JP2016148020A - Epoxy resin composition, prepreg and fiber-reinforced composite material - Google Patents
Epoxy resin composition, prepreg and fiber-reinforced composite material Download PDFInfo
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- JP2016148020A JP2016148020A JP2015236346A JP2015236346A JP2016148020A JP 2016148020 A JP2016148020 A JP 2016148020A JP 2015236346 A JP2015236346 A JP 2015236346A JP 2015236346 A JP2015236346 A JP 2015236346A JP 2016148020 A JP2016148020 A JP 2016148020A
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- epoxy resin
- resin composition
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- mass
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 185
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 185
- 239000000203 mixture Substances 0.000 title claims abstract description 123
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 21
- -1 boric acid ester Chemical class 0.000 claims abstract description 37
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 57
- 239000011342 resin composition Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 11
- 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 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 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 description 9
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 61
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 2
- 108010053481 Antifreeze Proteins Proteins 0.000 abstract 1
- 238000000034 method Methods 0.000 description 31
- 238000011156 evaluation Methods 0.000 description 22
- 238000005259 measurement Methods 0.000 description 20
- 238000005452 bending Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012783 reinforcing fiber Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 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 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 238000013001 point bending Methods 0.000 description 6
- 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 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 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 5
- 239000002131 composite material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 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 3
- 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 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 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 229920003319 Araldite® Polymers 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 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 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-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
- 229940018563 3-aminophenol Drugs 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZKVSZNUEJBIEHP-UHFFFAOYSA-N O1C2=CC=CC=C2OB2OC3=CC=CC=C3OB1OC1=CC=CC=C1O2 Chemical compound O1C2=CC=CC=C2OB2OC3=CC=CC=C3OB1OC1=CC=CC=C1O2 ZKVSZNUEJBIEHP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920003295 Radel® Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 238000004458 analytical method Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- RTMBXAOPKJNOGZ-UHFFFAOYSA-N tris(2-methylphenyl) borate Chemical compound CC1=CC=CC=C1OB(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RTMBXAOPKJNOGZ-UHFFFAOYSA-N 0.000 description 1
- FYAMVEZOQXNCIE-UHFFFAOYSA-N tris(3-methylphenyl) borate Chemical compound CC1=CC=CC(OB(OC=2C=C(C)C=CC=2)OC=2C=C(C)C=CC=2)=C1 FYAMVEZOQXNCIE-UHFFFAOYSA-N 0.000 description 1
- ROEKPHSQKWBJKS-UHFFFAOYSA-N tris(4-methylphenyl) borate Chemical compound C1=CC(C)=CC=C1OB(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 ROEKPHSQKWBJKS-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、スポーツ用途および一般産業用途に適した繊維強化複合材料のマトリックス樹脂として好ましく用いられるエポキシ樹脂組成物、ならびに、これをマトリックス樹脂としたプリプレグおよび繊維強化複合材料に関するものである。 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.
エポキシ樹脂はその優れた機械的特性をいかし、塗料、接着剤、電気電子情報材料、先端複合材料など、各種産業分野に広く使用されている。特に炭素繊維、ガラス繊維、アラミド繊維などの強化繊維とマトリックス樹脂からなる繊維強化複合材料ではエポキシ樹脂が多用されている。 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. In particular, 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.
繊維強化複合材料の製造は、炭素繊維の基材にあらかじめエポキシ樹脂を含浸させた、プリプレグが汎用される。プリプレグは、積層もしくはプリフォーム後、加熱してエポキシ樹脂を硬化させることで、成形品を与える。プリプレグに要求される特性は、成形品が優れた機械特性を示すことに加え、特に近年では、優れた生産性、すなわち速硬化性が求められている。この傾向は、特に生産性が要求される自動車などの産業用途で強い。 For the production of a fiber reinforced composite material, a prepreg obtained by impregnating a carbon fiber base material 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. In addition to the excellent mechanical properties of molded products, the properties required for prepregs are particularly demanded in recent years for excellent productivity, that is, fast curability. This tendency is particularly strong in industrial applications such as automobiles that require productivity.
また、現行のプリプレグは室温においても反応性があり、通常冷凍保管が必要である。それには冷凍設備の手配や使用前の解凍が要求されることから、常温で保管、取扱いが可能な、保管安定性に優れたプリプレグが求められている。 Also, current prepregs are reactive at room temperature and usually require refrigeration. For this, preparation of refrigeration equipment and thawing before use are required, and therefore, a prepreg excellent in storage stability that can be stored and handled at room temperature is required.
保管安定性を高める技術として、特許文献１には、粒径を制御したイミダゾール誘導体の粒子表面をホウ酸エステル化合物でコーティングする方法が開示されており、良好な保管安定性と硬化速度の両立が可能であると記載されている。 As a technique for improving storage stability, Patent Document 1 discloses a method of coating the particle surface of an imidazole derivative with a controlled particle size with a borate ester compound, which achieves both good storage stability and curing speed. It is stated that it is possible.
特許文献２には、エポキシ樹脂中の加水分解塩素量を適切な範囲に制御することにより、長期保存安定性を有するエポキシ樹脂組成物が得られると記載されている。 Patent Document 2 describes that an epoxy resin composition having long-term storage stability can be obtained by controlling the amount of hydrolyzed chlorine in the epoxy resin within an appropriate range.
特許文献３には、硬化開始温度から硬化度が一定に達するまでの時間を制御し、粒径や硬化温度を限定した硬化剤を用いる方法が開示されており、保管安定性と速硬化性を両立したと記載されている。 Patent Document 3 discloses a method of controlling the time from the curing start temperature until the degree of curing reaches a certain level, and using a curing agent that limits the particle size and the curing temperature, and provides storage stability and fast curability. It is described as compatible.
しかし、特許文献１に記載された方法では、活性の高いイミダゾール誘導体を用いるため、樹脂の調合時やプリプレグ作製時およびプリプレグ保管・輸送時の熱履歴により、長期保存安定性が失われる場合があった。 However, since the method described in Patent Document 1 uses a highly active imidazole derivative, long-term storage stability may be lost due to thermal history during resin preparation, prepreg preparation, and prepreg storage / transport. It was.
また、特許文献２および３には、比較的高い保存安定性をもつ樹脂組成物が示されているものの、保存安定性は十分とは言えなかった。また炭素繊維複合材料の力学特性に重要な、樹脂硬化物の弾性率や撓みに関する言及もなかった。 Patent Documents 2 and 3 show resin compositions having relatively high storage stability, but the storage stability was not sufficient. There was no mention of the elastic modulus and deflection of the cured resin, which is important for the mechanical properties of the carbon fiber composite material.
そこで、本発明は、製造プロセスや保管・輸送時の熱履歴に対し安定で、保管安定性を高いレベルで有するエポキシ樹脂組成物およびプリプレグを提供すること、かつ繊維強化複合材料として優れた機械特性を示すエポキシ樹脂組成物を提供することを課題とする。 Therefore, the present invention provides an epoxy resin composition and a prepreg that are stable with respect to the heat history during the manufacturing process and storage / transport, have a high level of storage stability, and have excellent mechanical properties as a fiber-reinforced composite material. It is an object to provide an epoxy resin composition exhibiting
本発明者らは、前記課題を解決すべく鋭意検討した結果、下記構成からなるエポキシ樹脂組成物を見いだし、本発明を完成させるに至った。すなわち本発明のエポキシ樹脂組成物は、以下の構成からなる。 As a result of intensive studies to solve the above problems, 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.
次の成分［Ａ］、［Ｂ］、［Ｃ］、［Ｄ］を含み、下記条件［ａ］および［ｂ］を満たすことを特徴とするエポキシ樹脂組成物。
［Ａ］：エポキシ樹脂
［Ｂ］：ジシアンジアミド
［Ｃ］：芳香族ウレア
［Ｄ］：ホウ酸エステル
［ａ］：窒素気流下、１００℃の等温で示差走査熱量分析計によりエポキシ樹脂組成物を分析したとき、１００℃に達してから熱流量がピークトップに至るまでの時間が６０分以下
［ｂ］：窒素気流下、６０℃の等温で示差走査熱量分析計によりエポキシ樹脂組成物を分析したとき、６０℃に達してから熱流量がピークトップに至るまでの時間が２５時間以上。
An epoxy resin composition comprising the following components [A], [B], [C], and [D] and satisfying the following conditions [a] and [b]:
[A]: Epoxy resin [B]: Dicyandiamide [C]: Aromatic urea [D]: Boric acid ester [a]: Analyzing the epoxy resin composition by differential scanning calorimetry at 100 ° C. under nitrogen flow When the epoxy resin composition is analyzed by a differential scanning calorimeter at 60 ° C. under a nitrogen stream at a time from the time when the temperature reaches 100 ° C. until the heat flow reaches the peak top, 60 minutes or less. The time from reaching 60 ° C. until the heat flow reaches the peak top is 25 hours or more.
また、本発明のプリプレグは、前記エポキシ樹脂組成物と炭素繊維からなるプリプレグである。 Moreover, the prepreg of this invention is a prepreg which consists of the said epoxy resin composition and carbon fiber.
また、本発明の繊維強化複合材料は、前記プリプレグを硬化して得られる繊維強化複合材料である。 The fiber reinforced composite material of the present invention is a fiber reinforced composite material obtained by curing the prepreg.
本発明によれば、製造プロセスおよび保管・輸送時の熱履歴に対し安定で、保管安定性に極めて優れるとともに、プリプレグを成形して得られる繊維強化複合材料が高い機械特性を有するエポキシ樹脂組成物、ならびに、該エポキシ樹脂組成物を用いたプリプレグおよび繊維強化複合材料を提供することができる。 According to the present invention, an epoxy resin composition that is stable with respect to the manufacturing process and thermal history during storage / transport, has excellent storage stability, and has a high mechanical property in a fiber-reinforced composite material obtained by molding a prepreg. And a prepreg and a fiber-reinforced composite material using the epoxy resin composition can be provided.
本発明のエポキシ樹脂組成物は、成分［Ａ］：エポキシ樹脂、成分［Ｂ］：ジシアンジアミド、成分［Ｃ］：芳香族ウレア化合物、成分［Ｄ］ホウ酸エステルを必須成分として含む。まずはこれらの構成要素について説明する。 The epoxy resin composition of the present invention contains component [A]: epoxy resin, component [B]: dicyandiamide, component [C]: aromatic urea compound, and component [D] boric acid ester as essential components. First, these components will be described.
（成分［Ａ］）
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Ａ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ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が挙げられる。エポキシ樹脂は、これらを単独で用いても、複数種類を組み合わせても良い。
(Ingredient [A])
Component [A] in the present invention is an epoxy resin. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, novolac type epoxy resin, epoxy resin having fluorene skeleton, phenol compound and dicyclopentadiene Polymer-based epoxy resin, diglycidyl resorcinol, glycidyl ether type epoxy resin such as tetrakis (glycidyloxyphenyl) ethane, tris (glycidyloxyphenyl) methane, tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylamino Examples thereof include glycidylamine type epoxy resins such as cresol and tetraglycidylxylenediamine. Epoxy resins may be used alone or in combination.
成分［Ａ］としては、３官能以上の多官能エポキシ樹脂を含むことが好ましい。３官能以上の多官能エポキシ樹脂を含むことにより、極めて高い保管安定性を有しながら、硬化速度も良好なエポキシ樹脂組成物が得られる。 Component [A] preferably contains a trifunctional or higher polyfunctional epoxy resin. By including a trifunctional or higher polyfunctional epoxy resin, an epoxy resin composition having a very high storage stability and a good curing rate can be obtained.
