JP2003238657A - Epoxy resin composition, cured resin, prepreg and fiber reinforced composite material - Google Patents
Epoxy resin composition, cured resin, prepreg and fiber reinforced composite materialInfo
- Publication number
- JP2003238657A JP2003238657A JP2002036352A JP2002036352A JP2003238657A JP 2003238657 A JP2003238657 A JP 2003238657A JP 2002036352 A JP2002036352 A JP 2002036352A JP 2002036352 A JP2002036352 A JP 2002036352A JP 2003238657 A JP2003238657 A JP 2003238657A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- component
- weight
- parts
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 135
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 127
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 22
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 title claims description 42
- 239000011347 resin Substances 0.000 title claims description 42
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 150000004985 diamines Chemical class 0.000 claims abstract description 5
- 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 17
- 239000012783 reinforcing fiber Substances 0.000 claims description 16
- 239000011342 resin composition Substances 0.000 claims description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004305 biphenyl Substances 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 4
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920005649 polyetherethersulfone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 36
- 239000000047 product Substances 0.000 description 59
- 239000002131 composite material Substances 0.000 description 23
- 238000001723 curing Methods 0.000 description 22
- 230000009477 glass transition Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 239000005060 rubber Substances 0.000 description 13
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 229920003319 Araldite® Polymers 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- -1 glycidyl ester Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229920003295 Radel® Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Chemical group 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 239000011146 organic particle Substances 0.000 description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 2
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 2
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VAUOPRZOGIRSMI-UHFFFAOYSA-N n-(oxiran-2-ylmethyl)aniline Chemical class C1OC1CNC1=CC=CC=C1 VAUOPRZOGIRSMI-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- RSRRIQLNAWPWCJ-UHFFFAOYSA-N 1,1-dichloro-3,3-dimethylurea Chemical compound CN(C)C(=O)N(Cl)Cl RSRRIQLNAWPWCJ-UHFFFAOYSA-N 0.000 description 1
- WBQDXWRDENKVSJ-UHFFFAOYSA-N 1-(dichloromethyl)-3-methyl-1-phenylurea Chemical compound CNC(=O)N(C(Cl)Cl)C1=CC=CC=C1 WBQDXWRDENKVSJ-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- JBCUKQQIWSWEOK-UHFFFAOYSA-N 2-(benzenesulfonyl)aniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 JBCUKQQIWSWEOK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 102100029203 F-box only protein 8 Human genes 0.000 description 1
- 101100334493 Homo sapiens FBXO8 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 229920004748 ULTEM® 1010 Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011242 organic-inorganic particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006162 poly(etherimide sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はスポーツ用途、航空
機用途、一般産業用途に適した繊維強化複合材料、これ
を得るための中間基材であるプリプレグ、そのマトリッ
クス樹脂として好適に用いられるエポキシ樹脂組成物に
関するものである。TECHNICAL FIELD The present invention relates to a fiber reinforced composite material suitable for sports applications, aircraft applications and general industrial applications, a prepreg which is an intermediate base material for obtaining the fiber reinforced composite material, and an epoxy resin composition which is preferably used as its matrix resin. It is about things.
【０００２】[0002]
【従来の技術】近年、炭素繊維やアラミド繊維などを強
化繊維として用いた繊維強化複合材料は、その高い比強
度・比弾性率を利用して、航空機や自動車などの構造材
料や、テニスラケット、ゴルフシャフト、釣り竿などの
スポーツ・一般産業用途などに利用されてきた。繊推強
化複合材料の製造には、強化繊維に未硬化のマトリック
ス樹脂が含浸されたシート状中間基材であるプリプレグ
を用いる方法や、モールド中に並べた繊維に液状の樹脂
を流し込み硬化させるレジン・トランスファー・モール
ディング法などが用いられている。このうちプリプレグ
を用いる方法では、通常、プリプレグを複数枚積層した
後、加熱加圧することによって複合材料成形物を得てい
る。このプリプレグに用いられる樹脂としては生産性の
面から、熱硬化性樹脂、特にエポキシ樹脂が用いられる
ことが多い。2. Description of the Related Art In recent years, fiber-reinforced composite materials using carbon fibers, aramid fibers, etc. as reinforcing fibers utilize structural properties such as aircraft and automobiles, tennis rackets, and the like due to their high specific strength and elastic modulus. It has been used for sports and general industrial applications such as golf shafts and fishing rods. For the production of fiber-reinforced composite materials, a method of using a prepreg, which is a sheet-shaped intermediate base material in which uncured matrix resin is impregnated into reinforcing fibers, or a resin in which liquid resin is poured into the fibers arranged in a mold and cured -The transfer molding method is used. In the method using a prepreg, a composite material molded product is usually obtained by laminating a plurality of prepregs and then heating and pressing. From the viewpoint of productivity, a thermosetting resin, particularly an epoxy resin, is often used as the resin used in this prepreg.
【０００３】エポキシ樹脂からなるマトリックス樹脂は
優れた耐熱性と良好な機械物性を示す一方で、エポキシ
樹脂の伸度および／または靱性が熱可塑性樹脂に対して
低いため、複合材料としたとき、靱性や耐衝撃性が低く
なることが指摘され、改善を要求されてきた。特に、航
空機の一次構造材として利用する場合、離着陸時におけ
る小石の跳ね上げや整備時の工具の落下などの外部から
の衝撃によって破損する恐れがある。このため、複合材
料に衝撃後残存圧縮強度に代表される耐衝撃性を付与す
ることは重要な課題となっている。A matrix resin made of an epoxy resin exhibits excellent heat resistance and good mechanical properties, while the elongation and / or toughness of the epoxy resin is lower than that of a thermoplastic resin. It has been pointed out that the impact resistance is low and that the improvement has been demanded. In particular, when it is used as a primary structural material for an aircraft, it may be damaged by an external impact such as a pebbles bouncing at the time of takeoff and landing or a tool dropping during maintenance. Therefore, it is an important issue to impart impact resistance represented by the residual compressive strength after impact to the composite material.
【０００４】複合材料の耐衝撃性を上げるためには、複
合材料を構成する繊維の伸度やマトリックス樹脂の伸度
や靱性を向上させる必要がある。これらのうち、特にマ
トリックス樹脂の靱性を向上させることが重要かつ有効
であるとされ、エポキシ樹脂の改質が試みられてきた。In order to improve the impact resistance of the composite material, it is necessary to improve the elongation of the fibers constituting the composite material and the elongation and toughness of the matrix resin. Of these, it is considered to be important and effective to improve the toughness of the matrix resin, and attempts have been made to modify the epoxy resin.
【０００５】エポキシ樹脂の靱性を向上させる方法とし
ては靱性に優れるゴム成分や熱可塑性樹脂を配合する方
法などが試されてきた。As a method of improving the toughness of the epoxy resin, a method of blending a rubber component having excellent toughness and a thermoplastic resin has been tried.
【０００６】ゴム成分を配合することによりエポキシ樹
脂の靱性が改善されることは１９７０年代より検討され
ており、一般によく知られている。しかしながら、ゴム
成分は耐熱性低下や弾性率低下を引き起こす上、ゴム成
分による靱性改質効果を十分に得るためにはゴム成分を
多量に配合する必要がある。このため、エポキシ樹脂本
来の耐熱性や機械物性が低下し、良好な物性を有する複
合材料が得られないという欠点があった。It has been studied since the 1970s that the toughness of an epoxy resin is improved by blending a rubber component, and it is generally well known. However, the rubber component causes a decrease in heat resistance and a decrease in elastic modulus, and it is necessary to add a large amount of the rubber component in order to sufficiently obtain the effect of modifying the toughness by the rubber component. As a result, the heat resistance and mechanical properties inherent to the epoxy resin are deteriorated, and there is a drawback in that a composite material having good physical properties cannot be obtained.
【０００７】また、熱可塑性樹脂を配合する方法として
は、特公平６−４３５０８公報に述べられているように
熱可塑性樹脂をエポキシ樹脂に溶解、あるいは微粉末で
配合し溶解することにより樹脂中に均一に分散させる方
法があり、エポキシ樹脂の持つ機械物性を損なうことな
しに靱性を向上し、耐衝撃性に優れる複合材料が得られ
ることが知られている。しかし、一般的に熱可塑性樹脂
はエポキシ樹脂と相溶性が低く、得られる樹脂硬化物や
複合材料の機械物性が低下するという問題があった。ま
た、特公平６−５３７９１公報では高分子量固形ビスフ
ェノールＡ型エポキシ樹脂、ポリアリールエーテルスル
ホン、また、硬化剤としてジシアンジアミドを必須成分
とした樹脂組成物が開示されている。しかし、ジシアン
ジアミドは反応性が高いため、樹脂組成物の調製条件や
硬化条件によりエポキシ樹脂と熱可塑性樹脂との相溶性
が変化しやすく、これら樹脂間の界面接着性が低下する
恐れがあった。さらに、ジシアンジアミドを用いた樹脂
組成物の硬化物は機械物性、特に高温条件での機械物性
が不足することが多く、得られる複合材料の耐熱性が低
下する懸念があった。As a method of blending the thermoplastic resin, as described in Japanese Patent Publication No. 6-43508, the thermoplastic resin is dissolved in an epoxy resin, or a fine powder is blended and dissolved in the resin. It is known that there is a method of uniformly dispersing, and it is known that a composite material having improved impact resistance and improved toughness can be obtained without impairing the mechanical properties of the epoxy resin. However, the thermoplastic resin generally has low compatibility with the epoxy resin, and there is a problem that mechanical properties of the obtained resin cured product or composite material are deteriorated. Further, Japanese Patent Publication No. 6-53791 discloses a resin composition containing a high molecular weight solid bisphenol A type epoxy resin, polyaryl ether sulfone, and dicyandiamide as an essential component as a curing agent. However, since dicyandiamide is highly reactive, the compatibility between the epoxy resin and the thermoplastic resin is likely to change depending on the preparation conditions and curing conditions of the resin composition, and there is a risk that the interfacial adhesion between these resins may be reduced. Furthermore, the cured product of the resin composition using dicyandiamide often lacks mechanical properties, particularly under high temperature conditions, and there is a concern that the heat resistance of the resulting composite material may deteriorate.
