす組成に近いものの条件(a)を満たさないため、エポキシ樹脂硬化物の弾性率が実施例1に比べて低かった。
表4に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表4に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物のTg、弾性率、織物CFRPの外観は良好であった。しかし、全エポキシ樹脂100質量部中[A1]の含有量が40質量部を超え、<i>を満たす組成に近いものの条件(a)を満たさないため、エポキシ樹脂硬化物の黄色度が実施例9に比べて不良であった。
表5に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表5に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物の弾性率、黄色度、織物CFRPの外観は良好であった。しかし、[A2]の平均エポキシ当量が220g/eqに満たず、<i>を満たす組成に近いものの条件(c)を満たさないため、エポキシ樹脂硬化物のTgが実施例1に比べて低かった。
表5に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表5に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物の弾性率、黄色度、織物CFRPの外観は良好であった。しかし、[A2]の平均エポキシ当量が500g/eqを超え、<i>を満たす組成に近いものの条件(c)を満たさないため、エポキシ樹脂硬化物のTgが実施例1に比べて低かった。
表5に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表5に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物のTg、黄色度、織物CFRPの外観は良好であった。しかし、[A3]の含有量が少なく、<ii>を満たす組成に近いものの条件(d)を満たさないため、エポキシ樹脂硬化物の弾性率が実施例3に比べて低かった。
表5に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表5に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物の弾性率、織物CFRPの外観は良好であった。しかし、全エポキシ樹脂の平均エポキシ当量が165g/eqに満たず、<ii>を満たす組成に近いものの条件(e)を満たさないため、エポキシ樹脂硬化物のTgと黄色度が実施例3に比べて不良であった。
表5に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表5に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物の弾性率、黄色度、織物CFRPの外観は良好であった。しかし、全エポキシ樹脂の平均エポキシ当量が265g/eqを超え、<ii>を満たす組成に近いものの条件(e)を満たさないため、エポキシ樹脂硬化物のTgが実施例3に比べて不良であった。
表5に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表5に併せて示した。エポキシ樹脂組成物の保管安定性、エポキシ樹脂硬化物のTg、弾性率、黄色度は良好であったが、ジシアンジアミドを含んでいるため、織物CFRPに白色析出物が認められた。
(比較例13)
表5に示した樹脂組成について、実施例1と同じ方法でエポキシ樹脂組成物、エポキシ樹脂硬化物、織物CFRPを作製した。物性評価結果は表5に併せて示した。成分[C]を含まないため、実施例3と比較してエポキシ樹脂組成物の保管安定性が悪化した。
Claims (10)
- 成分[A]としてエポキシ樹脂、成分[B]として[B1]芳香族ウレアおよび/または[B2]イミダゾール化合物、および成分[C]としてホウ酸エステル化合物を含み、ジシアンジアミドの含有量が全エポキシ樹脂100質量部に対し0.5質量部以下であって、かつ、下記<i>または<ii>を満たすエポキシ樹脂組成物。
<i>以下の条件(a)、条件(b)および条件(c)を満たす。
<ii>以下の条件(d)および条件(e)を満たす。
(a):成分[A]として[A1]イソシアヌル酸型エポキシ樹脂を、全エポキシ樹脂100質量部中10~40質量部含む。
(b):成分[A]として[A2]ビスフェノール型エポキシ樹脂を、全エポキシ樹脂100質量部中40~90質量部含む。
(c):[A2]の平均エポキシ当量が、220~500g/eqである。
(d):成分[A]として[A3]一般式(I)で示されるエポキシ樹脂を、全エポキシ樹脂100質量部中50~100質量部含む。
(e):全エポキシ樹脂の平均エポキシ当量が、165~265g/eqである。 - ジシアンジアミドの含有量が全エポキシ樹脂100質量部に対し0.2質量部以下である、請求項1に記載のエポキシ樹脂組成物。
- 樹脂組成物中にジシアンジアミドを含まない、請求項1に記載のエポキシ樹脂組成物。
- 成分[B]として実質的に[B1]芳香族ウレアのみを含み、[B1]の含有量が全エポキシ樹脂100質量部に対し2.5~7.5質量部である、請求項1~3のいずれかに記載のエポキシ樹脂組成物。
- 成分[B]として[B1]芳香族ウレアおよび[B2]イミダゾール化合物を含み、[B1]の含有量が全エポキシ樹脂100質量部に対し0.5~5質量部であり、[B2]の含有量が全エポキシ樹脂100質量部に対し0.5~5質量部であって、[B1]と[B2]の含有量の合計が、全エポキシ樹脂100質量部に対し2.5~7.5質量部である、請求項1~3のいずれかに記載のエポキシ樹脂組成物。
- 請求項1~6のいずれかに記載のエポキシ樹脂組成物と強化繊維からなるプリプレグ。
- 強化繊維が織物の形態である、請求項7に記載のプリプレグ。
- 強化繊維が炭素繊維である、請求項7または8に記載のプリプレグ。
- 請求項9のいずれかに記載のプリプレグを硬化させてなる繊維強化複合材料。
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