３官能以上の多官能エポキシ樹脂としては、硬化速度と保管安定性、および硬化物の力学特性のバランスの観点から、成分［Ａ１］下記式（Ｉ）および／または下記式（ＩＩ）で示されるエポキシ樹脂であることが好ましい。成分［Ａ１］は、一般にフェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、またはジシクロペンタジエン型エポキシ樹脂として知られているものであり、２官能以上の多官能エポキシ樹脂の混合物として市販されている。 The trifunctional or higher polyfunctional epoxy resin is represented by the component [A1] represented by the following formula (I) and / or the following formula (II) from the viewpoint of the balance between curing speed, storage stability, and mechanical properties of the cured product. An epoxy resin is preferred. Component [A1] is generally known as a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, or a dicyclopentadiene type epoxy resin, and is commercially available as a mixture of bifunctional or higher polyfunctional epoxy resins. .
成分［Ａ１］は、エポキシ樹脂組成物に含まれる全エポキシ樹脂１００質量部中１０質量部〜５０質量部含むことが、保管安定性と硬化速度のバランスの観点から好ましい。また、硬化速度の観点から、成分［Ａ１］中の３官能以上の多官能エポキシ樹脂の割合は多いほうが好ましく、その観点から、成分［Ａ１］のエポキシ基の平均官能基数は３．０個以上であることが好ましい。 Component [A1] is preferably contained in an amount of 10 to 50 parts by mass in 100 parts by mass of the total epoxy resin contained in the epoxy resin composition, from the viewpoint of the balance between storage stability and curing rate. From the viewpoint of curing speed, the proportion of the trifunctional or higher polyfunctional epoxy resin in the component [A1] is preferably large. From this viewpoint, the average number of functional groups of the epoxy group of the component [A1] is 3.0 or more. It is preferable that
（式中、Ｒ１、Ｒ２、Ｒ３は、水素原子またはメチル基を表す。また、ｎは１以上の整数を表す。） (Wherein R 1 , R 2 and R 3 represent a hydrogen atom or a methyl group, and n represents an integer of 1 or more.)
（ｎは１以上の整数を表す）。 (N represents an integer of 1 or more).
成分［Ａ１］の市販品としては、“ｊＥＲ（登録商標）”１５２、１５４、１８０S（以上、三菱化学（株）製）、“エピクロン（登録商標）”Ｎ−７４０，Ｎ−７７０，Ｎ−７７５，Ｎ−６６０，Ｎ−６６５，Ｎ−６８０，Ｎ−６９５，ＨＰ７２００Ｌ，ＨＰ７２００，ＨＰ７２００Ｈ，ＨＰ７２００ＨＨ，ＨＰ７２００ＨＨＨ（以上、ＤＩＣ（株）製）、ＰＹ３０７，ＥＰＮ１１７９，ＥＰＮ１１８０，ＥＣＮ９５１１，ＥＣＮ１２７３，ＥＣＮ１２８０，ＥＣＮ１２８５，ＥＣＮ１２９９（以上、ハンツマン・アドバンスト・マテリアル社製）、ＹＤＰＮ６３８，ＹＤＰＮ６３８Ｐ，ＹＤＣＮ−７０１，ＹＤＣＮ−７０２，ＹＤＣＮ−７０３，ＹＤＣＮ−７０４（以上、東都化成（株）製）、ＤＥＮ４３１，ＤＥＮ４３８，ＤＥＮ４３９（以上、ダウケミカル社製）などがある。 Commercially available components [A1] include “jER (registered trademark)” 152, 154, 180S (manufactured by Mitsubishi Chemical Corporation), “Epiclon (registered trademark)” N-740, N-770, N-. 775, N-660, N-665, N-680, N-695, HP7200L, HP7200, HP7200H, HP7200HH, HP7200HHH (manufactured by DIC Corporation), PY307, EPN1179, EPN1180, ECN9511, ECN1273, ECN1280, ECN1285 ECN1299 (above, manufactured by Huntsman Advanced Materials), YDPN638, YDPN638P, YDCN-701, YDCN-702, YDCN-703, YDCN-704 (above, manufactured by Toto Kasei Co., Ltd.), DEN431, DEN438, DEN439 (Above, manufactured by Dow Chemical Company).
また、３官能以上の多官能エポキシ樹脂として、成分［Ａ２］３官能以上のグリシジルアミン型エポキシ樹脂を含むことが好ましい。 Moreover, as a trifunctional or more polyfunctional epoxy resin, it is preferable to contain the component [A2] trifunctional or more glycidylamine type epoxy resin.
成分［Ａ２］の具体例としては、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リレンジアミンなどが挙げられる。 Specific examples of component [A2] include tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylylenediamine, and the like.
成分［Ａ２］の市販品としては、テトラグリシジルジアミノジフェニルメタンとして、“スミエポキシ（登録商標）”ＥＬＭ４３４（住友化学工業（株）製）、ＹＨ４３４Ｌ（東都化成（株）製）、“ｊＥＲ（登録商標）”６０４（三菱化学（株）製）、“アラルダイト（登録商標）”ＭＹ７２０、ＭＹ７２１（ハンツマン・アドバンスト・マテリアルズ社製）等を使用することができる。トリグリシジルアミノフェノール又はトリグリシジルアミノクレゾールとしては、“スミエポキシ（登録商標）”ＥＬＭ１００、ＥＬＭ１２０（住友化学工業（株）製）、“アラルダイト（登録商標）”ＭＹ０５００、ＭＹ０５１０、ＭＹ０６００（ハンツマン・アドバンスト・マテリアルズ社製）、“ｊＥＲ（登録商標）”６３０（三菱化学（株）製）等を使用することができる。テトラグリシジルキシリレンジアミンおよびその水素添加品として、“ＴＥＴＲＡＤ（登録商標）”−Ｘ、“ＴＥＴＲＡＤ（登録商標）”−Ｃ（三菱ガス化学（株）製）等を使用することができる。 Commercially available components [A2] include tetraglycidyldiaminodiphenylmethane, “Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), YH434L (manufactured by Tohto Kasei Co., Ltd.), “jER (registered trademark). “604 (manufactured by Mitsubishi Chemical Corporation)”, “Araldite (registered trademark)” MY720, MY721 (manufactured by Huntsman Advanced Materials), etc. can be used. As triglycidylaminophenol or triglycidylaminocresol, “Sumiepoxy (registered trademark)” ELM100, ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY0500, MY0510, MY0600 (Huntsman Advanced Material) And “jER (registered trademark)” 630 (manufactured by Mitsubishi Chemical Corporation), etc. can be used. As tetraglycidylxylylenediamine and hydrogenated products thereof, “TETRAD (registered trademark)”-X, “TETRAD (registered trademark)”-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) and the like can be used.
成分［Ａ２］は、全エポキシ樹脂１００質量部中１０質量部〜５０質量部含むことが、保管安定性と硬化速度のバランスの観点から好ましい。 Component [A2] preferably contains 10 to 50 parts by mass in 100 parts by mass of the total epoxy resin from the viewpoint of the balance between storage stability and curing rate.
成分［Ａ］として、成分［Ａ３］ビスフェノールＦ型エポキシ樹脂を含むことも、保管安定性と樹脂硬化物の弾性率のバランスの観点から好ましい。成分［Ａ３］は、全エポキシ樹脂１００質量部中２０質量部〜９０質量部含むことが好ましい。 It is also preferable that component [A3] bisphenol F type epoxy resin is included as component [A] from the viewpoint of the balance between storage stability and elastic modulus of the cured resin. It is preferable that component [A3] contains 20 mass parts-90 mass parts in 100 mass parts of all the epoxy resins.
成分［Ａ３］の市販品としては、例えば“ｊＥＲ（登録商標）”８０６、８０７、４００２Ｐ、４００４Ｐ、４００７Ｐ、４００９Ｐ（以上三菱化学（株）製）、“エポトート（登録商標）”ＹＤＦ−２００１、ＹＤＦ−２００４（以上東都化成（株）製）などが挙げられる。 Examples of commercially available components [A3] include “jER (registered trademark)” 806, 807, 4002P, 4004P, 4007P, 4009P (manufactured by Mitsubishi Chemical Corporation), “Epototo (registered trademark)” YDF-2001, YDF-2004 (manufactured by Toto Kasei Co., Ltd.) and the like.
（成分［Ｂ］）
本発明における成分［Ｂ］は、ジシアンジアミドである。ジシアンジアミドは、化学式（Ｈ２Ｎ）２Ｃ＝Ｎ−ＣＮであらわされる化合物である。ジシアンジアミドは、樹脂硬化物に高い力学特性や耐熱性を与える点で優れており、エポキシ樹脂の硬化剤として広く用いられる。かかるジシアンジアミドの市販品としては、ＤＩＣＹ７、ＤＩＣＹ１５（以上、三菱化学（株）製）などが挙げられる。
(Ingredient [B])
Component [B] in the present invention is dicyandiamide. Dicyandiamide is a compound represented by the chemical formula (H 2 N) 2 C═N—CN. Dicyandiamide is excellent in terms of imparting high mechanical properties and heat resistance to the cured resin, and is widely used as a curing agent for epoxy resins. Examples of such commercially available dicyandiamide include DICY7 and DICY15 (manufactured by Mitsubishi Chemical Corporation).
ジシアンジアミド［Ｂ］を粉体としてエポキシ樹脂組成物に配合することは、室温での保管安定性や、プリプレグ製造時の粘度安定性の観点から好ましい。また、ジシアンジアミド［Ｂ］を予め成分［Ａ］のエポキシ樹脂の一部に三本ロールなどを用いて分散させておくことは、エポキシ樹脂組成物を均一にし、硬化物の物性を向上させるため好ましい。 It is preferable to blend dicyandiamide [B] as a powder into the epoxy resin composition from the viewpoint of storage stability at room temperature and viscosity stability during prepreg production. In addition, it is preferable to disperse dicyandiamide [B] in advance in a part of the epoxy resin of component [A] using a three roll or the like in order to make the epoxy resin composition uniform and improve the physical properties of the cured product. .
ジシアンジアミドを粉体として樹脂に配合する場合、その平均粒径は１０μｍ以下であることが好ましく、さらに好ましくは７μｍ以下である。例えば、プリプレグ製造工程において加熱加圧により強化繊維束にエポキシ樹脂組成物を含浸させる際、平均粒径が１０μｍ以下であれば、繊維束内部への樹脂の含浸性が良好となる。 When dicyandiamide is blended into the resin as a powder, the average particle size is preferably 10 μm or less, more preferably 7 μm or less. For example, when the reinforcing fiber bundle is impregnated with the epoxy resin composition by heating and pressing in the prepreg manufacturing process, if the average particle diameter is 10 μm or less, the resin impregnation property inside the fiber bundle is good.
また、ジシアンジアミド［Ｂ］の総量は、エポキシ樹脂組成物に含まれる全エポキシ樹脂成分のエポキシ基に対し、活性水素基が０．３〜１．２当量、さらに０．３〜０．７当量の範囲となる量とすることが好ましい。活性水素基の量がこの範囲となることにより、耐熱性と機械特性のバランスに優れた樹脂硬化物を得ることができる。 The total amount of dicyandiamide [B] is 0.3 to 1.2 equivalents of active hydrogen groups, and further 0.3 to 0.7 equivalents of the epoxy groups of all epoxy resin components contained in the epoxy resin composition. It is preferable to set the amount within a range. When the amount of active hydrogen groups falls within this range, a cured resin product having an excellent balance between heat resistance and mechanical properties can be obtained.