【０００８】この欠点を改善する方法として、特公平６
−６８０１５公報では熱可塑性樹脂の末端官能基がエポ
キシ樹脂と反応性を持つものを用い、かつ硬化剤として
芳香族ジアミンを用いることにより前述問題を解決し、
エポキシ樹脂の靱性向上を行う方法が開示されている。
しかし、この方法においても、樹脂組成物の調製条件や
硬化条件によりエポキシ樹脂と熱可塑性樹脂との相溶性
が低下し、エポキシ樹脂と熱可塑性樹脂との界面接着性
低下に起因する樹脂硬化物の機械物性低下、ひいては複
合材料の機械物性低下の懸念は払拭されていない。As a method for improving this drawback, Japanese Patent Publication No.
In the -68015 publication, the above-mentioned problem is solved by using a thermoplastic resin having a terminal functional group reactive with an epoxy resin and using an aromatic diamine as a curing agent.
A method for improving the toughness of an epoxy resin is disclosed.
However, even in this method, the compatibility between the epoxy resin and the thermoplastic resin is reduced due to the preparation conditions and curing conditions of the resin composition, and the resin cured product resulting from the decrease in the interfacial adhesion between the epoxy resin and the thermoplastic resin The concern about deterioration of mechanical properties, and eventually of mechanical properties of composite materials, has not been eliminated.
【０００９】この相溶性不足を解決するために、特開平
２−２０２９１３公報では、フェノキシ樹脂や平均分子
量５，０００以上のエポキシ樹脂などを高分子量乳化剤
として用いる方法が提案されている。ところが、これら
高分子量乳化剤を配合すると樹脂組成物の粘度が高くな
り、樹脂組成物やプリプレグ製造時におけるプロセス性
や、得られるプリプレグの取り扱い性が悪くなるという
本質的な問題があった。In order to solve this lack of compatibility, JP-A-2-202913 proposes a method of using a phenoxy resin or an epoxy resin having an average molecular weight of 5,000 or more as a high molecular weight emulsifier. However, when these high molecular weight emulsifiers are blended, the viscosity of the resin composition becomes high, and there is an essential problem that the processability at the time of producing the resin composition and the prepreg and the handleability of the obtained prepreg are deteriorated.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、エポキシ樹
脂と熱可塑性樹脂との界面接着性に優れ、それにより優
れた靱性のみならず、高度な耐熱性および機械物性を有
し、かつプロセス性、取り扱い性に優れたエポキシ樹脂
組成物を提供することにある。DISCLOSURE OF THE INVENTION The present invention has excellent interfacial adhesion between an epoxy resin and a thermoplastic resin, whereby not only excellent toughness, but also high heat resistance and mechanical properties, and processability Another object of the present invention is to provide an epoxy resin composition having excellent handleability.
【００１１】[0011]
【課題を解決するための手段】上記課題を解決するため
に本発明は次の構成を有する。すなわち下記［Ａ］、
［Ｂ］、［Ｃ］および［Ｄ］の成分を含んでなるエポキ
シ樹脂組成物である。
［Ａ］分子中に少なくとも２個以上のエポキシ基を有
し、かつ平均分子量Ｍａが１５０以上８００以下である
エポキシ樹脂
［Ｂ］分子中に２個のエポキシ基を有し、平均分子量Ｍ
ｂが９００以上５０００以下であるエポキシ樹脂
［Ｃ］熱可塑性樹脂であって、その平均分子量Ｍｃが
［Ｂ］のエポキシ樹脂成分の分子量Ｍｂに対して、３≦
Ｍｃ／Ｍｂ≦１００を満たす熱可塑性樹脂
［Ｄ］分子内に芳香族環を有するジアミン硬化剤
または、上記エポキシ樹脂組成物を強化繊維に含浸して
なることを特徴とするプリプレグである。In order to solve the above problems, the present invention has the following constitution. That is, the following [A],
An epoxy resin composition containing the components [B], [C] and [D]. [A] Epoxy resin having at least two epoxy groups in the molecule and having an average molecular weight Ma of 150 or more and 800 or less [B] Having two epoxy groups in the molecule and having an average molecular weight M
It is an epoxy resin [C] thermoplastic resin in which b is 900 or more and 5000 or less, and 3 ≦ with respect to the molecular weight Mb of the epoxy resin component whose average molecular weight Mc is [B].
A thermoplastic resin [D] satisfying Mc / Mb ≦ 100 is a prepreg obtained by impregnating reinforcing fibers with a diamine curing agent having an aromatic ring in the molecule or with the above epoxy resin composition.
【００１２】さらには、上記エポキシ樹脂組成物を硬化
してなる樹脂硬化物と強化繊維からなることを特徴とす
る繊維強化複合材料である。Further, it is a fiber-reinforced composite material comprising a cured resin obtained by curing the above epoxy resin composition and a reinforcing fiber.
【００１３】[0013]
【発明の実施の形態】以下、本発明について詳細に説明
する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
【００１４】本発明の要するところは下記のごとく、マ
トリックス樹脂中に特定エポキシ樹脂、特定の熱可塑性
樹脂、および特定の硬化剤を用いることにより、エポキ
シ樹脂の機械物性を落とすことなく熱可塑性樹脂の耐衝
撃性を兼ね備え、かつ優れたプロセス性および取り扱い
性を有するエポキシ樹脂組成物となることを見出した点
にある。The point of the present invention is as follows, by using a specific epoxy resin, a specific thermoplastic resin, and a specific curing agent in the matrix resin, the thermoplastic resin can be formed without deteriorating the mechanical properties of the epoxy resin. It is a point to find out that the epoxy resin composition has impact resistance and excellent processability and handleability.
【００１５】本発明における［Ａ］成分は高い耐熱性お
よび高度の機械物性、特に高い弾性率を有する樹脂硬化
物を与えるために必要な成分である。The component [A] in the present invention is a component necessary for providing a cured resin product having high heat resistance and high mechanical properties, particularly high elastic modulus.
【００１６】［Ａ］成分は分子中に２個以上のエポキシ
基を有し、かつ、その平均分子量Ｍａが１５０以上８０
０以下のものであればどのようなものでも使用できる。The component [A] has two or more epoxy groups in the molecule and has an average molecular weight Ma of 150 or more and 80 or more.
Any one can be used as long as it is 0 or less.
【００１７】分子中に２個以上のエポキシ基を有するエ
ポキシ樹脂としては、例えば、分子内に水酸基を有する
化合物から得られるグリシジルエーテル型エポキシ樹
脂、分子内にアミノ基を有する化合物から得られるグリ
シジルアミン型エポキシ樹脂、分子内にカルボキシル基
を有する化合物から得られるグリシジルエステル型エポ
キシ樹脂、分子内に不飽和結合を有する化合物から得ら
れる環式脂肪族エポキシ樹脂、トリグリシジルイソシア
ネートなどの複素環式エポキシ樹脂、あるいはこれらか
ら選ばれる２種類以上のタイプが分子内に混在するエポ
キシ樹脂などを用いることができる。As the epoxy resin having two or more epoxy groups in the molecule, for example, a glycidyl ether type epoxy resin obtained from a compound having a hydroxyl group in the molecule, a glycidyl amine obtained from a compound having an amino group in the molecule Type epoxy resin, glycidyl ester type epoxy resin obtained from compound having carboxyl group in molecule, cycloaliphatic epoxy resin obtained from compound having unsaturated bond in molecule, heterocyclic epoxy resin such as triglycidyl isocyanate Alternatively, an epoxy resin in which two or more types selected from these are mixed in the molecule can be used.
【００１８】グリシジルエーテル型エポキシ樹脂の具体
例としては、ビスフェノールＡとエピクロロヒドリンの
反応により得られるビスフェノールＡ型エポキシ樹脂、
ビスフェノールＦとエピクロロヒドリンの反応により得
られるビスフェノールＦ型エポキシ樹脂、ビフェニルと
エピクロロヒドリンの反応により得られるビフェニル型
エポキシ樹脂、レゾルシノールとエピクロロヒドリンの
反応により得られるレゾルシノール型エポキシ樹脂、ビ
スフェノールＳとエピクロロヒドリンの反応により得ら
れるビスフェノールＳ型エポキシ樹脂、そのほかポリエ
チレングリコール型エポキシ樹脂、ポリプロピレングリ
コール型エポキシ樹脂、ナフタレン型エポキシ樹脂、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、およびこれらのハロゲンあるいは
アルキル置換体などが挙げられる。Specific examples of the glycidyl ether type epoxy resin include a bisphenol A type epoxy resin obtained by a reaction of bisphenol A and epichlorohydrin,
Bisphenol F type epoxy resin obtained by reaction of bisphenol F and epichlorohydrin, biphenyl type epoxy resin obtained by reaction of biphenyl and epichlorohydrin, resorcinol type epoxy resin obtained by reaction of resorcinol and epichlorohydrin, Bisphenol S type epoxy resin obtained by reaction of bisphenol S and epichlorohydrin, other polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and these And halogen- or alkyl-substituted products thereof.
【００１９】平均分子量Ｍａが１５０以上８００以下で
あるビスフェノールＡ型エポキシ樹脂の市販品として
は、エピコート（登録商標）８２５、エピコート８２
８、エピコート８３４（以上ジャパンエポキシレジン社
製）、エポトート（登録商標）ＹＤ-１２８(東都化成社
製)、ＤＥＲ−３３１（ダウケミカル社製）などが挙げ
られる。Commercially available bisphenol A type epoxy resins having an average molecular weight Ma of 150 to 800 are Epicoat (registered trademark) 825 and Epicoat 82.