ジシアンジアミド[Ｂ]は、後述の成分[Ｃ]と併用することにより、成分[Ｂ]を単独で配合した場合と比較し、樹脂組成物の硬化温度を下げることができる。本願発明においては、良好な硬化速度を得るために、成分[Ｂ]と成分[Ｃ]を併用することが必要である。 When dicyandiamide [B] is used in combination with component [C] described later, the curing temperature of the resin composition can be lowered as compared with the case where component [B] is blended alone. In the present invention, in order to obtain a good curing rate, it is necessary to use the component [B] and the component [C] in combination.
（成分［Ｃ］）
本発明のエポキシ樹脂組成物には、成分［Ｃ］として、芳香族ウレア化合物が含まれている必要がある。成分［Ｃ］は硬化促進剤としてはたらき、成分[Ｂ]と併用した場合に良好な硬化速度を得ることができる。
(Ingredient [C])
The epoxy resin composition of the present invention needs to contain an aromatic urea compound as component [C]. Component [C] serves as a curing accelerator, and a good curing rate can be obtained when used in combination with component [B].
成分[Ｃ]における芳香族ウレア化合物の具体例としては、３−（３，４−ジクロロフェニル）−１，１−ジメチルウレア、３−（４−クロロフェニル）−１，１−ジメチルウレア、フェニルジメチルウレア、トルエンビスジメチルウレアなどが挙げられる。また、芳香族ウレア化合物の市販品としては、ＤＣＭＵ−９９（保土ヶ谷化学工業（株）製）、“Ｏｍｉｃｕｒｅ（登録商標）”２４（ピィ・ティ・アイ・ジャパン（株）製）などを使用することができる。 Specific examples of the aromatic urea compound in component [C] include 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, phenyldimethylurea. And toluenebisdimethylurea. Moreover, as a commercial item of an aromatic urea compound, DCMU-99 (made by Hodogaya Chemical Industry Co., Ltd.), "Omicure (registered trademark)" 24 (made by PTI Japan Co., Ltd.), etc. are used. be able to.
成分［Ｃ］における芳香族ウレア化合物の配合量は、成分［Ａ］のエポキシ樹脂１００質量部に対し、好ましくは１〜８質量部であり、より好ましくは１．５〜６質量部であり、さらに好ましくは２〜４質量部である。成分[Ｃ]をこの範囲で配合することにより、保管安定性と硬化速度のバランスに優れ、物性が良好な樹脂硬化物を与えるエポキシ樹脂組成物が得られる。 The amount of the aromatic urea compound in component [C] is preferably 1 to 8 parts by mass, more preferably 1.5 to 6 parts by mass, relative to 100 parts by mass of the epoxy resin of component [A]. More preferably, it is 2-4 mass parts. By blending component [C] within this range, an epoxy resin composition is obtained that gives a cured resin product with excellent balance between storage stability and curing speed and good physical properties.
なお、成分［Ｃ］は比較的保管安定性が高い硬化促進剤として知られているが、室温でもゆっくりとエポキシ樹脂との反応が進行するため、長期の保管安定性は必ずしも十分ではなかった。エポキシ樹脂と成分［Ｃ］の反応メカニズムには諸説あるが、ウレア基の分解により遊離したアミン化合物が、エポキシ樹脂と反応するメカニズムが提唱されている。本願発明者らは、室温において長期の安定性が得られない理由について、以下のように考えた。すなわち、ウレア基の解離反応は可逆反応であるため、成分［Ｃ］を含むエポキシ樹脂組成物中には、微量のアミン化合物が遊離して含まれていると考えられる。一方で、アミン化合物とエポキシ樹脂の求核反応は不可逆反応である。遊離した大半のアミン化合物は可逆反応によりウレアに戻るが、一部エポキシ基と反応すれば、不可逆に架橋反応が進行する。これが繰り返されることで、樹脂組成物の長期の安定性が損なわれるのではないかと考えた。そこで、極めて高い保管安定性を得るためには、後述する成分［Ｄ］との併用が必要である。 In addition, although component [C] is known as a curing accelerator having relatively high storage stability, since the reaction with the epoxy resin proceeds slowly even at room temperature, long-term storage stability is not always sufficient. Although there are various theories on the reaction mechanism between the epoxy resin and component [C], a mechanism has been proposed in which an amine compound liberated by the decomposition of the urea group reacts with the epoxy resin. The present inventors considered the reason why long-term stability cannot be obtained at room temperature as follows. That is, since the urea group dissociation reaction is a reversible reaction, it is considered that a small amount of amine compound is contained in the epoxy resin composition containing the component [C]. On the other hand, the nucleophilic reaction between the amine compound and the epoxy resin is an irreversible reaction. Most of the liberated amine compound returns to urea by a reversible reaction, but if it partially reacts with an epoxy group, a crosslinking reaction proceeds irreversibly. It was thought that by repeating this, the long-term stability of the resin composition might be impaired. Therefore, in order to obtain extremely high storage stability, it is necessary to use in combination with component [D] described later.
（成分［Ｄ］）
本発明のエポキシ樹脂組成物には、成分［Ｄ］として、ホウ酸エステルが含まれている必要がある。成分［Ｃ］と成分［Ｄ］とを併用することにより、保管温度における成分［Ｃ］とエポキシ樹脂の反応が抑制されるため、プリプレグの保管安定性が著しく向上する。そのメカニズムは定かではないが、成分[Ｄ]はルイス酸性を持つため、成分［Ｃ］から遊離したアミン化合物と成分[Ｄ]が相互作用し、アミン化合物の反応性を低下させているのではないかと考えている。
(Ingredient [D])
The epoxy resin composition of the present invention needs to contain a borate ester as component [D]. By using the component [C] and the component [D] in combination, the reaction between the component [C] and the epoxy resin at the storage temperature is suppressed, so that the storage stability of the prepreg is significantly improved. Although the mechanism is not clear, since the component [D] has Lewis acidity, the amine compound liberated from the component [C] and the component [D] interact to reduce the reactivity of the amine compound. I think that there is not.
また、成分［Ｃ］と成分[Ｄ]を併用することにより、熱履歴への安定性に優れた樹脂組成物が得られる。成分[Ｄ]を用いたアミン化合物の安定化についてはこれまで知られていた（例えば、特許文献１に記載されている）が、この技術は、エポキシ樹脂との反応性が高いアミン化合物を安定化するものであった。樹脂組成物の調合工程や、強化繊維とあわせてプリプレグとする場合における強化繊維への含浸工程などでは、樹脂組成物に熱を加えることがあるが、反応性の高いアミン化合物と成分[Ｄ]の併用では、その際の熱履歴への安定性が十分ではなかった。一方で、本願のように、成分［Ｃ］と成分［Ｄ］を併用した場合には、成分［Ｃ］から遊離するアミン化合物の量は限定的であるため、成分［Ｃ］を単独で用いた場合よりも優れた熱履歴への安定性が得られる。この観点においても、成分［Ｃ］と成分［Ｄ］を併用する必要がある。 Further, by using the component [C] and the component [D] in combination, a resin composition having excellent stability to heat history can be obtained. Although stabilization of an amine compound using the component [D] has been known so far (for example, described in Patent Document 1), this technique stabilizes an amine compound having high reactivity with an epoxy resin. It was to become. In the resin composition blending step or the step of impregnating the reinforcing fiber in the case where the prepreg is combined with the reinforcing fiber, heat may be applied to the resin composition, but the highly reactive amine compound and component [D] In the combined use, stability to heat history at that time was not sufficient. On the other hand, when the component [C] and the component [D] are used together as in the present application, the amount of the amine compound liberated from the component [C] is limited, so the component [C] is used alone. Better stability to thermal history than if Also from this viewpoint, it is necessary to use the component [C] and the component [D] in combination.
成分［Ｄ］のホウ酸エステルの具体例としては、トリメチルボレート、トリエチルボレート、トリブチルボレート、トリｎ−オクチルボレート、トリ（トリエチレングリコールメチルエーテル）ホウ酸エステル、トリシクロヘキシルボレート、トリメンチルボレートなどのアルキルホウ酸エステル、トリｏ−クレジルボレート、トリｍ−クレジルボレート、トリｐ−クレジルボレート、トリフェニルボレートなどの芳香族ホウ酸エステル、トリ（１，３−ブタンジオール）ビボレート、トリ（２−メチル−２，４−ペンタンジオール）ビボレート、トリオクチレングリコールジボレートなどが挙げられる。 Specific examples of the boric acid ester of component [D] include trimethyl borate, triethyl borate, tributyl borate, tri n-octyl borate, tri (triethylene glycol methyl ether) boric acid ester, tricyclohexyl borate, and trimenthyl borate. Aromatic borate esters such as alkyl borate ester, tri-o-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.
また、ホウ酸エステルとして、分子内に環状構造を有する環状ホウ酸エステルを用いることもできる。環状ホウ酸エステルとしては、トリス−ｏ−フェニレンビスボレート、ビス−ｏ−フェニレンピロボレート、ビス−２，３−ジメチルエチレンフェニレンピロボレート、ビス−２，２−ジメチルトリメチレンピロボレートなどが挙げられる。 Further, as the borate ester, a cyclic borate ester having a cyclic structure in the molecule can also be used. Examples of cyclic borate esters include tris-o-phenylene bisborate, bis-o-phenylene pyroborate, bis-2,3-dimethylethylenephenylene pyroborate, bis-2,2-dimethyltrimethylene pyroborate, and the like. .
かかるホウ酸エステルを含む製品としては、たとえば、“キュアダクト（登録商標）”Ｌ−０１Ｂ（四国化成工業（株））、“キュアダクト（登録商標）”Ｌ−０７Ｎ（四国化成工業（株））がある。 Examples of products containing such boric acid esters include “Cureduct (registered trademark)” L-01B (Shikoku Kasei Kogyo Co., Ltd.) and “Cureduct (registered trademark)” L-07N (Shikoku Kasei Kogyo Co., Ltd.). )
かかる成分［Ｄ］の配合量は、成分[Ａ]のエポキシ樹脂１００質量部に対し、好ましくは０．１〜８質量部であり、より好ましくは０．１５〜５質量部であり、さらに好ましくは０．２〜４質量部である。成分[Ｄ]をこの範囲で配合することにより、保管安定性と硬化速度のバランスに優れ、物性が良好な樹脂硬化物を与えるエポキシ樹脂組成物が得られる。 The compounding amount of the component [D] is preferably 0.1 to 8 parts by mass, more preferably 0.15 to 5 parts by mass, further preferably 100 parts by mass of the epoxy resin of the component [A]. Is 0.2-4 parts by mass. By blending component [D] within this range, an epoxy resin composition can be obtained that gives a resin cured product with excellent balance between storage stability and curing speed and good physical properties.
（示差走査熱量分析計を用いたエポキシ樹脂組成物の分析）
本発明において、エポキシ樹脂組成物の硬化速度の測定には、たとえば示差走査熱量分析計を用いた熱分析が用いられる。
(Analysis of epoxy resin composition using differential scanning calorimeter)
In the present invention, for example, thermal analysis using a differential scanning calorimeter is used to measure the curing rate of the epoxy resin composition.
示差走査熱量分析計で観測できる発熱は、エポキシ樹脂組成物の反応によって生じるものである。従って、等温測定において、発熱が現れるまでの時間は、エポキシ樹脂組成物の反応速度と関係がある。等温測定における発熱のピークトップは、その温度で反応が最も活発化する時を表しており、反応性の指標として用いることができる。 The exotherm that can be observed with a differential scanning calorimeter is caused by the reaction of the epoxy resin composition. Therefore, in the isothermal measurement, the time until exotherm appears is related to the reaction rate of the epoxy resin composition. The peak top of the exotherm in the isothermal measurement represents the time when the reaction is most active at that temperature, and can be used as an index of reactivity.
（示差走査熱量分析計を用いたエポキシ樹脂組成物の１００℃等温測定）
本発明のエポキシ樹脂組成物は、示差走査熱量分析計で１００℃の等温測定を行った場合、１００℃に達してから熱流量が発熱ピークトップに至るまでの時間をＴ（１００）としたとき、Ｔ（１００）が６０分以下であることを特徴とし、４５分以下であることがより好ましく、３０分以下であることがさらに好ましい。Ｔ（１００）が６０分以下であるエポキシ樹脂組成物をマトリックス樹脂として用いることにより、生産性を損なわない範囲での硬化速度を与えることができる。Ｔ（１００）が６０分より大きくなるエポキシ樹脂組成物をマトリックス樹脂として用いたプリプレグでは、硬化速度が不十分なものとなる。
(100 ° C isothermal measurement of an epoxy resin composition using a differential scanning calorimeter)
In the epoxy resin composition of the present invention, when the isothermal measurement at 100 ° C. is performed with a differential scanning calorimeter, the time from when the temperature reaches 100 ° C. until the heat flow reaches the top of the exothermic peak is defined as T (100). , T (100) is 60 minutes or less, more preferably 45 minutes or less, and even more preferably 30 minutes or less. By using an epoxy resin composition having T (100) of 60 minutes or less as a matrix resin, it is possible to give a curing rate within a range that does not impair productivity. A prepreg using an epoxy resin composition having a T (100) greater than 60 minutes as a matrix resin has an insufficient curing rate.
（示差走査熱量分析計を用いたエポキシ樹脂組成物の６０℃等温測定）
また、本発明のエポキシ樹脂組成物は、６０℃で等温測定を行った場合、６０℃に達してから熱流量が発熱ピークトップに至るまでの時間をＴ（６０）としたとき、Ｔ（６０）が２５時間以上であることを特徴とし、２８時間以上であることがより好ましい。Ｔ（６０）が２５時間以上であるエポキシ樹脂組成物をマトリックス樹脂として用いることにより、プリプレグに長期的な保管安定性を与えることができる。２５時間未満となるエポキシ樹脂組成物をマトリックス樹脂として用いたプリプレグは、室温における保管安定性が不十分なものとなる。
(60 ° C isothermal measurement of epoxy resin composition using differential scanning calorimeter)
In addition, when the isothermal measurement is performed at 60 ° C., the epoxy resin composition of the present invention has T (60) when T (60) is the time from reaching 60 ° C. until the heat flow reaches the exothermic peak top. ) Is 25 hours or longer, more preferably 28 hours or longer. By using an epoxy resin composition having T (60) of 25 hours or longer as a matrix resin, long-term storage stability can be imparted to the prepreg. A prepreg using an epoxy resin composition that is less than 25 hours as a matrix resin has insufficient storage stability at room temperature.
（成分［Ｅ］）
本発明のエポキシ樹脂組成物には、本発明の効果を失わない範囲において、成分［Ｅ］として熱可塑性樹脂を配合することができる。熱可塑性樹脂は本発明に必須の成分ではないが、エポキシ樹脂組成物に配合することにより、粘弾性を制御したり、硬化物に靭性を付与したりすることができる。
(Ingredient [E])
In the epoxy resin composition of the present invention, a thermoplastic resin can be blended as component [E] within a range not losing the effects of the present invention. Although a thermoplastic resin is not an essential component in the present invention, it can control viscoelasticity or impart toughness to a cured product by blending it in an epoxy resin composition.
このような熱可塑性樹脂の例としては、ポリメタクリル酸メチル、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアセタール、ポリビニルピロリドン、芳香族ビニル単量体・シアン化ビニル単量体・ゴム質重合体から選ばれる少なくとも２種類を構成成分とする重合体、ポリアミド、ポリエステル、ポリカーボネート、ポリアリーレンオキシド、ポリスルホン、ポリエーテルスルホン、ポリイミドなどが挙げられる。芳香族ビニル単量体・シアン化ビニル単量体・ゴム質重合体から選ばれる少なくとも２種類を構成成分とする重合体の例としては、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、アクリロニトリル−スチレン共重合体（ＡＳ樹脂）などが挙げられる。ポリスルホン、ポリイミドは、主鎖にエーテル結合や、アミド結合を有するものであってもよい。 Examples of such thermoplastic resins include at least selected from polymethyl methacrylate, polyvinyl formal, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, aromatic vinyl monomer / vinyl cyanide monomer / rubber polymer. Examples thereof include polymers having two types as constituents, polyamide, polyester, polycarbonate, polyarylene oxide, polysulfone, polyethersulfone, and polyimide. Examples of polymers comprising at least two kinds selected from aromatic vinyl monomers, vinyl cyanide monomers, and rubbery polymers include acrylonitrile-butadiene-styrene copolymers (ABS resins) and acrylonitrile. -Styrene copolymer (AS resin) etc. are mentioned. Polysulfone and polyimide may have an ether bond or an amide bond in the main chain.
ポリメタクリル酸メチル、ポリビニルホルマール、ポリビニルブチラール、ポリビニルピロリドンは、ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂などの多くの種類のエポキシ樹脂と良好な相溶性を有し、エポキシ樹脂組成物の流動性制御の効果が大きい点で好ましく、ポリビニルホルマールが特に好ましい。これらの熱可塑性樹脂の市販品を例示すると、“デンカブチラール（登録商標）”および“デンカホルマール（登録商標）”（電気化学工業（株）製）、“ビニレック（登録商標）”（ＪＮＣ（株）製）などがある。 Polymethyl methacrylate, polyvinyl formal, polyvinyl butyral, and polyvinyl pyrrolidone have good compatibility with many kinds of epoxy resins such as bisphenol A type epoxy resin and novolac type epoxy resin, and control the flowability of the epoxy resin composition. In view of the large effect, polyvinyl formal is particularly preferable. Examples of commercially available products of these thermoplastic resins include “Denka Butyral (registered trademark)” and “Denka Formal (registered trademark)” (manufactured by Denki Kagaku Kogyo Co., Ltd.), “Vinilec (registered trademark)” (JNC Corporation ) Made).
また、ポリスルホン、ポリエーテルスルホン、ポリイミドは、樹脂そのものが耐熱性に優れるほか、耐熱性が要求される用途、例えば航空機の構造部材などによく用いられるエポキシ樹脂である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と適度な相溶性を有する樹脂骨格をもつ重合体があり、これを使用するとエポキシ樹脂組成物の流動性制御の効果が大きいほか、繊維強化樹脂複合材料の耐衝撃性を高める効果があるため好ましい。このような重合体の例としては、ポリスルホンでは“レーデル（登録商標）”Ａ（ソルベイアドバンスドポリマーズ社製）、“スミカエクセル（登録商標）”ＰＥＳ（住友化学（株）製）など、ポリイミドでは“ウルテム（登録商標）”（ジーイープラスチックス社製）、“Ｍａｔｒｉｍｉｄ（登録商標）”５２１８（ハンツマン社製）などが挙げられる。 Polysulfone, polyethersulfone, and polyimide are not only excellent in heat resistance but also in applications where heat resistance is required, such as tetraglycidyldiaminodiphenylmethane and triglycidylamino, which are epoxy resins often used for aircraft structural members. There is a polymer having a resin skeleton having moderate compatibility with a glycidylamine type epoxy resin such as phenol, triglycidylaminocresol, and tetraglycidylxylenediamine, and when this is used, the fluidity control effect of the epoxy resin composition is effective. In addition to being large, it is preferable because it has an effect of improving the impact resistance of the fiber-reinforced resin composite material. Examples of such polymers include “Radel (registered trademark)” A (manufactured by Solvay Advanced Polymers) for polysulfone, “Sumika Excel (registered trademark)” PES (manufactured by Sumitomo Chemical Co., Ltd.), and “ Ultem (registered trademark) "(manufactured by GE Plastics)," Matrimid (registered trademark) "5218 (manufactured by Huntsman), and the like.
本発明のエポキシ樹脂組成物において、熱可塑性樹脂を含む場合は、エポキシ樹脂組成物に含まれるエポキシ樹脂１００質量部に対して、１〜６０質量部含まれることが好ましい。 In the epoxy resin composition of this invention, when a thermoplastic resin is included, it is preferable that 1-60 mass parts is contained with respect to 100 mass parts of epoxy resins contained in an epoxy resin composition.
（粒子の配合）
本発明のエポキシ樹脂組成物は、本発明の効果を妨げない範囲で、カップリング剤や、熱硬化性樹脂粒子、または、カーボンブラック、カーボン粒子や金属めっき有機粒子等の導電性粒子、あるいはシリカゲル、クレー等の無機フィラーを配合することができる。これらの添加には、エポキシ樹脂組成物の粘度を高め、樹脂フローを小さくする粘度調整効果、樹脂硬化物の弾性率、耐熱性を向上させる効果、耐摩耗性を向上させる効果がある。
(Formulation of particles)
The epoxy resin composition of the present invention is a coupling agent, thermosetting resin particles, or conductive particles such as carbon black, carbon particles and metal plating organic particles, or silica gel as long as the effects of the present invention are not hindered. An inorganic filler such as clay can be blended. These additions have the effect of increasing the viscosity of the epoxy resin composition and reducing the resin flow, the effect of improving the elastic modulus and heat resistance of the cured resin, and the effect of improving wear resistance.
（エポキシ樹脂組成物の調製方法）
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。
(Method for preparing epoxy resin composition)
For the preparation of the epoxy resin composition of the present invention, for example, 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.
（エポキシ樹脂硬化物の曲げ特性）
本発明のエポキシ樹脂組成物を１３０℃で２時間硬化させた際の樹脂硬化物の曲げ弾性率は、３．５ＧＰａ以上であることが好ましく、３．７ＧＰａ以上であることがより好ましい。弾性率が３．５ＧＰａ以上であると、静的強度に優れた繊維強化複合材料が得られる。曲げ弾性率の上限は、一般には５．０ＧＰａ以下である。
(Bending characteristics of cured epoxy resin)
The flexural modulus of the cured resin when the epoxy resin composition of the present invention is cured at 130 ° C. for 2 hours is preferably 3.5 GPa or more, and more preferably 3.7 GPa or more. When the elastic modulus is 3.5 GPa or more, a fiber-reinforced composite material having excellent static strength can be obtained. The upper limit of the flexural modulus is generally 5.0 GPa or less.
ここで、樹脂硬化物の曲げ弾性率および曲げ撓み量の測定法は以下の通りである。スペーサーにより厚み２ｍｍとなるように設定したモールド中で１３０℃の温度で２時間硬化させ、厚さ２ｍｍの樹脂硬化物を得る。この樹脂硬化物から幅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、スパン間長さを３２ｍｍ、クロスヘッドスピードを２．５ｍｍ／分とし、ＪＩＳ Ｋ７１７１（１９９４）に従って３点曲げ試験を実施することにより、曲げ弾性率および曲げ撓み量が測定できる。 Here, the measuring method of the bending elastic modulus and bending amount of the cured resin is as follows. Curing is performed at a temperature of 130 ° C. for 2 hours in a mold set to have a thickness of 2 mm with a spacer to obtain a cured resin having a thickness of 2 mm. A test piece having a width of 10 mm and a length of 60 mm was cut out from the cured resin, and the span length was set to 32 mm and the crosshead speed was set to 2.5 mm / min using an Instron universal testing machine (manufactured by Instron). By carrying out a three-point bending test according to K7171 (1994), the bending elastic modulus and the bending deflection can be measured.