8, Epicoat 834 (all manufactured by Japan Epoxy Resins Co., Ltd.), Epotote (registered trademark) YD-128 (manufactured by Toto Kasei Co., Ltd.), DER-331 (manufactured by Dow Chemical Co., Ltd.) and the like.
【００２０】平均分子量Ｍａが１５０以上８００以下で
あるビスフェノールＦ型エポキシ樹脂の市販品としては
エピコート８０６、エピコート８０７（以上ジャパンエ
ポキシレジン社製）、エピクロン（登録商標）８３０
(大日本インキ化学工業製)、エポトートＹＤ-１７０、
エポトートＹＤ−１７５(以上東都化成社製)などが挙げ
られる。Commercially available bisphenol F type epoxy resins having an average molecular weight Ma of 150 to 800 are Epicoat 806, Epicoat 807 (all manufactured by Japan Epoxy Resins Co., Ltd.) and Epicron (registered trademark) 830.
(Manufactured by Dainippon Ink and Chemicals), Epotote YD-170,
Epotote YD-175 (all manufactured by Tohto Kasei Co., Ltd.) and the like can be mentioned.
【００２１】平均分子量Ｍａが１５０以上８００以下で
あるビフェニル型エポキシ樹脂の市販品としてはエピコ
ートＹＸ４０００、エピコートＹＸ４０００Ｈ（以上ジ
ャパンエポキシレジン社製）などが挙げられる。Commercially available biphenyl type epoxy resins having an average molecular weight Ma of 150 or more and 800 or less include Epicoat YX4000 and Epicoat YX4000H (all manufactured by Japan Epoxy Resins Co., Ltd.).
【００２２】平均分子量Ｍａが１５０以上８００以下で
あるレゾルシノール型エポキシ樹脂の具体例としては、
ヘロキシ（登録商標）６９（ウイルミングトンケミカル
社製）、デナコール（登録商標）ＥＸ−２０１(ナガセ
ケムテックス製)などが挙げられる。Specific examples of the resorcinol type epoxy resin having an average molecular weight Ma of 150 or more and 800 or less include:
Heroxy (registered trademark) 69 (manufactured by Wilmington Chemical Co., Ltd.), Denacol (registered trademark) EX-201 (manufactured by Nagase Chemtex) and the like can be mentioned.
【００２３】グリシジルアミン型エポキシ樹脂の具体例
としては、テトラグリシジルジアミノジフェニルメタン
類、アミノフェノールのグリシジル化合物類、グリシジ
ルアニリン類などが挙げられる。Specific examples of the glycidyl amine type epoxy resin include tetraglycidyl diaminodiphenylmethanes, aminophenol glycidyl compounds and glycidyl anilines.
【００２４】平均分子量Ｍａが１５０以上８００以下で
あるテトラグリシジルジアミノジフェニルメタン類の市
販品としてはＥＬＭ４３４（住友化学社製）、アラルダ
イト（登録商標）ＭＹ７２０、アラルダイトＭＹ７２
１、アラルダイトＭＹ７２２、アラルダイトＭＹ９５１
２、アラルダイトＭＹ９６１２、アラルダイトＭＹ９６
３４、アラルダイトＭＹ９６６３（以上Ｖａｎｔｉｃｏ
社製）、エポトートＹＨ−４３４（東都化成社製）、エ
ピコート６０４（ジャパンエポキシレジン社製）などが
挙げられる。Commercially available tetraglycidyldiaminodiphenylmethanes having an average molecular weight Ma of 150 to 800 are ELM434 (Sumitomo Chemical Co., Ltd.), Araldite (registered trademark) MY720, Araldite MY72.
1, Araldite MY722, Araldite MY951
2, Araldite MY9612, Araldite MY96
34, Araldite MY9663 (above Vantico
Company), Epotote YH-434 (manufactured by Toto Kasei Co., Ltd.), Epicoat 604 (manufactured by Japan Epoxy Resins Co., Ltd.) and the like.
【００２５】平均分子量Ｍａが１５０以上８００以下で
あるアミノフェノールのグリシジル化合物類の市販品と
しては、ＥＬＭ１２０、ＥＬＭ１００（以上住友化学社
製）、エピコート６３０（ジャパンエポキシレジン社
製）、アラルダイトＭＹ０５００、アラルダイトＭＹ０
５１０（以上Ｖａｎｔｉｃｏ社製）などが挙げられる。Commercially available glycidyl compounds of aminophenol having an average molecular weight Ma of 150 or more and 800 or less are ELM120, ELM100 (all manufactured by Sumitomo Chemical Co., Ltd.), Epicoat 630 (manufactured by Japan Epoxy Resins Co., Ltd.), Araldite MY0500, Araldite. MY0
510 (above manufactured by Vantico) and the like.
【００２６】グリシジルアニリン類の市販品としては、
ＧＡＮ、ＧＯＴ（以上日本化薬製）などが挙げられる。Commercial products of glycidyl anilines include:
GAN, GOT (manufactured by Nippon Kayaku) and the like can be mentioned.
【００２７】平均分子量Ｍａが１５０以上８００以下で
あるグリシジルエステル型エポキシ樹脂の具体例として
は、フタル酸ジグリシジルエステルや、テレフタル酸ジ
グリシジルエステル、ヘキサヒドロフタル酸ジグリシジ
ルエステル、イソフタル酸ジグリシジルエステル、およ
びこれらのハロゲンあるいはアルキル置換体などが挙げ
られる。Specific examples of the glycidyl ester type epoxy resin having an average molecular weight Ma of 150 or more and 800 or less include phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and isophthalic acid diglycidyl ester. , And halogen- or alkyl-substituted products thereof.
【００２８】平均分子量Ｍａが１５０以上８００以下で
あるフタル酸ジグリシジルエステルの市販品としてはエ
ポミック（登録商標）Ｒ５０８（三井化学製）、デナコ
ールＥＸ−７２１（ナガセケムテックス製）などが挙げ
られる。Examples of commercially available phthalic acid diglycidyl ester having an average molecular weight Ma of 150 or more and 800 or less include Epomic (registered trademark) R508 (manufactured by Mitsui Chemicals) and Denacol EX-721 (manufactured by Nagase Chemtex).
【００２９】平均分子量Ｍａが１５０以上８００以下で
あるテレフタル酸ジグリシジルエステルの市販品として
はデナコールＥＸ−７１１（ナガセケムテックス製）が
挙げられる。As a commercial product of terephthalic acid diglycidyl ester having an average molecular weight Ma of 150 or more and 800 or less, Denacol EX-711 (manufactured by Nagase Chemtex) can be mentioned.
【００３０】平均分子量Ｍａが１５０以上８００以下で
あるヘキサヒドロフタル酸ジグリシジルエステルの市販
品としてはエポミックＲ５４０（三井化学製）、ＡＫ−
６０１（日本化薬）などが挙げられる。Commercially available hexahydrophthalic acid diglycidyl ester having an average molecular weight Ma of 150 to 800 is Epomic R540 (manufactured by Mitsui Chemicals), AK-
601 (Nippon Kayaku) and the like.
【００３１】平均分子量Ｍａが１５０以上８００以下で
ある脂環式エポキシ樹脂の市販品としては、セロキサイ
ド（登録商標）２０２１、セロキサイド２０８０（以上
ダイセル化学工業社製）、ＣＹ１７９（Ｖａｎｔｉｃｏ
社製）が挙げられる。Commercially available alicyclic epoxy resins having an average molecular weight Ma of 150 or more and 800 or less include Celoxide (registered trademark) 2021, Celoxide 2080 (all manufactured by Daicel Chemical Industries, Ltd.), and CY179 (Vantico).
Manufactured by the company).
【００３２】平均分子量Ｍａが１５０以上８００以下で
あるウレタン変性ビスフェノールＡ型エポキシ樹脂の市
販品としては、ＡＥＲ４１５２（旭化成エポキシ社製）
が挙げられる。これら[Ａ]成分のエポキシ樹脂は単独で
も混合物でも使用できる。耐熱性が必要な場合、グリシ
ジルアミン型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やアミノフェノールのグリシジル
化合物等のような耐熱性に優れたエポキシ樹脂が［Ａ］
成分１００重量部中に５０重量部以上用られていること
が望ましい。A commercially available urethane-modified bisphenol A type epoxy resin having an average molecular weight Ma of 150 or more and 800 or less is AER4152 (manufactured by Asahi Kasei Epoxy Co., Ltd.).
Is mentioned. These [A] component epoxy resins may be used alone or in a mixture. When heat resistance is required, an epoxy resin having excellent heat resistance such as tetraglycidyl diaminodiphenylmethane which is a glycidyl amine type epoxy resin or a glycidyl compound of aminophenol [A] is used.
It is desirable that 50 parts by weight or more be used in 100 parts by weight of the component.
【００３３】なお、本発明で言う平均分子量とは、ゲル
パーミエーションクロマトグラフィーによって得られる
数平均分子量のことを指す。数平均分子量の測定方法と
しては例えば、カラムに、Ｓｈｏｄｅｘ８０Ｍ（登録商
標、昭和電工製）２本と、Ｓｈｏｄｅｘ８０２（昭和電
工製）１本を用い、サンプルを０．３μＬ注入し、流速
１ｍＬ／ｍｉｎで測定したサンプルの保持時間を、ポリ
スチレンの校正用サンプルの保持時間を用いて分子量に
換算して求める方法などが使用できる。なお、液体クロ
マトグラフィーで複数のピークが観測される場合は、目
的成分を分離して個々のピークについて分子量の換算を
行うことができる。The average molecular weight referred to in the present invention means the number average molecular weight obtained by gel permeation chromatography. As a method for measuring the number average molecular weight, for example, two Shodex 80M (registered trademark, manufactured by Showa Denko) and one Shodex 802 (manufactured by Showa Denko) are used in a column, and 0.3 μL of a sample is injected at a flow rate of 1 mL / min. A method can be used in which the measured retention time of the sample is converted to a molecular weight using the retention time of the polystyrene calibration sample, and the like. When a plurality of peaks are observed by liquid chromatography, the target component can be separated and the molecular weight of each peak can be converted.