なお、樹脂硬化物を得るための硬化温度や硬化時間は特に限定されず、成形品の形状や厚みにより最適な条件は変わるため、使用者により任意に選択されるものであるが、暴走反応を抑えつつ、短時間で成形する観点から、１３０℃〜１５０℃の温度で９０分〜２時間硬化させる条件が好ましい。 The curing temperature and curing time for obtaining the resin cured product are not particularly limited, and the optimum conditions vary depending on the shape and thickness of the molded product. From the viewpoint of molding in a short time while suppressing, conditions for curing at a temperature of 130 ° C. to 150 ° C. for 90 minutes to 2 hours are preferable.
（繊維強化複合材料）
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。
(Fiber reinforced composite material)
Next, the fiber reinforced composite material will be described. 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.
本発明に用いられる強化繊維は特に限定されるものではなく、ガラス繊維、炭素繊維、アラミド繊維、ボロン繊維、アルミナ繊維、炭化ケイ素繊維などが用いられる。これらの繊維を２種以上混合して用いても構わない。この中で、軽量かつ高剛性な繊維強化複合材料が得られる炭素繊維を用いることが好ましい。 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 from which a lightweight and highly rigid fiber-reinforced composite material can be obtained.
（プリプレグ）
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が好ましい。プリプレグ繊維の配置および樹脂の割合を精密に制御でき、複合材料の特性を最大限に引き出すことのできる材料形態である。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）などの公知の方法を挙げることができる。
(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. This is a material form in which the arrangement of the prepreg fibers and the ratio of the resin can be precisely controlled, and the characteristics of the composite material can be maximized. 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 known methods such as a hot melt method (dry method).
ホットメルト法は、加熱により低粘度化したエポキシ樹脂組成物を直接強化繊維に含浸させる方法、または離型紙などの上にエポキシ樹脂組成物をコーティングしたフィルムを作製しておき、次いで強化繊維の両側または片側から前記フィルムを重ね、加熱加圧することにより強化繊維に樹脂を含浸させる方法である。 The hot melt method is a method in which a reinforcing fiber is impregnated directly with an epoxy resin composition whose viscosity is reduced by heating, or a film in which an epoxy resin composition is coated on a release paper is prepared, and then both sides of the reinforcing fiber are prepared. Alternatively, it is a method of impregnating a reinforcing fiber with a resin by overlapping the film from one side and heating and pressing.
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。 In the prepreg lamination 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.
本発明のエポキシ樹脂組成物の硬化物と、強化繊維を含む繊維強化複合材料は、スポーツ用途、一般産業用途および航空宇宙用途に好ましく用いられる。より具体的には、スポーツ用途では、ゴルフシャフト、釣り竿、テニスやバドミントンのラケット、ホッケーなどのスティック、およびスキーポールなどに好ましく用いられる。さらに一般産業用途では、自動車、自転車、船舶および鉄道車両などの移動体の構造材、ドライブシャフト、板バネ、風車ブレード、圧力容器、フライホイール、製紙用ローラ、屋根材、ケーブル、および補修補強材料などに好ましく用いられる。 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 for moving bodies such as automobiles, bicycles, ships and railway vehicles, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, paper rollers, roofing materials, cables, and repair reinforcement materials It is preferably used for such as.
以下に実施例を示し、本発明をさらに具体的に説明するが、本発明はこれら実施例の記載に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.
本実施例で用いる構成要素は以下の通りである。 The components used in this embodiment are as follows.
＜使用した材料＞
・エポキシ樹脂［Ａ］
［Ａ１］−１ “ｊＥＲ（登録商標）”１５４（フェノールノボラック型エポキシ樹脂、エポキシ当量：１７８、平均官能基数：３．０個／分子、三菱化学（株）製）
［Ａ１］−２ “エピクロン（登録商標）”Ｎ−７７５（フェノールノボラック型エポキシ樹脂、エポキシ当量：１９０、平均官能基数：６．５個／分子、ＤＩＣ（株）製）
［Ａ１］−３ “エピクロン（登録商標）”ＨＰ−７２００Ｈ（ジシクロペンタジエン型エポキシ樹脂、エポキシ当量：２７９、平均官能基数：３．０個／分子、ＤＩＣ（株）製）
［Ａ１］−４ “ｊＥＲ（登録商標）”１５２（フェノールノボラック型エポキシ樹脂、エポキシ当量：１７７、平均官能基数：２．２個／分子、三菱化学（株）製）
［Ａ２］−１ “スミエポキシ（登録商標）”ＥＬＭ４３４（テトラグリシジルジアミノジフェニルメタン、エポキシ当量：１２５、住友化学工業（株）製）
［Ａ２］−２ “アラルダイト（登録商標）”ＭＹ０６００（トリグリシジルｍ−アミノフェノール、エポキシ当量：１１８、ハンツマン・アドバンスト・マテリアルズ社製）
［Ａ３］−１ “エピクロン（登録商標）”８３０（液状ビスフェノールＦ型エポキシ樹脂、エポキシ当量：１６８、ＤＩＣ（株）製）
［Ａ３］−２ “エポトート（登録商標）”ＹＤＦ−２００１（固形ビスフェノールＦ型エポキシ樹脂、エポキシ当量：４７５、東都化成（株）製）
［Ａ］−１ “ｊＥＲ（登録商標）”８２８（液状ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８９、三菱化学（株）製）
［Ａ］−２ “ｊＥＲ（登録商標）”１００１（固形ビスフェノールＡ型エポキシ樹脂、エポキシ当量：４７５、三菱化学（株）製）。
<Materials used>
・ Epoxy resin [A]
[A1] -1 “jER (registered trademark)” 154 (phenol novolac type epoxy resin, epoxy equivalent: 178, average number of functional groups: 3.0 / molecule, manufactured by Mitsubishi Chemical Corporation)
[A1] -2 “Epicron (registered trademark)” N-775 (phenol novolac type epoxy resin, epoxy equivalent: 190, average functional group number: 6.5 / molecule, manufactured by DIC Corporation)
[A1] -3 “Epiclon (registered trademark)” HP-7200H (dicyclopentadiene type epoxy resin, epoxy equivalent: 279, average number of functional groups: 3.0 / molecule, manufactured by DIC Corporation)
[A1] -4 “jER (registered trademark)” 152 (phenol novolac type epoxy resin, epoxy equivalent: 177, average number of functional groups: 2.2 / molecule, manufactured by Mitsubishi Chemical Corporation)
[A2] -1 “Sumiepoxy (registered trademark)” ELM434 (tetraglycidyldiaminodiphenylmethane, epoxy equivalent: 125, manufactured by Sumitomo Chemical Co., Ltd.)
[A2] -2 “Araldite (registered trademark)” MY0600 (triglycidyl m-aminophenol, epoxy equivalent: 118, manufactured by Huntsman Advanced Materials)
[A3] -1 “Epiclon (registered trademark)” 830 (liquid bisphenol F type epoxy resin, epoxy equivalent: 168, manufactured by DIC Corporation)
[A3] -2 “Epototo (registered trademark)” YDF-2001 (solid bisphenol F type epoxy resin, epoxy equivalent: 475, manufactured by Tohto Kasei Co., Ltd.)
[A] -1 “jER (registered trademark)” 828 (liquid bisphenol A type epoxy resin, epoxy equivalent: 189, manufactured by Mitsubishi Chemical Corporation)
[A] -2 “jER (registered trademark)” 1001 (solid bisphenol A type epoxy resin, epoxy equivalent: 475, manufactured by Mitsubishi Chemical Corporation).
・ジシアンジアミド［Ｂ］
［Ｂ］−１ ＤＩＣＹ７（ジシアンジアミド、三菱化学（株）製）。
・ Dicyandiamide [B]
[B] -1 DICY7 (dicyandiamide, manufactured by Mitsubishi Chemical Corporation).
・芳香族ウレア化合物［Ｃ］
［Ｃ］−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）
［Ｃ］−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）。
・ Aromatic urea compounds [C]
[C] -1 DCMU99 (3- (3,4-dichlorophenyl) -1,1-dimethylurea, manufactured by Hodogaya Chemical Co., Ltd.)
[C] -2 “Omicure (registered trademark)” 24 (4,4′-methylenebis (phenyldimethylurea, manufactured by PTI Japan).
・芳香族ウレア化合物以外の硬化促進剤［Ｃ’］
［Ｃ’］−１ “キュアゾール（登録商標）”２ＰＨＺ−ＰＷ（２−フェニル−４，５−ジヒドロキシメチルイミダゾール、四国化成工業(株)製）
［Ｃ’］−２ “キュアゾール（登録商標）”２Ｐ４ＭＨＺ−ＰＷ（２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、四国化成工業(株)製）
［Ｃ’］−３ “キュアダクト（登録商標）”Ｐ−０５０５（エポキシ−イミダゾールアダクト、四国化成工業(株)製）。
・ Curing accelerators other than aromatic urea compounds [C ']
[C ′]-1 “Curazole (registered trademark)” 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
[C ′]-2 “Curazole (registered trademark)” 2P4MHZ-PW (2-phenyl-4-methyl-5-hydroxymethylimidazole, manufactured by Shikoku Chemicals Co., Ltd.)
[C ′]-3 “Cureduct (registered trademark)” P-0505 (epoxy-imidazole adduct, manufactured by Shikoku Kasei Kogyo Co., Ltd.).
・ホウ酸エステルを含む混合物［Ｄ］
［Ｄ］−１ “キュアダクト（登録商標）”Ｌ−０７Ｎ（ホウ酸エステル化合物を５質量部含む組成物、四国化成工業(株)製）。
-Mixture containing borate ester [D]
[D] -1 “Cureduct (registered trademark)” L-07N (a composition containing 5 parts by mass of a borate ester compound, manufactured by Shikoku Kasei Kogyo Co., Ltd.).
・熱可塑性樹脂［Ｅ］
［Ｅ］−１ “ビニレック（登録商標）”Ｋ（ポリビニルホルマール、ＪＮＣ(株)製）。
・ Thermoplastic resin [E]
[E] -1 “Vinylec (registered trademark)” K (polyvinyl formal, manufactured by JNC Corporation).
・その他の化合物
ビスフェノールＳ（東京化成工業（株）製ビス（ヒドロキシフェニル）スルホンをハンマーミルで粉砕した後、ふるいで分級したもの。平均粒径１４．８μｍ。）。
-Other compounds bisphenol S (bis (hydroxyphenyl) sulfone manufactured by Tokyo Chemical Industry Co., Ltd. was pulverized with a hammer mill and classified by sieving. Average particle diameter of 14.8 μm).
＜エポキシ樹脂組成物の調製方法＞
（１）硬化促進剤マスター、硬化剤マスターの作製方法
液状樹脂である［Ａ３］−１（“エピクロン（登録商標）”８３０）または［Ａ］−１（“ｊＥＲ（登録商標）”８２８）１０質量部（エポキシ樹脂［Ａ］１００質量部のうちの１０質量部）に対し、芳香族ウレア化合物［Ｃ］または硬化促進剤［Ｃ’］、および、ホウ酸エステルを含む混合物［Ｄ］を添加し、ニーダーを用いて室温で混練した。三本ロールを用いて混合物をロール間に２回通し、硬化促進剤マスターを調製した。硬化促進剤マスターにジシアンジアミド［Ｂ］、およびビスフェノールＳを含む場合はビスフェノールＳを添加し、ニーダーを用いて室温で混練した後、三本ロールを用いてロール間に２回通し、硬化剤マスターを作製した。
<Method for preparing epoxy resin composition>
(1) Curing Accelerator Master, Preparation Method of Curing Agent Master [A3] -1 (“Epiclon (registered trademark)” 830) or [A] -1 (“jER (registered trademark)” 828) 10 which is a liquid resin Addition of aromatic urea compound [C] or curing accelerator [C ′] and boric acid ester-containing mixture [D] to 10 parts by mass (10 parts by mass of epoxy resin [A] 100 parts by mass) And kneaded at room temperature using a kneader. The mixture was passed twice between the rolls using three rolls to prepare a curing accelerator master. In the case where dicyandiamide [B] and bisphenol S are included in the curing accelerator master, bisphenol S is added, kneaded at room temperature using a kneader, and then passed twice between the rolls using a three roll, Produced.
（２）エポキシ樹脂組成物の作製方法
ニーダー中に、エポキシ樹脂［Ａ］のうち前記（１）で使用した［Ａ３］−１（“エピクロン（登録商標）”８３０）または［Ａ］−１（“ｊＥＲ（登録商標）”８２８）１０質量部を除くエポキシ樹脂［Ａ］９０質量部および熱可塑性樹脂［Ｅ］を投入し、混練しながら１５０℃まで昇温し、１５０℃において１時間混練することで、透明な粘調液を得た。粘調液を６０℃まで混練しながら降温させた後、前記（１）で作製した硬化剤マスターを配合し、６０℃において３０分間混練することにより、エポキシ樹脂組成物を得た。
(2) Preparation method of epoxy resin composition In the kneader, [A3] -1 (“Epiclon (registered trademark)” 830) or [A] -1 ( “JER (registered trademark)” 828) Epoxy resin [A] excluding 10 parts by mass and 90 parts by mass of thermoplastic resin [E] are charged, heated to 150 ° C. while kneading, and kneaded at 150 ° C. for 1 hour. Thus, a transparent viscous liquid was obtained. The temperature of the viscous liquid was lowered while kneading to 60 ° C., and then the curing agent master prepared in (1) was blended and kneaded at 60 ° C. for 30 minutes to obtain an epoxy resin composition.
各実施例および比較例の成分配合比について表１〜５に示した。 It showed to Tables 1-5 about the component mixture ratio of each Example and the comparative example.
＜樹脂組成物特性の評価方法＞
（１）Ｔ（１００）
エポキシ樹脂組成物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、３０℃から１００℃／分で１００℃まで昇温した後に８時間の等温測定を行った。昇温開始時刻から４２秒後を等温測定開始時刻とし、等温測定開始時刻から熱流量が発熱ピークトップに至るまでの時間を測定し、１００℃の等温測定時のピークトップまでの時間として取得した。測定は１つの水準あたり３サンプルずつ行い、その平均値を採用した。以後、本測定で得られた平均値をＴ（１００）と表記する（ただし、Ｔ（１００）の単位は［分］である。）。
<Method for evaluating resin composition characteristics>
(1) T (100)
3 mg of the epoxy resin composition was weighed into a sample pan, and heated for 8 hours from 30 ° C. to 100 ° C./min using a differential scanning calorimeter (Q-2000: manufactured by TA Instruments). Isothermal measurements were made. 42 seconds after the temperature rise start time was set as the isothermal measurement start time, and the time from the isothermal measurement start time until the heat flow reached the exothermic peak top was measured and obtained as the time to the peak top during the 100 ° C. isothermal measurement. . The measurement was performed 3 samples per level, and the average value was adopted. Hereinafter, the average value obtained in this measurement is expressed as T (100) (however, the unit of T (100) is [minute]).
（２）Ｔ（６０）
エポキシ樹脂組成物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、３０℃から１００℃／分で６０℃まで昇温した後に４８時間の等温測定を行った。昇温開始時刻から１８秒後を等温測定開始時刻とし、等温測定開始時刻から熱流量が発熱ピークトップに至るまでの時間を測定し、６０℃の等温測定時のピークトップまでの時間として取得した。測定は１つの水準あたり３サンプルずつ行い、その平均値を採用した。以後、本測定で得られた平均値をＴ（６０）と表記する（ただし、Ｔ（６０）の単位は［時間］である。）。なお、４８時間たってもピークトップが現れなかった場合は、Ｔ（６０）の値は「４８以上」とした。
(2) T (60)
After weighing 3 mg of the epoxy resin composition into a sample pan and using a differential scanning calorimeter (Q-2000: manufactured by TA Instruments), the temperature was raised from 30 ° C. to 60 ° C. at 100 ° C./min for 48 hours. Isothermal measurements were made. The isothermal measurement start time is 18 seconds after the temperature rise start time, and the time from the isothermal measurement start time until the heat flow reaches the exothermic peak top is measured and obtained as the time to the peak top at the 60 ° C. isothermal measurement. . The measurement was performed 3 samples per level, and the average value was adopted. Hereinafter, the average value obtained in this measurement is expressed as T (60) (however, the unit of T (60) is [time]). In addition, when the peak top did not appear even after 48 hours, the value of T (60) was set to “48 or more”.
＜樹脂硬化物の作製方法と評価方法＞
（１）樹脂硬化物の弾性率と撓み
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の板状の樹脂硬化物を得た。この樹脂硬化物から、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、弾性率および撓みを測定した。サンプル数ｎ＝５で測定した値の平均値を弾性率と撓みの値とした。
<Production method and evaluation method of cured resin>
(1) Elastic Modulus and Flexure of Cured Resin Product After defoaming the epoxy resin composition in a vacuum, in a mold set to a thickness of 2 mm with a 2 mm thick “Teflon” (registered trademark) spacer, Curing was performed at a temperature of 90 ° C. for 90 minutes to obtain a plate-shaped resin cured product having a thickness of 2 mm. From this cured resin, a test piece having a width of 10 mm and a length of 60 mm was cut out, an Instron universal testing machine (manufactured by Instron) was used, the span was set to 32 mm, the crosshead speed was set to 100 mm / min, and JIS K7171 (1994). According to the above, three-point bending was performed, and the elastic modulus and deflection were measured. The average value of the values measured with the number of samples n = 5 was taken as the value of elastic modulus and deflection.
＜プリプレグの作製方法と評価方法＞
（１）プリプレグの作製方法
上記＜エポキシ樹脂組成物の作製方法＞に従い作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、目付が７４ｇ／ｍ２の樹脂フィルムを作製した。
<Prepreg production method and evaluation method>
(1) Preparation method of prepreg The epoxy resin composition prepared according to the above <Preparation method of epoxy resin composition> was applied onto release paper using a film coater, and a resin film having a basis weight of 74 g / m 2 was prepared. .
この樹脂フィルムをプリプレグ化装置にセットし、一方向に引き揃えたシート状にした炭素繊維“トレカ”（登録商標）Ｔ７００Ｓ（東レ（株）製、目付１５０ｇ／ｍ２）の両面から加熱加圧含浸し、樹脂含有率３３質量％のプリプレグを得た。 This resin film is set in a prepreg forming apparatus and heated and pressed from both sides of a carbon fiber “Torayca” (registered trademark) T700S (manufactured by Toray Industries, Inc., weight per unit: 150 g / m 2 ) that is aligned in one direction. Impregnation was performed to obtain a prepreg having a resin content of 33% by mass.
（２）プリプレグの硬化速度の評価方法
プリプレグの硬化速度は、プリプレグを２０ｃｍ四方に切り取り、厚さ１５０μｍの“テフロン（登録商標）”シートで挟み込み、１３０℃でプレスした後に、取り出した時の取り扱い性によって判定した。取り扱い性は以下の基準で判定し、Ａ〜Ｃを合格とした。
Ａ：２０分後に取り出した時にプリプレグが変形しなかった。
Ｂ：２０分後に取り出した時はプリプレグが変形したが、３０分後に取り出した時は変形しなかった。
Ｃ：３０分後に取り出した時はプリプレグが変形したが、４０分後に取り出した時は変形しなかった。
Ｄ：硬化速度が不十分で４０分後に取り出した場合にプリプレグが変形した。
(2) Evaluation method of curing rate of prepreg The curing rate of the prepreg was determined by cutting the prepreg into 20 cm squares, sandwiching it with a 150 μm thick “Teflon (registered trademark)” sheet, pressing it at 130 ° C., and taking it out. Judged by gender. The handleability was determined according to the following criteria, and A to C were regarded as acceptable.
A: The prepreg did not deform when taken out after 20 minutes.
B: The prepreg was deformed when removed after 20 minutes, but was not deformed when removed after 30 minutes.
C: The prepreg was deformed when taken out after 30 minutes, but was not deformed when taken out after 40 minutes.
D: The prepreg was deformed when the curing speed was insufficient and the film was taken out after 40 minutes.
（３）プリプレグの保管安定性の評価方法
プリプレグの保管安定性は、プリプレグを１０ｃｍ四方に切り取り、４０℃で６０日放置した場合のガラス転移温度の増加量によって判定した。ガラス転移温度は、保管後のプリプレグ８ｍｇをサンプルパンに測り取り、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５０℃まで１０℃／分で昇温して測定した。得られた発熱カーブの変曲点の中点をＴｇとして取得した。
(3) Evaluation method of storage stability of prepreg The storage stability of prepreg was determined by the amount of increase in glass transition temperature when prepreg was cut into 10 cm square and left at 40 ° C. for 60 days. The glass transition temperature was measured at 8 ° C./min from −50 ° C. to 50 ° C. using a differential scanning calorimeter (Q-2000: manufactured by TA Instruments) by measuring 8 mg of the prepreg after storage in a sample pan. Measured by warming. The midpoint of the inflection point of the obtained exothermic curve was obtained as Tg.
（４）プリプレグの８０℃１時間熱処理後の保管安定性の評価方法
熱履歴を加えた際の保管安定性の指標として、８０℃で１時間の熱処理を加えたプリプレグの保管安定性を評価した。プリプレグを１０ｃｍ四方に切り取り、８０℃に調製したプレス機の盤面にプリプレグを１時間静置し、その後室温のアルミ板の上で急冷し、熱履歴を加えたプリプレグサンプルを調製した。得られたサンプルについて、（３）と同様の方法で、４０℃で６０日放置した場合のガラス転移温度の増加量を測定することにより、保管安定性を評価した。
(4) Storage stability evaluation method after heat treatment at 80 ° C. for 1 hour of prepreg The storage stability of prepreg subjected to heat treatment at 80 ° C. for 1 hour was evaluated as an index of storage stability when heat history was applied. . The prepreg was cut into a 10 cm square and the prepreg was allowed to stand for 1 hour on the surface of a press machine prepared at 80 ° C., and then rapidly cooled on an aluminum plate at room temperature to prepare a prepreg sample to which a thermal history was added. About the obtained sample, storage stability was evaluated by measuring the increase amount of the glass transition temperature when it was left at 40 degreeC for 60 days by the method similar to (3).
＜炭素繊維複合材料（ＣＦＲＰ）の特性評価方法＞
（１）ＣＦＲＰの一方向積層板の作製方法
ＣＦＲＰの特性評価に用いる一方向積層板は、次の方法によって作製した。上記＜プリプレグの作製方法＞に従って作製した一方向プリプレグの繊維方向を揃え、１３ｐｌｙ積層した。積層したプリプレグをナイロンフィルムで隙間のないように覆い、これをオートクレーブ中で１３０℃、内圧０．３ＭＰａで２時間加熱加圧して硬化し、一方向積層板を作製した。
<Characteristic evaluation method of carbon fiber composite material (CFRP)>
(1) Production method of CFRP unidirectional laminate The unidirectional laminate used for CFRP characteristic evaluation was produced by the following method. The fiber direction of the unidirectional prepreg produced according to the above <prepreg production method> was aligned, and 13 ply was laminated. The laminated prepreg was covered with a nylon film so as not to have a gap, and was cured by heating and pressing at 130 ° C. and an internal pressure of 0.3 MPa for 2 hours in an autoclave to prepare a unidirectional laminate.