【００３４】本発明における［Ｂ］成分であるエポキシ
樹脂は、［Ａ］のエポキシ樹脂成分と［Ｃ］の熱可塑性
樹脂成分との相溶性を向上させ、エポキシ樹脂と熱可塑
性樹脂との高い界面接着性を実現することにより高度な
靱性を有する樹脂硬化物を得るために必要な成分であ
り、分子中に２個のエポキシ基を有し平均分子量Ｍｂが
９００以上５０００以下であるエポキシ樹脂であれば、
どのようなものでも良い。The epoxy resin which is the component [B] in the present invention improves the compatibility between the epoxy resin component of [A] and the thermoplastic resin component of [C], and provides a high interface between the epoxy resin and the thermoplastic resin. An epoxy resin which is a component necessary to obtain a resin cured product having a high degree of toughness by realizing adhesiveness, and which has two epoxy groups in the molecule and has an average molecular weight Mb of 900 or more and 5000 or less. If
Anything is fine.
【００３５】平均分子量Ｍｂが９００未満の場合、エポ
キシ樹脂と熱可塑性樹脂との界面接着性が不足すること
があり、十分な靱性の向上効果が得られないことがあ
る。一方、平均分子量Ｍｂが５０００を越える場合、樹
脂組成物の耐熱性などの機械物性が低下するばかりでな
く、プロセス性や取り扱い性が低下することがある。硬
化物の靱性の点から、さらに望ましくは平均分子量Ｍｂ
が１２００以上３０００以下である。If the average molecular weight Mb is less than 900, the interfacial adhesion between the epoxy resin and the thermoplastic resin may be insufficient, and a sufficient effect of improving toughness may not be obtained. On the other hand, when the average molecular weight Mb exceeds 5,000, not only the mechanical properties such as heat resistance of the resin composition are deteriorated, but also processability and handleability may be deteriorated. From the viewpoint of toughness of the cured product, more preferably the average molecular weight Mb.
Is 1200 or more and 3000 or less.
【００３６】分子中に２個以上のエポキシ基を有するエ
ポキシ樹脂としては、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、ビフェニル型エ
ポキシ樹脂、ポリエチレングリコール型エポキシ樹脂、
ポリプロピレングリコール型エポキシ樹脂、およびこれ
らのハロゲンあるいはアルキル置換体などが挙げられ
る。As the epoxy resin having two or more epoxy groups in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, polyethylene glycol type epoxy resin,
Examples thereof include polypropylene glycol type epoxy resins and halogen or alkyl substitution products thereof.
【００３７】中でも、高い界面接着性が得られる、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
キシ樹脂ならびに、ビフェニル型エポキシ樹脂がより好
ましい。Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin and biphenyl type epoxy resin, which can obtain high interfacial adhesion, are more preferable.
【００３８】平均分子量Ｍｂが９００以上５０００以下
であるビスフェノールＡ型エポキシ樹脂の市販品の具体
例としてはエピコート１００１、エピコート１００２、
エピコート１００３、エピコート１００４、エピコート
１００４ＡＦ、エピコート１００７、エピコート１００
９（以上ジャパンエポキシレジン社製）などが挙げられ
る。Specific examples of commercially available bisphenol A type epoxy resins having an average molecular weight Mb of 900 or more and 5000 or less include Epicoat 1001, Epicoat 1002,
Epicoat 1003, Epicoat 1004, Epicoat 1004AF, Epicoat 1007, Epicoat 100
9 (all manufactured by Japan Epoxy Resins Co., Ltd.) and the like.
【００３９】平均分子量Ｍｂが９００以上５０００以下
であるビスフェノールＦ型エポキシ樹脂の市販品の具体
例としてはエピコート４００４Ｐ、エピコート４００７
Ｐ、エピコート４００９Ｐ（以上ジャパンエポキシレジ
ン社製）、エポトートＹＤＦ２００１、エポトートＹＤ
Ｆ２００４（以上東都化成社製）などが挙げられる。Specific examples of commercially available bisphenol F type epoxy resins having an average molecular weight Mb of 900 or more and 5000 or less are Epicoat 4004P and Epicoat 4007.
P, Epicoat 4009P (all manufactured by Japan Epoxy Resins Co., Ltd.), Epotote YDF2001, Epotote YD
F2004 (above made by Tohto Kasei Co., Ltd.) and the like.
【００４０】平均分子量Ｍｂが９００以上５０００以下
であるビフェニル型エポキシ樹脂の市販品の具体例とし
てはエピコートＹＬ６６１６（ジャパンエポキシレジン
社製）が挙げられる。As a specific example of a commercially available biphenyl type epoxy resin having an average molecular weight Mb of 900 or more and 5000 or less, Epicoat YL6616 (manufactured by Japan Epoxy Resins Co., Ltd.) can be mentioned.
【００４１】平均分子量Ｍｂが９００以上５０００以下
であるポリエチレングリコール型エポキシ樹脂の市販品
の具体例としてはデナコールＥＸ−８６１（ナガセケム
テックス製）が挙げられる。Specific examples of commercially available polyethylene glycol type epoxy resins having an average molecular weight Mb of 900 or more and 5000 or less include Denacol EX-861 (manufactured by Nagase Chemtex).
【００４２】［Ｂ］成分の添加量は［Ａ］成分および
［Ｃ］成分の種類やその配合量にもよるが、［Ａ］成分
１００重量部に対して０．２重量部以上２５重量部以下
の範囲が好ましい。０．２重量部未満では［Ａ］成分と
［Ｃ］成分の界面を接着する効果が十分でない場合があ
り、また２５重量部を越えるとエポキシ樹脂組成物の耐
熱性が低下したり、粘度が高くなる恐れがある。０．２
重量部以上であれば十分な界面の接着効果が得られる
が、さらに望ましくは２重量部以上２５重量部以下であ
る。The amount of the component [B] added depends on the types of the components [A] and [C] and their blending amounts, but is 0.2 parts by weight or more and 25 parts by weight or more per 100 parts by weight of the component [A]. The following range is preferable. If the amount is less than 0.2 parts by weight, the effect of adhering the interface between the component [A] and the component [C] may not be sufficient, and if it exceeds 25 parts by weight, the heat resistance of the epoxy resin composition may be lowered and the viscosity may be low. There is a risk of becoming higher. 0.2
If it is at least parts by weight, a sufficient adhesive effect at the interface can be obtained, but more preferably at least 2 parts by weight and at most 25 parts by weight.
【００４３】本発明における［Ｃ］成分である熱可塑性
樹脂は高度な靱性を有する樹脂硬化物を与えるために必
要な成分であり、［Ｂ］のエポキシ樹脂成分の平均分子
量をＭｂとし、［Ｃ］の熱可塑性樹脂成分の平均分子量
をＭｃとしたとき、３≦Ｍｃ／Ｍｂ≦１００の範囲を満
たすことにより、［Ａ］のエポキシ樹脂成分と高い相溶
性を実現することができる成分である。［Ｃ］成分とし
て用いる熱可塑性樹脂としてはこの平均分子量範囲を満
たしていればどのようなものでも良い。Ｍｃ／Ｍｂが３
未満の場合、十分な靱性向上効果が得られないことがあ
り、Ｍｃ／Ｍｂが１００を越える場合、［Ａ］のエポキ
シ樹脂成分と［Ｃ］の熱可塑性樹脂成分の相溶性が低下
し、得られる樹脂硬化物の機械物性が低下することがあ
る。望ましくは、Ｍｃ／Ｍｂが３以上３０以下、より望
ましくは３以上２０以下である。The thermoplastic resin which is the component [C] in the present invention is a component necessary to give a cured resin product having a high degree of toughness, and the average molecular weight of the epoxy resin component [B] is Mb, and [C ] When the average molecular weight of the thermoplastic resin component is [Mc], by satisfying the range of 3 ≦ Mc / Mb ≦ 100, it is a component that can realize high compatibility with the epoxy resin component of [A]. Any thermoplastic resin may be used as the component [C] as long as it satisfies the average molecular weight range. Mc / Mb is 3
If it is less than 100%, a sufficient toughness improving effect may not be obtained, and if Mc / Mb exceeds 100, the compatibility of the epoxy resin component of [A] and the thermoplastic resin component of [C] decreases, and The mechanical properties of the cured resin obtained may deteriorate. Desirably, Mc / Mb is 3 or more and 30 or less, and more desirably 3 or more and 20 or less.
【００４４】なお、［Ｂ］成分を複数種用いる場合は、
少なくとも１つの［Ｂ］成分に対して［Ｃ］成分が３≦
Ｍｃ／Ｍｂ≦１００の関係を満たせば良く、全ての
［Ｂ］成分に対して３≦Ｍｃ／Ｍｂ≦１００を満たせば
より好ましい。When a plurality of kinds of the component [B] are used,
For at least one [B] component, the [C] component is 3 ≦
It is only necessary to satisfy the relationship of Mc / Mb ≦ 100, and it is more preferable to satisfy 3 ≦ Mc / Mb ≦ 100 for all [B] components.
【００４５】また［Ｃ］成分は複数種を用いることもで
きる。A plurality of kinds of the component [C] can be used.
【００４６】［Ｃ］成分として用いる熱可塑性樹脂とし
ては、得られる樹脂硬化物への靱性付与の観点から、平
均分子量Ｍｃが５０００以上１０００００以下の範囲に
あることが望ましい。熱可塑性樹脂は単独もしくは２種
以上のものを混合して用いてもよい。The thermoplastic resin used as the component [C] preferably has an average molecular weight Mc in the range of 5,000 to 100,000 from the viewpoint of imparting toughness to the cured resin obtained. The thermoplastic resins may be used alone or in combination of two or more.
【００４７】熱可塑性樹脂の種類としては、ポリエーテ
ルスルホン、ポリフェニルスルホン、ポリスルホン、ポ
リエーテルイミド、ポリフェニレンエーテル、ポリフェ
ニレンスルフィド、ポリカーボネート、ポリエーテルエ
ーテルケトン、ポリエーテルエーテルスルホンなどが挙
げられる。このうち、耐熱性、耐溶剤性や均一混合性の
面から、ポリエーテルスルホン、ポリフェニルスルホ
ン、ポリスルホン、ポリエーテルイミド、ポリエーテル
エーテルスルホンが望ましい。Examples of the thermoplastic resin include polyether sulfone, polyphenyl sulfone, polysulfone, polyether imide, polyphenylene ether, polyphenylene sulfide, polycarbonate, polyether ether ketone, and polyether ether sulfone. Of these, polyether sulfone, polyphenyl sulfone, polysulfone, polyetherimide, and polyether ether sulfone are preferable from the viewpoints of heat resistance, solvent resistance, and uniform mixing.
【００４８】これら熱可塑性樹脂の末端官能基として
は、第１級アミン、第２級アミン、水酸基、カルボキシ
ル基、チオール基、酸無水物やハロゲン類（塩素、臭
素）などのものが使用できる。このうち、保存安定性の
面からは、末端官能基はエポキシ樹脂との反応性が少な
いハロゲン類が望ましい。上記の末端官能基のうちハロ
ゲン類を除いたものは、エポキシ樹脂との反応性を有し
ている。これらの末端官能基がエポキシ樹脂と反応しう
る熱可塑性樹脂は、よりエポキシ樹脂と熱可塑性樹脂の
接着が必要な場合に好ましく用いられる。As the terminal functional group of these thermoplastic resins, primary amine, secondary amine, hydroxyl group, carboxyl group, thiol group, acid anhydride, halogens (chlorine, bromine) and the like can be used. Of these, halogens which are less reactive with the epoxy resin are desirable as the terminal functional group from the viewpoint of storage stability. The above-mentioned terminal functional groups excluding halogens have reactivity with epoxy resins. The thermoplastic resin whose terminal functional group can react with the epoxy resin is preferably used when more adhesion between the epoxy resin and the thermoplastic resin is required.
【００４９】ポリエーテルスルホンの市販品としては、
末端官能基が塩素のものとしてはスミカエクセル（登録
商標）３６００Ｐ、スミカエクセル４１００Ｐ、スミカ
エクセル５２００Ｐ、スミカエクセル７６００Ｐ、（以
上住友化学社製）、ＲＡＤＥＬ（登録商標）Ａ−１０
０、ＲＡＤＥＬ Ａ−２００、ＲＡＤＥＬ Ａ−３００
（以上ＢＰアモコ社製）などが挙げられ、末端官能基が
水酸基のものとしてはスミカエクセル５００３Ｐ（住友
化学社製）が挙げられる。Commercially available products of polyether sulfone include
As the terminal functional group having chlorine, SUMIKAEXCEL (registered trademark) 3600P, SUMIKAEXCEL 4100P, SUMIKAEXCEL 5200P, SUMIKAEXCEL 7600P (manufactured by Sumitomo Chemical Co., Ltd.), RADEL (registered trademark) A-10
0, RADEL A-200, RADEL A-300
(Above manufactured by BP Amoco) and the like, and as the terminal functional group having a hydroxyl group, SUMIKAEXCEL 5003P (manufactured by Sumitomo Chemical Co., Ltd.) can be mentioned.
【００５０】ポリフェニルスルホンの市販品としては末
端官能基が塩素のＲＡＤＥＬ Ｒ−５０００（ＢＰアモ
コ社製）などが挙げられる。Commercially available products of polyphenyl sulfone include RADEL R-5000 (made by BP Amoco) whose terminal functional group is chlorine.
【００５１】ポリスルホンの市販品としては末端官能基
が塩素のＵＤＥＬ（登録商標） Ｐ−１７００、ＵＤＥ
Ｌ Ｐ−３５００（以上ＢＰアモコ社製）などが挙げら
れる。Commercially available products of polysulfone include UDEL (registered trademark) P-1700 and UDE having chlorine as a terminal functional group.
LP-3500 (above manufactured by BP Amoco) and the like can be mentioned.
【００５２】またポリエーテルイミドの市販品としては
末端官能基がアミンと酸無水物の両方を含むＵｌｔｅｍ
（登録商標）１０００、Ｕｌｔｅｍ１０１０、Ｕｌｔｅ
ｍ１０４０(以上ジェネラル・エレクトリック社製)など
が挙げられる。このような熱可塑性樹脂の中から所望の
平均分子量のものを選択する。Further, as a commercially available product of polyetherimide, Ultem containing both an amine and an acid anhydride as a terminal functional group is used.
(Registered trademark) 1000, Ultem 1010, Ulte
m1040 (all manufactured by General Electric Co.) and the like. A thermoplastic resin having a desired average molecular weight is selected from such thermoplastic resins.
【００５３】［Ｃ］成分の添加量は［Ａ］成分および
［Ｂ］成分の種類や使用する熱可塑性樹脂の種類による
が、［Ａ］成分１００重量部に対して１２重量部以上６
０重量部以下であることが好ましい。１２重量部未満で
は十分な靭性向上効果が得られないことがあり、６０重
量部を越えるとエポキシ樹脂組成物の粘度が高くなり作
業性が低下する場合がある。より望ましくは２０重量部
以上４５重量部以下である.本発明における［Ｄ］成分
である硬化剤は、耐熱性および機械物性に優れた硬化物
を与え、かつ［Ｂ］のエポキシ樹脂成分と同時に用いる
ことにより［Ａ］のエポキシ樹脂成分と［Ｃ］の熱可塑
性樹脂成分との相溶性をより高めるために必要な成分で
あり、分子内に芳香族環を有するジアミン硬化剤であ
る。特に例示するならば、１−メチル−３，５−ジエチ
ル−２，６−ジアミノベンゼン、１−メチル−３，５−
ジエチル−２，４−ジアミノベンゼン、４，４’−ジア
ミノジフェニルスルホン、４，４’−ジアミノジフェニ
ルメタン、３，４’−ジアミノジフェニルスルホン、
３，４’−ジアミノジフェニルメタン、３，３’−ジア
ミノジフェニルスルホン、３，３’−ジアミノジフェニ
ルメタン、およびそれらの芳香族環の水素が炭素数３以
下のアルキル基あるいはハロゲン基により置換された誘
導体等が挙げられるが、これだけに限らない。このうち
エポキシ樹脂組成物の硬化物が高い機械物性を与える
３，３’−ジアミノジフェニルスルホン、３，４’−ジ
アミノジフェニルスルホン、４，４’−ジアミノジフェ
ニルスルホンが望ましい。さらに望ましくはエポキシ樹
脂組成物の硬化物に特に室温下および高温高湿下にて高
い弾性率および低い吸水率を与える３，３’−ジアミノ
ジフェニルスルホン、３，４’−ジアミノジフェニルス
ルホンである。硬化剤はモノマー、オリゴマーいずれの
形でも使用できる。他成分との混合時は粉体、液体いず
れの形態でも良く、粉体と液体のものを混合して用いて
も良い。The amount of the component [C] added depends on the types of the components [A] and [B] and the type of thermoplastic resin used, but is 12 parts by weight or more and 6 parts by weight or more per 100 parts by weight of the component [A].
It is preferably 0 parts by weight or less. If it is less than 12 parts by weight, a sufficient effect of improving the toughness may not be obtained, and if it exceeds 60 parts by weight, the viscosity of the epoxy resin composition may be increased and the workability may be deteriorated. More preferably 20 parts by weight or more and 45 parts by weight or less. The curing agent as the component [D] in the present invention gives a cured product excellent in heat resistance and mechanical properties, and at the same time as the epoxy resin component [B]. When used, it is a component necessary for further improving the compatibility between the epoxy resin component [A] and the thermoplastic resin component [C], and is a diamine curing agent having an aromatic ring in the molecule. As a specific example, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1-methyl-3,5-
Diethyl-2,4-diaminobenzene, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone,
3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, and derivatives in which the hydrogen of the aromatic ring is substituted with an alkyl group having 3 or less carbon atoms or a halogen group However, the present invention is not limited to this. Of these, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfone, which give a cured product of the epoxy resin composition high mechanical properties, are desirable. More desirable are 3,3′-diaminodiphenyl sulfone and 3,4′-diaminodiphenyl sulfone, which give a cured product of an epoxy resin composition a high elastic modulus and a low water absorption rate at room temperature and high temperature and high humidity. The curing agent can be used in either monomer or oligomer form. When mixed with other components, it may be in the form of powder or liquid, and powder and liquid may be mixed and used.
【００５４】［Ｄ］成分の添加量は用いる［Ａ］、
［Ｂ］成分の種類・量によって変わるが、［Ａ］成分１
００重量部に対して、２５重量部以上７０重量部以下の
範囲で配合することができる。２５重量部未満の場合、
十分な靱性が得られない場合があり、７０重量部を越え
る場合、機械物性が低下することがある。これらは単独
もしくは２種以上混合して用いても良い。The addition amount of the component [D] is [A],
Depending on the type and amount of [B] component, [A] component 1
It can be added in an amount of 25 parts by weight or more and 70 parts by weight or less with respect to 00 parts by weight. If less than 25 parts by weight,
In some cases, sufficient toughness may not be obtained, and if it exceeds 70 parts by weight, mechanical properties may deteriorate. You may use these individually or in mixture of 2 or more types.