（２）ＣＦＲＰの０°曲げ強度の評価方法
上記に従い作製した一方向積層板を、厚み２ｍｍ、幅１５ｍｍ、長さ１００ｍｍとなるように切り出した。インストロン万能試験機（インストロン社製）を用いＪＩＳ Ｋ７０７４（１９８８）に従って３点曲げを実施した。スパンを８０ｍｍ、クロスヘッドスピードを５．０ｍｍ／分、厚子径１０ｍｍ、支点径４．０ｍｍで測定を行い、０°曲げ強度を測定した。サンプル数ｎ＝６で測定した値の平均値を０°曲げ強度の値とした。
(2) Evaluation method of 0 ° bending strength of CFRP The unidirectional laminate produced according to the above was cut out to have a thickness of 2 mm, a width of 15 mm, and a length of 100 mm. Three-point bending was performed according to JIS K7074 (1988) using an Instron universal testing machine (Instron). Measurement was performed at a span of 80 mm, a crosshead speed of 5.0 mm / min, a thickness of 10 mm, a fulcrum diameter of 4.0 mm, and a 0 ° bending strength was measured. The average value of the values measured with the number of samples n = 6 was taken as the value of 0 ° bending strength.
（３）ＣＦＲＰの９０°曲げ強度の評価方法
上記に従い作製した一方向積層板を、厚み２ｍｍ、幅１５ｍｍ、長さ６０ｍｍとなるように切り出した。インストロン万能試験機（インストロン社製）を用いＪＩＳ Ｋ７０７４（１９８８）に従って３点曲げを実施した。スパンを４０ｍｍ、クロスヘッドスピードを１．０ｍｍ／分、厚子径１０ｍｍ、支点径４．０ｍｍで測定を行い、９０°曲げ強度を測定した。サンプル数ｎ＝６で測定した値の平均値を９０°曲げ強度の値とした。
(3) Evaluation Method of 90 ° Bending Strength of CFRP The unidirectional laminate produced according to the above was cut out to have a thickness of 2 mm, a width of 15 mm, and a length of 60 mm. Three-point bending was performed according to JIS K7074 (1988) using an Instron universal testing machine (Instron). Measurement was performed at a span of 40 mm, a crosshead speed of 1.0 mm / min, a thickness of 10 mm, a fulcrum diameter of 4.0 mm, and a 90 ° bending strength was measured. The average value of the values measured with the number of samples n = 6 was taken as the value of 90 ° bending strength.
（実施例１）
[Ａ]エポキシ樹脂として“ｊＥＲ（登録商標）”１５４を３０質量部、“ｊＥＲ（登録商標）”８２８を４０質量部、ｊＥＲ（登録商標）”１００１を３０質量部、[Ｂ]ジシアンジアミドとしてＤＩＣＹ７を５．３質量部、および[Ｃ]芳香族ウレア化合物としてＤＣＭＵ９９を３．０質量部、[Ｄ]ホウ酸エステルを含む混合物として“キュアダクト（登録商標）”Ｌ−０７Ｎを３．０質量部、熱可塑樹脂として“ビニレック（登録商標）”Ｋを３．０質量部用い、上記＜エポキシ樹脂組成物の作製方法＞に従ってエポキシ樹脂組成物を作製した。すなわち、液状樹脂である［Ａ］−１（“ｊＥＲ（登録商標）”８２８）１０質量部（エポキシ樹脂［Ａ］１００質量部のうちの１０質量部）に対し、ＤＣＭＵ９９を３．０質量部、および“キュアダクト（登録商標）”Ｌ−０７Ｎを３．０質量部添加しニーダーを用いて室温で混練した。三本ロールを用いて混合物をロール間に２回通し、硬化促進剤マスターを調製した。硬化促進剤マスターにＤＩＣＹ７を５．３質量部添加し、ニーダーを用いて室温で混練した後、三本ロールを用いてロール間に２回通し、硬化剤マスターを作製した。
Example 1
[A] 30 parts by mass of “jER (registered trademark)” 154 as epoxy resin, 40 parts by mass of “jER (registered trademark)” 828, 30 parts by mass of jER (registered trademark) 1001, and [B] DICY7 as dicyandiamide 5.3 parts by weight, and [C] 3.0 parts by weight of DCMU99 as an aromatic urea compound, [D] 3.0 parts by weight of “Cureduct (registered trademark)” L-07N as a mixture containing a boric acid ester The epoxy resin composition was prepared using 3.0 parts by mass of “Vinylec (registered trademark)” K as a thermoplastic resin according to the above <Method for producing epoxy resin composition>, that is, a liquid resin [A]. -1 (“jER (registered trademark)” 828) 10 parts by mass (10 parts by mass of 100 parts by mass of the epoxy resin [A]), 3.0 parts by mass of DCMU99, and “Cure 3.0 parts by mass of Kut (registered trademark) “L-07N” was added, and the mixture was kneaded at room temperature using a kneader. The mixture was passed twice between rolls using a three roll to prepare a curing accelerator master. After 5.3 parts by mass of DICY7 was added to the accelerator master and kneaded at room temperature using a kneader, it was passed twice between the rolls using a three roll to produce a curing agent master.
ニーダー中に、残りのエポキシ樹脂[Ａ]９０質量部として、“ｊＥＲ（登録商標）”１５４を３０質量部、“ｊＥＲ（登録商標）”８２８を３０質量部、ｊＥＲ（登録商標）”１００１を３０質量部投入し、さらに“ビニレック（登録商標）”Ｋを３．０質量部投入した。混練しながら１５０℃まで昇温し、１５０℃において１時間混練することで、透明な粘調液を得た。粘調液を６０℃まで混練しながら降温させた後、上記で作製した硬化剤マスターを配合し、６０℃において３０分間混練することにより、エポキシ樹脂組成物を得た。 In the kneader, as the remaining epoxy resin [A] 90 parts by mass, 30 parts by mass of “jER (registered trademark)” 154, 30 parts by mass of “jER (registered trademark)” 828, and jER (registered trademark) “1001” 30 parts by mass was added, and 3.0 parts by mass of “Vinylec (registered trademark)” K. The mixture was heated to 150 ° C. while kneading, and kneaded at 150 ° C. for 1 hour to obtain a transparent viscous liquid. After the temperature of the viscous liquid was lowered while kneading to 60 ° C., the curing agent master prepared above was blended and kneaded at 60 ° C. for 30 minutes to obtain an epoxy resin composition.
このエポキシ樹脂組成物について、Ｔ（１００）およびＴ（６０）を測定したところ、Ｔ（１００）は４３分、Ｔ（６０）は２９時間であった。 When T (100) and T (60) of this epoxy resin composition were measured, T (100) was 43 minutes and T (60) was 29 hours.
また、エポキシ樹脂組成物を上記＜樹脂硬化物の作製方法と評価方法＞に記載の方法で硬化して樹脂硬化物を作製し、同記載の３点曲げ試験を行った結果、弾性率は３．３ＧＰａ、撓みは１０．２ｍｍと、樹脂硬化物の力学特性も良好であった。 Moreover, the epoxy resin composition was cured by the method described in the above <Method for producing and evaluating resin cured product> to produce a resin cured product, and the three-point bending test described above was performed. The mechanical properties of the cured resin were also good with 3 GPa and deflection of 10.2 mm.
さらに、得られたエポキシ樹脂組成物から、＜プリプレグの作製方法と評価方法＞に記載の方法でプリプレグを作製した。得られたプリプレグは十分なタック性・ドレープ性を有していた。得られたプリプレグに関し、同記載の硬化速度と保管安定性の評価を行ったところ、１３０℃において３０分以内にプリプレグは変形しなくなる程度まで硬化し、また、４０℃において６０日間保管後にＴｇは２℃の上昇に留まり、プリプレグは十分な硬化速度と保管安定性を有していた。さらに、熱履歴への安定性について、８０℃で１時間熱処理後のプリプレグの保管安定性を評価したところ、４０℃において６０日間保管後にＴｇは３℃の上昇に留まり、８０℃での熱処理前とほぼ同等の保管安定性を有していた。 Furthermore, a prepreg was produced from the obtained epoxy resin composition by the method described in <Preparation Method and Evaluation Method of Prepreg>. The obtained prepreg had sufficient tack and drape properties. The obtained prepreg was evaluated for the curing speed and storage stability described in the above, and as a result, the prepreg was cured within 130 minutes at 130 ° C. until it was not deformed. The prepreg had only a sufficient curing rate and storage stability. Furthermore, as to the stability to the thermal history, the storage stability of the prepreg after heat treatment at 80 ° C. for 1 hour was evaluated. After storage for 60 days at 40 ° C., the Tg remained at 3 ° C., and before the heat treatment at 80 ° C. It had almost the same storage stability.
＜炭素繊維複合材料（ＣＦＲＰ）の評価方法＞に記載の方法で積層・硬化して一方向積層板を作製し、３点曲げ試験を行った結果、０°曲げ強度は１４２０ＭＰａ、９０°曲げ強度は１０５ＭＰａと、ＣＦＲＰの力学特性も良好であった。 As a result of producing a unidirectional laminate by laminating and curing by the method described in <Method for evaluating carbon fiber composite material (CFRP)> and performing a three-point bending test, the 0 ° bending strength is 1420 MPa and the 90 ° bending strength. Was 105 MPa, and the mechanical properties of CFRP were also good.
（実施例２〜１６）
樹脂組成をそれぞれ表１〜３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、樹脂硬化物、およびプリプレグを作製した。得られたプリプレグは、実施例１と同様、いずれも十分なタック性・ドレープ性を示した。
(Examples 2 to 16)
An epoxy resin composition, a cured resin, and a prepreg were produced in the same manner as in Example 1 except that the resin composition was changed as shown in Tables 1 to 3, respectively. The obtained prepregs showed sufficient tack and drape properties as in Example 1.
各実施例のエポキシ樹脂組成物に関して、Ｔ（１００）、Ｔ（６０）は、それぞれ表１〜３に記載の通りであった。 Regarding the epoxy resin composition of each Example, T (100) and T (60) were as shown in Tables 1 to 3, respectively.
プリプレグの硬化速度と保管安定性、および熱履歴への安定性について、実施例１と同様の評価を行った結果、全ての水準において十分な硬化速度と保管安定性、熱履歴への安定性を示した。 As a result of the same evaluation as in Example 1 regarding the curing speed and storage stability of the prepreg and the stability to thermal history, sufficient curing speed, storage stability and stability to thermal history were obtained at all levels. Indicated.
また、樹脂硬化物の弾性率と撓みの値は、いずれも良好であり、ＣＦＲＰの力学特性も良好であった。 Moreover, the elastic modulus and the value of deflection of the cured resin were both good, and the mechanical properties of CFRP were also good.
（比較例１）
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、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表４に示した。エポキシ樹脂組成物のＴ（６０）の値が２３時間と２５時間未満であり、プリプレグの保管安定性は不十分であった。また、８０℃で１時間熱処理後のプリプレグの保管安定性を評価したところ、ビスフェノールＳを含むためか、Ｔｇは４４℃と大きく上昇し、熱履歴への安定性は得られなかった。
(Comparative Example 1)
About the resin composition shown in Table 4, the epoxy resin composition, the prepreg, and the resin cured material were produced by the same method as Example 1. The resin composition characteristics and evaluation results are shown in Table 4. The T (60) value of the epoxy resin composition was 23 hours and less than 25 hours, and the storage stability of the prepreg was insufficient. Moreover, when the storage stability of the prepreg after heat treatment at 80 ° C. for 1 hour was evaluated, Tg was greatly increased to 44 ° C. because of containing bisphenol S, and stability to thermal history was not obtained.