【００５５】また、必要に応じて、［Ｄ］成分以外のエ
ポキシ樹脂硬化剤や硬化促進剤を併用することも可能で
ある。［Ｄ］成分以外のエポキシ樹脂硬化剤の例として
はイソホロンジアミンなどの脂環式アミンやジシアンジ
アミドなどが、また硬化促進剤としてはジクロロジメチ
ルウレアなどの尿素化合物、イミダゾール類、３級アミ
ン、有機金属塩などをそれぞれ挙げることができる。If necessary, an epoxy resin curing agent or a curing accelerator other than the component [D] can be used in combination. Examples of epoxy resin curing agents other than the component [D] include alicyclic amines such as isophoronediamine and dicyandiamide, and examples of curing accelerators include urea compounds such as dichlorodimethylurea, imidazoles, tertiary amines, and organic metals. Salt and the like can be mentioned respectively.
【００５６】本発明の樹脂組成物には、必要に応じて、
上記［Ａ］〜［Ｄ］成分のほかに有機粒子、無機粒子な
どの粒子や、平均分子量が５０００を超えるエポキシ樹
脂や分子中に1個のエポキシ基を持つエポキシ樹脂など
の［Ａ］成分および［Ｂ］成分以外のエポキシ樹脂や、
シアネートエステル樹脂、ビスマレイミド樹脂、ベンゾ
オキサジン樹脂、フェノール樹脂、ウレタン樹脂、ユリ
ア樹脂などの熱硬化性樹脂や、樹脂組成物の機械物性を
損なわない範囲で、粘度調整などのために、[Ｃ]成分と
は異なる熱可塑性樹脂などを少量添加することも可能で
ある。In the resin composition of the present invention, if necessary,
In addition to the above [A] to [D] components, particles such as organic particles and inorganic particles, [A] components such as epoxy resins having an average molecular weight of more than 5000 and epoxy resins having one epoxy group in the molecule, and Epoxy resin other than [B] component,
Cyanine ester resin, bismaleimide resin, benzoxazine resin, phenol resin, urethane resin, urea resin and other thermosetting resins, and to adjust the viscosity, etc. to the extent that the mechanical properties of the resin composition are not impaired, [C] It is also possible to add a small amount of a thermoplastic resin different from the components.
【００５７】本発明では、樹脂の靭性や、得られる複合
材料の耐衝撃性をさらに高めるため、エポキシ樹脂組成
物にゴム粒子および熱可塑性樹脂粒子等の有機粒子を配
合することができる。In the present invention, in order to further improve the toughness of the resin and the impact resistance of the resulting composite material, organic particles such as rubber particles and thermoplastic resin particles can be added to the epoxy resin composition.
【００５８】ゴム粒子としては、架橋ゴム粒子、および
架橋ゴム粒子の表面に異種ポリマーをグラフト重合した
コアシェルゴム粒子が、取り扱い性等の観点から好まし
く用いられる。As the rubber particles, crosslinked rubber particles and core-shell rubber particles obtained by graft-polymerizing a different polymer on the surface of the crosslinked rubber particles are preferably used from the viewpoint of handleability and the like.
【００５９】架橋ゴム粒子の市販品としては、カルボキ
シル変性のブタジエン−アクリロニトリル共重合体の架
橋物からなるＸＥＲ−９１（型番、日本合成ゴム工業社
製）、アクリルゴム微粒子からなるＣＸ−ＭＮシリーズ
（型番、日本触媒製）、ＹＲ−５００シリーズ（型番、
東都化成製）等を使用することができる。Commercially available crosslinked rubber particles include XER-91 (model number, manufactured by Japan Synthetic Rubber Industry Co., Ltd.), which is a crosslinked product of a carboxyl-modified butadiene-acrylonitrile copolymer, and CX-MN series (which is made of acrylic rubber fine particles). Model number, manufactured by Nippon Shokubai, YR-500 series (model number,
Toto Kasei) etc. can be used.
【００６０】コアシェルゴム粒子の市販品としては、例
えば、ブタジエン・メタクリル酸アルキル・スチレン共
重合物からなるパラロイド（登録商標）ＥＸＬ−２６５
５（呉羽化学工業製）、アクリル酸エステル・メタクリ
ル酸エステル共重合体からなるスタフィロイド（登録商
標）ＡＣ−３３５５、ＴＲ−２１２２（以上武田薬品工
業製）、アクリル酸ブチル・メタクリル酸メチル共重合
物からなるＰＡＲＡＬＯＩＤ（登録商標）ＥＸＬ−２６
１１、ＥＸＬ−３３８７（以上Ｒｏｈｍ＆Ｈａａｓ社
製）等を使用することができる。Examples of commercially available core-shell rubber particles include, for example, Paraloid (registered trademark) EXL-265 made of a butadiene / alkyl methacrylate / styrene copolymer.
5 (manufactured by Kureha Chemical Industry Co., Ltd.), Staphyloid (registered trademark) AC-3355 composed of an acrylic acid ester / methacrylic acid ester copolymer, TR-2122 (all manufactured by Takeda Pharmaceutical Co., Ltd.), butyl acrylate / methyl methacrylate copolymerized PARALOID (registered trademark) EXL-26
11, EXL-3387 (all manufactured by Rohm & Haas) and the like can be used.
【００６１】熱可塑性樹脂粒子としては、ポリアミド粒
子やポリイミド粒子が好ましく用いられ、ポリアミド粒
子の市販品として、ＳＰ−５００（型番、東レ製）、オ
ルガソール（登録商標、ＡＴＯＣＨＥＭ社製）等を使用
することができる。As the thermoplastic resin particles, polyamide particles or polyimide particles are preferably used, and as commercially available polyamide particles, SP-500 (model number, manufactured by Toray), Orgasol (registered trademark, manufactured by ATOCHEM), etc. are used. can do.
【００６２】本発明における、ゴム粒子および熱可塑性
樹脂粒子等の有機粒子の配合量は、得られる樹脂硬化物
の弾性率と靱性を両立させる点から、[Ａ]成分と[Ｂ]成
分を合計した重量部１００重量部に対して、０．１重量
部以上５０重量部以下が好ましく、１重量部以上３５重
量部以下配合するのがさらに好ましい。In the present invention, the compounding amount of the organic particles such as rubber particles and thermoplastic resin particles is such that the total amount of the [A] component and the [B] component is in consideration of achieving both the elastic modulus and toughness of the obtained resin cured product. 0.1 part by weight or more and 50 parts by weight or less is preferable, and 1 part by weight or more and 35 parts by weight or less is more preferably blended with 100 parts by weight of the above.
【００６３】本発明では、樹脂組成物の増粘等の粘弾性
制御、揺変性付与のため、エポキシ樹脂組成物にシリ
カ、アルミナ、スメクタイト、合成マイカ等の無機粒子
を配合することができる。In the present invention, in order to control viscoelasticity such as thickening of the resin composition and impart thixotropy, inorganic particles such as silica, alumina, smectite and synthetic mica can be blended with the epoxy resin composition.
【００６４】本発明では、無機粒子はエポキシ樹脂組成
物に適度な粘弾性を与え、優れた取り扱い性のプリプレ
グ、良質な複合材料が得られるため、[Ａ]成分と[Ｂ]成
分を合計した重量部１００重量部に対して、好ましくは
０．００１重量部以上２０重量部以下、より好ましくは
０．０１重量部以上１０重量部以下配合するのが好まし
い。In the present invention, the inorganic particles give the epoxy resin composition an appropriate viscoelasticity, and a prepreg having excellent handleability and a good quality composite material can be obtained. Therefore, the components [A] and [B] are added together. It is preferable to add 0.001 parts by weight or more and 20 parts by weight or less, more preferably 0.01 parts by weight or more and 10 parts by weight or less to 100 parts by weight.
【００６５】本発明の樹脂組成物を加熱硬化せしめて得
られる硬化物（以下硬化物という）のガラス転移温度は
１５０℃以上２５０℃以下であることが好ましい。より
好ましくは１７０℃以上２３０℃以下であり、特に好ま
しくは１７５℃以上２２０℃以下である。硬化物のガラ
ス転移温度が２５０℃を超えると、繊維強化複合材料に
残留する熱応力が大きくなったり、硬化物が脆くなりが
ちであり、得られる繊維強化複合材料の強度特性が低下
する場合がある。The glass transition temperature of a cured product (hereinafter referred to as a cured product) obtained by heating and curing the resin composition of the present invention is preferably 150 ° C. or higher and 250 ° C. or lower. The temperature is more preferably 170 ° C or higher and 230 ° C or lower, and particularly preferably 175 ° C or higher and 220 ° C or lower. If the glass transition temperature of the cured product exceeds 250 ° C., the thermal stress remaining in the fiber-reinforced composite material tends to be large, or the cured product tends to be brittle, and the strength characteristics of the resulting fiber-reinforced composite material may deteriorate. is there.
【００６６】ガラス転移温度が１５０℃未満であると、
繊維強化複合材料に成形後、表面を研磨するとき、熱に
より軟化した樹脂が研磨機に目詰まりを起こさせる場合
があったり、材料として使用時に熱による変形を起こし
やすくなる場合がある。When the glass transition temperature is less than 150 ° C.,
When the surface is polished after being molded into a fiber-reinforced composite material, the resin softened by heat may cause clogging of the polishing machine, or may be easily deformed by heat when used as a material.
【００６７】なお、ガラス転移温度は、樹脂組成物を１
２０℃〜２３０℃の範囲から選ばれる一定温度で１２０
〜１８０分間加熱処理して得られる硬化物について、示
差走査熱量測定法（ＤＳＣ）によって測定される値であ
る。The glass transition temperature is 1 for the resin composition.
120 at a constant temperature selected from the range of 20 ° C to 230 ° C
It is a value measured by differential scanning calorimetry (DSC) for a cured product obtained by heat treatment for 180 minutes.
【００６８】また、繊維強化複合材料から切り出したサ
ンプルについて測定することによって、繊維強化複合材
料に含まれる樹脂硬化物のガラス転移温度を測定でき
る。The glass transition temperature of the resin cured product contained in the fiber reinforced composite material can be measured by measuring the sample cut out from the fiber reinforced composite material.
【００６９】さらに、本発明の樹脂組成物は、硬化物の
靭性が０．９０〜１．８０ＭＰａ・ｍ-1/2であることが
好ましい。ここで、硬化物の靭性とは変形モードＩ（開
口型）の臨界応力強度のことを指し、後述するようにＡ
ＳＴＭ Ｄ５０４５に従って求めることができる値であ
る。一般的にこの値が大きいほど硬化物の靱性ならびに
耐衝撃性は高くなる。かかる硬化物の靭性が０．９０未
満であると繊維強化複合材料の耐衝撃性例えば衝撃付与
後の残存圧縮強度などが不足する場合があり、１．８０
を超えると切削性など加工性が低下して繊維強化複合材
料の機械物性の低下をまねく場合がある。Further, the resin composition of the present invention preferably has a toughness of a cured product of 0.90 to 1.80 MPa · m −1/2 . Here, the toughness of the cured product refers to the critical stress intensity of the deformation mode I (open type), and as described later, A
It is a value that can be obtained according to STM D5045. Generally, the larger this value, the higher the toughness and impact resistance of the cured product. If the toughness of such a cured product is less than 0.90, the impact resistance of the fiber-reinforced composite material, for example, the residual compressive strength after impact may be insufficient, and may be 1.80.
If it exceeds, the machinability such as machinability may be deteriorated and the mechanical properties of the fiber-reinforced composite material may be deteriorated.
【００７０】本発明のプリプレグに用いる強化繊維とし
ては、ガラス繊維、炭素繊維、黒鉛繊維、アラミド繊
維、ボロン繊維、アルミナ繊維、炭化ケイ素繊維等が好
ましく用いられる。これらの繊維を２種以上混合して用
いても構わないが、より軽量で、より耐久性の高い成形
品を得るために、炭素繊維や黒鉛繊維を用いるのが良
い。As the reinforcing fiber used in the prepreg of the present invention, glass fiber, carbon fiber, graphite fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like are preferably used. Two or more kinds of these fibers may be mixed and used, but it is preferable to use carbon fiber or graphite fiber in order to obtain a molded product that is lighter and has higher durability.
【００７１】本発明においては、用途に応じてあらゆる
種類の炭素繊維や黒鉛繊維を用いることが可能である
が、耐衝撃性に優れ、高い剛性および機械強度を有する
複合材料が得られることから、ＪＩＳ Ｒ７６０１に記
載の方法によるストランド引張試験における引張弾性率
が２００ＧＰａ以上、引張強度４ ．４ＧＰａ以上 、引
張伸度１ ．７％以上の高強度高伸度炭素繊維が最も適
している。In the present invention, all kinds of carbon fibers and graphite fibers can be used depending on the application, but since a composite material having excellent impact resistance, high rigidity and mechanical strength can be obtained, 3. A tensile elastic modulus in a strand tensile test according to the method described in JIS R7601 is 200 GPa or more, and a tensile strength is 4. 4 GPa or more, tensile elongation 1. High strength and high elongation carbon fiber of 7% or more is most suitable.
【００７２】強化繊維の形態は特に限定されるものでは
なく、例えば、一方向に引き揃えた長繊維、トウ、織
物、マット、ニット、組み紐などが用いられる。また、
特に、比強度、比弾性率が高いことを要求される用途に
は強化繊維が単一方向に引き揃えられた配列が最も適し
ているが、取り扱いの容易な織物状の配列も本発明には
適している。The form of the reinforcing fiber is not particularly limited, and for example, unidirectionally aligned long fibers, tows, woven fabrics, mats, knits, braids and the like can be used. Also,
In particular, the arrangement in which the reinforcing fibers are aligned in a single direction is most suitable for applications requiring high specific strength and high specific elastic modulus, but a woven fabric arrangement that is easy to handle is also included in the present invention. Are suitable.
【００７３】本発明のプリプレグは、マトリックス樹脂
をメチルエチルケトン、メタノール等の溶媒に溶解して
低粘度化し、含浸させるウェット法と、加熱により低粘
度化し、含浸させるホットメルト法（ドライ法）等によ
り作製することができる。The prepreg of the present invention is prepared by a wet method in which a matrix resin is dissolved in a solvent such as methyl ethyl ketone or methanol to reduce its viscosity and then impregnated, and a hot melt method (dry method) in which it is reduced in viscosity by heating and impregnated. can do.
【００７４】ウェット法は、強化繊維をエポキシ樹脂組
成物の溶液に浸漬した後、引き上げ、オーブン等を用い
て溶媒を蒸発させる方法であり、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、または一旦エポキシ樹脂組成物を
離型紙等の上に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。ホットメルト法によれば、プリプレ
グ中に残留する溶媒が実質上皆無となるため好ましい。The wet method is a method in which the reinforcing fiber is dipped in a solution of the epoxy resin composition, then pulled up, and the solvent is evaporated using an oven or the like. The hot melt method is an epoxy resin composition whose viscosity is reduced by heating. By directly impregnating the reinforcing fiber with the product, or by once preparing a film in which the epoxy resin composition is coated on the release paper or the like, and then stacking the film from both sides or one side of the reinforcing fiber, and heating and pressing. This is a method of impregnating a reinforcing fiber with a resin. According to the hot melt method, the solvent remaining in the prepreg is substantially eliminated, which is preferable.
【００７５】得られたプリプレグを積層後、積層物に圧
力を付与しながら樹脂を加熱硬化させる方法等により、
本発明による複合材料が作製される。After the obtained prepregs are laminated, the resin is heat-cured while applying pressure to the laminate, and the like.
A composite material according to the present invention is made.
【００７６】ここで熱および圧力を付与する方法には、
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、内圧成形法等が採用されるな
お、本発明の繊維強化複合材料は、プリプレグを介さ
ず、エポキシ樹脂組成物を直接強化繊維に含浸させた
後、加熱硬化せしめる方法、例えばハンド・レイアップ
法、フィラメント・ワインディング法、プルトルージョ
ン法、レジン・インジェクション・モールディング法、
レジン・トランスファー・モールディング法等の成形法
によっても作製できる。これらの方法では、エポキシ樹
脂からなる主剤と硬化剤との２液を使用直前に混合して
樹脂組成物を調製するのが好ましい。Here, the method of applying heat and pressure includes
A press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, or the like is adopted.The fiber-reinforced composite material of the present invention directly impregnates a reinforcing fiber with an epoxy resin composition without using a prepreg. After curing, heat curing, for example, hand layup method, filament winding method, pultrusion method, resin injection molding method,
It can also be produced by a molding method such as a resin transfer molding method. In these methods, it is preferable to prepare a resin composition by mixing two liquids of a main agent composed of an epoxy resin and a curing agent immediately before use.
【００７７】[0077]
【実施例】エポキシ樹脂硬化物の靱性試験方法はインス
トロン万能試験機（インストロン社製）を用い、ＡＳＴ
Ｍ Ｄ５０４５に従って実験を行った。ここで樹脂硬化
物の靱性は変形モードＩ（開口型）の臨界応力強度のこ
とを指すものである。硬化物のガラス転移温度はＤＳＣ
法で測定した。ここでは、ＴＡインスツルメンツ社製Ｄ
ＳＣ２９１０を用い、昇温速度１０℃／ｍｉｎで測定し
た。[Example] The toughness test method of the cured epoxy resin is ASTRON universal testing machine (manufactured by Instron Co., Ltd.)
Experiments were conducted according to MD 5045. Here, the toughness of the cured resin refers to the critical stress intensity of deformation mode I (open type). The glass transition temperature of the cured product is DSC
It was measured by the method. Here, D manufactured by TA Instruments
It measured using SC2910 at a temperature rising rate of 10 ° C./min.
【００７８】プリプレグは、以下の様に作成した。未硬
化の樹脂組成物をナイフコーターを用いてフィルム化
し、このフィルム上に炭素繊維トレカ（登録商標）Ｔ８
００Ｈ（東レ社製、引張弾性率２９０ＧＰａ、引張強度
５．９ＧＰａ）を並べ、加熱、含浸させて得られた炭素
繊維目付１９０ｇ／ｍ2、樹脂含有率３６重量％の一方
向プリプレグを得た。The prepreg was prepared as follows. The uncured resin composition is formed into a film by using a knife coater, and carbon fiber Torayca (registered trademark) T8 is formed on the film.
00H (manufactured by Toray Industries, Inc., tensile elastic modulus 290 GPa, tensile strength 5.9 GPa) were arranged, heated and impregnated to obtain a carbon fiber basis weight of 190 g / m 2 and a resin content of 36% by weight of a unidirectional prepreg.
【００７９】コンポジットの耐衝撃性試験は、以下の様
にして行った。ここでコンポジットの耐衝撃性とは、衝
撃後の残存圧縮強度のことを指す。The impact resistance test of the composite was performed as follows. Here, the impact resistance of the composite refers to the residual compressive strength after impact.