（比較例２）
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、プリプレグ、および樹脂硬化物を作製した。本組成は、比較例１からビスフェノールＳを除いた組成にあたる。樹脂組成物特性および評価結果は表４に示した。プリプレグの保管安定性および硬化物特性は良好であり、熱履歴への安定性も有したが、エポキシ樹脂組成物のＴ（１００）の値が７０分と６０分より長く、得られたプリプレグの硬化速度が不十分であった。
(Comparative Example 2)
About the resin composition shown in Table 4, the epoxy resin composition, the prepreg, and the resin cured material were produced by the same method as Example 1. This composition corresponds to a composition obtained by removing bisphenol S from Comparative Example 1. The resin composition characteristics and evaluation results are shown in Table 4. Although the storage stability and cured product properties of the prepreg were good and had stability to thermal history, the T (100) value of the epoxy resin composition was longer than 70 minutes and 60 minutes, and the obtained prepreg The curing rate was insufficient.
（比較例３）
成分[Ｄ]を添加しなかった以外は、実施例４と同じ方法でエポキシ樹脂組成物、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表４に示した。エポキシ樹脂組成物のＴ（６０）の値が１９時間と２５時間未満であり、プリプレグの保管安定性は不十分であった。また、８０℃で１時間熱処理後のプリプレグの保管安定性を評価したところ、Ｔｇは４３℃と大きく上昇し、熱履歴への安定性は得られなかった。
(Comparative Example 3)
An epoxy resin composition, a prepreg, and a cured resin were prepared in the same manner as in Example 4 except that Component [D] was not added. The resin composition characteristics and evaluation results are shown in Table 4. The T (60) value of the epoxy resin composition was 19 hours and less than 25 hours, and the storage stability of the prepreg was insufficient. Further, when the storage stability of the prepreg after heat treatment at 80 ° C. for 1 hour was evaluated, the Tg greatly increased to 43 ° C., and stability to thermal history was not obtained.
（比較例４）
硬化促進剤を“キュアゾール（登録商標）”２ＰＨＺ−ＰＷ（１．０質量部）に変更し、成分[Ｄ]を添加しなかった以外は、実施例２と同じ方法でエポキシ樹脂組成物、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表４に示した。プリプレグの保管安定性および硬化物特性は良好であり、熱履歴への安定性も有したが、エポキシ樹脂組成物のＴ（１００）の値が３００分と６０分より極めて長く、得られたプリプレグの硬化速度が不十分であった。
(Comparative Example 4)
The epoxy resin composition and prepreg were prepared in the same manner as in Example 2 except that the curing accelerator was changed to “CUREZOL (registered trademark)” 2PHZ-PW (1.0 part by mass) and component [D] was not added. And a cured resin product. The resin composition characteristics and evaluation results are shown in Table 4. The storage stability and cured product properties of the prepreg were good and had stability to thermal history, but the T (100) value of the epoxy resin composition was much longer than 300 minutes and 60 minutes. The curing speed of was insufficient.
（比較例５）
硬化促進剤を“キュアゾール（登録商標）”２Ｐ４ＭＨＺ−ＰＷ（１．０質量部）に変更し、成分[Ｄ]を添加しなかった以外は、実施例２と同じ方法でエポキシ樹脂組成物、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表４に示した。エポキシ樹脂組成物のＴ（６０）の値が２４時間と２５時間未満であり、プリプレグの保管安定性は不十分であった。また、８０℃で１時間熱処理後のプリプレグの保管安定性を評価したところ、Ｔｇは４４℃と大きく上昇し、熱履歴への安定性は得られなかった。
(Comparative Example 5)
An epoxy resin composition and a prepreg were prepared in the same manner as in Example 2 except that the curing accelerator was changed to “CUREZOL (registered trademark)” 2P4MHZ-PW (1.0 part by mass) and component [D] was not added. And a cured resin product. The resin composition characteristics and evaluation results are shown in Table 4. The value of T (60) of the epoxy resin composition was 24 hours and less than 25 hours, and the storage stability of the prepreg was insufficient. Further, when the storage stability of the prepreg after heat treatment at 80 ° C. for 1 hour was evaluated, the Tg greatly increased to 44 ° C., and stability to thermal history was not obtained.
（比較例６）
樹脂組成をそれぞれ表５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、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表５に示した。エポキシ樹脂組成物のＴ（６０）の値が１５時間と２５時間未満であり、プリプレグの保管安定性は不十分であった。また、８０℃で１時間熱処理後のプリプレグの保管安定性を評価したところ、Ｔｇは４２℃と大きく上昇し、熱履歴への安定性は得られなかった。また、樹脂硬化物の弾性率と撓みのバランスが悪化し、ＣＦＲＰの９０°曲げ強度は８３ＭＰａと低いものであった。
(Comparative Example 6)
An epoxy resin composition, a prepreg, and a cured resin were prepared in the same manner as in Example 1 except that the resin composition was changed as shown in Table 5. The resin composition characteristics and evaluation results are shown in Table 5. The value of T (60) of the epoxy resin composition was 15 hours and less than 25 hours, and the storage stability of the prepreg was insufficient. Further, when the storage stability of the prepreg after heat treatment at 80 ° C. for 1 hour was evaluated, Tg increased greatly to 42 ° C., and stability to thermal history was not obtained. Further, the balance between the elastic modulus and the bending of the cured resin was deteriorated, and the 90 ° bending strength of CFRP was as low as 83 MPa.
（比較例７）
樹脂組成をそれぞれ表５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、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表５に示した。プリプレグの保管安定性および硬化物特性は良好であり、熱履歴への安定性も有したが、エポキシ樹脂組成物のＴ（１００）の値が７０分と６０分より極めて長く、得られたプリプレグの硬化速度が不十分であった。
(Comparative Example 7)
An epoxy resin composition, a prepreg, and a cured resin were prepared in the same manner as in Example 1 except that the resin composition was changed as shown in Table 5. The resin composition characteristics and evaluation results are shown in Table 5. Although the storage stability and cured product properties of the prepreg were good and the thermal history was stable, the T (100) value of the epoxy resin composition was much longer than 70 minutes and 60 minutes, and the obtained prepreg The curing speed of was insufficient.
（比較例８）
樹脂組成をそれぞれ表５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、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表５に示した。エポキシ樹脂組成物のＴ（６０）の値が２４時間と２５時間未満であり、プリプレグの保管安定性は不十分であった。
(Comparative Example 8)
An epoxy resin composition, a prepreg, and a cured resin were prepared in the same manner as in Example 1 except that the resin composition was changed as shown in Table 5. The resin composition characteristics and evaluation results are shown in Table 5. The value of T (60) of the epoxy resin composition was 24 hours and less than 25 hours, and the storage stability of the prepreg was insufficient.
（比較例９）
樹脂組成をそれぞれ表５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、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表５に示した。プリプレグの保管安定性および硬化物特性は良好であり、熱履歴への安定性も有したが、エポキシ樹脂組成物のＴ（１００）の値が６５分と６０分より極めて長く、得られたプリプレグの硬化速度が不十分であった。
(Comparative Example 9)
An epoxy resin composition, a prepreg, and a cured resin were prepared in the same manner as in Example 1 except that the resin composition was changed as shown in Table 5. The resin composition characteristics and evaluation results are shown in Table 5. Although the storage stability and cured product properties of the prepreg were good and the thermal history was stable, the T (100) value of the epoxy resin composition was much longer than 65 minutes and 60 minutes, and the obtained prepreg was obtained. The curing speed of was insufficient.
（比較例１０）
樹脂組成をそれぞれ表５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、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表５に示した。エポキシ樹脂組成物のＴ（６０）の値が２２時間と２５時間未満であり、プリプレグの保管安定性は不十分であった。
(Comparative Example 10)
An epoxy resin composition, a prepreg, and a cured resin were prepared in the same manner as in Example 1 except that the resin composition was changed as shown in Table 5. The resin composition characteristics and evaluation results are shown in Table 5. The value of T (60) of the epoxy resin composition was 22 hours and less than 25 hours, and the storage stability of the prepreg was insufficient.
（比較例１１）
樹脂組成をそれぞれ表５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、プリプレグ、および樹脂硬化物を作製した。樹脂組成物特性および評価結果は表５に示した。エポキシ樹脂組成物のＴ（６０）の値が１３時間と２５時間未満であり、プリプレグの保管安定性は不十分であった。また、８０℃で１時間熱処理後のプリプレグの保管安定性を評価したところ、Ｔｇは４３℃と大きく上昇し、熱履歴への安定性は得られなかった。また、樹脂硬化物の弾性率と撓みのバランスが悪化し、ＣＦＲＰの９０°曲げ強度は７３ＭＰａと低いものであった。
(Comparative Example 11)
An epoxy resin composition, a prepreg, and a cured resin were prepared in the same manner as in Example 1 except that the resin composition was changed as shown in Table 5. The resin composition characteristics and evaluation results are shown in Table 5. The T (60) value of the epoxy resin composition was 13 hours and less than 25 hours, and the storage stability of the prepreg was insufficient. Further, when the storage stability of the prepreg after heat treatment at 80 ° C. for 1 hour was evaluated, the Tg greatly increased to 43 ° C., and stability to thermal history was not obtained. Further, the balance between the elastic modulus and the bending of the cured resin was deteriorated, and the 90 ° bending strength of CFRP was as low as 73 MPa.
本発明のエポキシ樹脂組成物は、保管安定性が極めて優れており、硬化したときの力学特性にも優れるため、繊維強化複合材料のマトリックス樹脂として好適に用いられる。また、本発明のプリプレグおよび繊維強化複合材料は、スポーツ用途、一般産業用途および航空宇宙用途に好ましく用いられる。 The epoxy resin composition of the present invention is excellent in storage stability and excellent in mechanical properties when cured, and therefore is suitably used as a matrix resin for fiber-reinforced composite materials. The prepreg and fiber-reinforced composite material of the present invention are preferably used for sports applications, general industrial applications, and aerospace applications.
Claims (9)
［Ａ］：エポキシ樹脂
［Ｂ］：ジシアンジアミド
［Ｃ］：芳香族ウレア
［Ｄ］：ホウ酸エステル
［ａ］：窒素気流下、１００℃の等温で示差走査熱量分析計によりエポキシ樹脂組成物を分析したとき、１００℃に達してから熱流量がピークトップに至るまでの時間が６０分以下
［ｂ］：窒素気流下、６０℃の等温で示差走査熱量分析計によりエポキシ樹脂組成物を分析したとき、６０℃に達してから熱流量がピークトップに至るまでの時間が２５時間以上 An epoxy resin composition comprising the following components [A], [B], [C], and [D] and satisfying the following conditions [a] and [b]:
[A]: Epoxy resin [B]: Dicyandiamide [C]: Aromatic urea [D]: Boric acid ester [a]: Analyzing the epoxy resin composition by differential scanning calorimetry at 100 ° C. under nitrogen flow When the epoxy resin composition is analyzed by a differential scanning calorimeter at 60 ° C. under a nitrogen stream at a time from the time when the temperature reaches 100 ° C. until the heat flow reaches the peak top, 60 minutes or less. , The time from reaching 60 ° C until the heat flow reaches the peak top is 25 hours or more
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| WO2019017365A1 (en) | 2017-07-21 | 2019-01-24 | 東レ株式会社 | Epoxy resin composition, prepreg, and fiber-reinforced composite material |
| JP2019023282A (en) * | 2017-07-21 | 2019-02-14 | 東レ株式会社 | Epoxy resin composition, prepreg, and fiber-reinforced composite material |
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