【００８０】プリプレグを（＋４５°／０°／−４５°
／９０°）３ｓ構成で、疑似等方的に２４枚積層し、オ
ートクレーブにて、成形し積層体を作製した。この積層
体から、縦１５０ｍｍ×横１００ｍｍの試験片を切り出
し、ＡＳＴＭ Ｄ６９５に従い、ガードナー衝撃装置を
用いて試験片の中心部に６．７Ｊ／ｍｍの落錘衝撃を与
え、インストロン万能試験機を用いて衝撃後の圧縮強度
を求めた。
（実施例１）［Ａ］成分としてＥＬＭ４３４（平均分子
量５００）を５０重量部と、エピコート６３０（平均分
子量３００）とＧＡＮ（平均分子量２５０）をそれぞれ
２５重量部、［Ｂ］成分としてエピコート１００４（平
均分子量１８００）を１０重量部、［Ｃ］成分としてス
ミカエクセル３６００Ｐ（末端塩素、平均分子量１６０
００）を３５重量部混合し、１５０℃で１時間加熱撹拌
を行い透明な粘稠液を得た。この組成物を冷却し、温度
が７０℃以下になったところで［Ｄ］成分として３，
３’−ジアミノジフェニルスルホン５６重量部を加え均
一に拡散させて得た組成物をモールド中で１８０℃で２
時間硬化させ硬化物を得た。このとき硬化物の靱性は
１．１２ＭＰａ・ｍ-1/2であり、ガラス転移温度は１９
９℃であった。また、昇温速度１．５℃／分とし０．５
９ＭＰａの圧力下、１８０℃で２時間で硬化させたコン
ポジットの耐衝撃性は２４０ＭＰａ・ｍｍ-2であった。
結果を表１に示す。
（実施例２）［Ａ］成分としてＥＬＭ４３４を４５重量
部とエピコート６３０を２５重量部、ＧＡＮを３０重量
部、［Ｂ］成分としてエピコート４００４Ｐ（平均分子
量１６００）を１０重量部、［Ｃ］成分としてスミカエ
クセル３６００Ｐを３５重量部混合し、１５０℃で１時
間加熱撹拌を行い透明な粘稠液を得た。この組成物を冷
却し、温度が７０℃以下になったところで［Ｄ］成分と
して３，３’−ジアミノジフェニルスルホン５０重量部
を加え均一に拡散させて得た組成物をモールド中で１８
０℃で２時間硬化させ硬化物を得た。この硬化物の靱性
は１．１０ＭＰａ・ｍ-1/2であり、ガラス転移温度は１
９５℃であった。また、昇温速度１．５℃／分とし０．
５９ＭＰａの圧力下、１８０℃で２時間で硬化させたコ
ンポジットの耐衝撃性を測定したところ、２４０ＭＰａ
・ｍｍ-2であった。結果を表１に示す。また、この樹脂
を１００℃で１時間、１８０℃で３時間の硬化条件で硬
化させたところ、靱性は１．１０ＭＰａ・ｍ-1/2であ
り、ガラス転移温度は１９６℃であった。さらに、昇温
速度１．５℃／分とし０．５９ＭＰａの圧力下、１００
℃で１時間、１８０℃で３時間硬化させたコンポジット
の耐衝撃性は２４０ＭＰａ・ｍｍ-2となり、硬化条件に
よる機械物性の低下は見られなかった。
（実施例３）［Ａ］成分としてＥＬＭ４３４とエピコー
ト６３０をそれぞれ５０重量部と、［Ｂ］成分としてエ
ピコート１００４を３重量部、［Ｃ］成分としてスミカ
エクセル５２００Ｐ（末端塩素、平均分子量３５００
０）を３０重量部混合し、１５０℃で１時間加熱撹拌を
行い透明な粘稠液を得た。この組成物を冷却し、温度が
７０℃以下になったところで［Ｄ］成分の３，３’−ジ
アミノジフェニルスルホン３４．６重量部を均一に拡散
させて得た組成物をモールド中で１８０℃で２時間硬化
させ硬化物を得た。この硬化物の靱性は１．０８ＭＰａ
・ｍ-1 /2であっり、ガラス転移温度は２０４℃であっ
た。また、昇温速度１．５℃／分とし０．５９ＭＰａの
圧力下、１８０℃で２時間で硬化させたコンポジットの
耐衝撃性を測定したところ、２３５ＭＰａ・ｍｍ-2であ
った。結果を表１に示す。
（実施例４）［Ａ］成分としてＥＬＭ４３４を５０重量
部とエピコート６３０を２５重量部、ＧＡＮを２５重量
部、［Ｂ］成分としてエピコート４００７Ｐ（平均分子
量４０００）を１０重量部、［Ｃ］成分としてスミカエ
クセル３６００Ｐを３５重量部混合し、１５０℃で１時
間加熱撹拌を行い透明な粘稠液を得た。この組成物を冷
却し、温度が７０℃以下になったところで［Ｄ］成分と
して３，３’−ジアミノジフェニルスルホン５６重量部
を加え均一に拡散させて得た組成物をモールド中で１８
０℃で２時間硬化させ硬化物を得た。この硬化物の靱性
は１．０８ＭＰａ・ｍ-1/2であっり、ガラス転移温度は
２００℃であった。また、昇温速度１．５℃／分とし
０．５９ＭＰａの圧力下、１８０℃で２時間で硬化させ
たコンポジットの耐衝撃性を測定したところ、２３５Ｍ
Ｐａ・ｍｍ-2であった。結果を表１に示す。
（実施例５）［Ａ］成分としてＥＬＭ４３４を５０重量
部とエピコート６３０を２５重量部、ＧＡＮを２５重量
部、［Ｂ］成分としてエピコートＹＬ６６１６（平均分
子量１０００）を１０重量部、［Ｃ］成分としてスミカ
エクセル３６００Ｐを３５重量部混合し、１５０℃で１
時間加熱撹拌を行い透明な粘稠液を得た。この組成物を
冷却し、温度が７０℃以下になったところで［Ｄ］成分
として３，３’−ジアミノジフェニルスルホン５７．２
重量部を加え均一に拡散させて得た組成物をモールド中
で１８０℃で２時間硬化させ硬化物を得た。この硬化物
の靱性は１．０６ＭＰａ・ｍ-1/2であり、ガラス転移温
度は２０９℃であった。また、昇温速度１．５℃／分と
し０．５９ＭＰａの圧力下、１８０℃で２時間で硬化さ
せたコンポジットの耐衝撃性を測定したところ、２３５
ＭＰａ・ｍｍ-2であった。結果を表１に示す。
（実施例６）［Ａ］成分としてＥＬＭ４３４を９０重量
部と、エポトートＹＤ−１２８（平均分子量３５０）を
１０重量部加え［Ｂ］成分としてエピコート１００４を
３重量部、［Ｃ］成分としてスミカエクセル５００３Ｐ
（末端水酸基、平均分子量３００００）を３５重量部混
合し、１５０℃で１時間加熱撹拌を行い透明な粘稠液を
得た。この組成物を冷却し、温度が７０℃以下になった
ところで、［Ｄ］成分として４，４’−ジアミノジフェ
ニルスルホン４４重量部を加え均一に拡散させて得た組
成物をモールド中で１８０℃で２時間硬化させ硬化物を
得た。このとき硬化物の靱性は１．０５ＭＰａ・ｍ-1/2
であり、ガラス転移温度は２０８℃であった。また、昇
温速度１．５℃／分とし０．５９ＭＰａの圧力下、１８
０℃で２時間で硬化させたコンポジットの耐衝撃性を測
定したところ、２３０ＭＰａ・ｍｍ-2であった。結果を
表２に示す。
（実施例７）［Ａ］成分としてエピコート６３０を５０
重量部と、ＧＡＮを５０重量部加え［Ｂ］成分としてエ
ピコート１００４を３重量部、［Ｃ］成分としてＵｌｔ
ｅｍ１０１０（末端酸無水物ならびに末端アミノ基、平
均分子量３２０００）を３８．５重量部混合し、１５０
℃で１時間加熱撹拌を行い透明な粘稠液を得た。この組
成物を冷却し、温度が７０℃以下になったところで、
［Ｄ］成分として３，３’−ジアミノジフェニルスルホ
ン５４重量部を加え均一に拡散させて得た組成物をモー
ルド中で１８０℃で２時間硬化させ硬化物を得た。この
とき硬化物の靱性は１．６０ＭＰａ・ｍ-1/2であり、ガ
ラス転移温度は１９０℃であった。また、昇温速度１．
５℃／分とし０．５９ＭＰａの圧力下、１８０℃で２時
間で硬化させたコンポジットの耐衝撃性を測定したとこ
ろ、２２０ＭＰａ・ｍｍ -2であった。結果を表２に示
す。
（比較例１）［Ａ］成分としてＥＬＭ４３４とエピコー
ト８０６（平均分子量３５０）をそれぞれ５０重量部、
［Ｃ］成分としてスミカエクセル５００３Ｐを２５重量
部混合し、１５０℃で１時間加熱撹拌を行い透明な粘稠
液を得た。この組成物を冷却し、温度が７０℃以下にな
ったところで、［Ｄ］成分として４，４’−ジアミノジ
フェニルスルホン、４４．３重量部を加え均一に拡散さ
せて得た組成物をモールド中で１８０℃で２時間硬化さ
せ硬化物を得た。このとき硬化物の靱性は０．６６ＭＰ
ａ・ｍ-1/2であった。この硬化物のガラス転移温度は１
９２℃であった。昇温速度１．５℃／分とし０．５９Ｍ
Ｐａの圧力下、１８０℃で２時間で硬化させた、コンポ
ジットの耐衝撃性を測定したところ、１６５ＭＰａ・ｍ
ｍ-2であった。結果を表３に示す。１００℃で１時間、
１８０℃で３時間の硬化条件で硬化させたところ、靱性
は０．８０ＭＰａ・ｍ-1/2であり、ガラス転移温度は２
０２℃であった。また昇温速度１．５℃／分とし０．５
９ＭＰａの圧力下、オートクレーブ中で１００℃で１時
間、１８０℃で３時間の硬化させたコンポジットの耐衝
撃性は１７５ＭＰａ・ｍｍ-2となり、硬化条件による樹
脂物性に変化が見られた。
（比較例２）実施例１の原料のうち［Ｂ］成分にあたる
エピコート１００４のかわりに、エピコート１２５６
（平均分子量５００００）を３重量部加えた以外は実施
例１と同様にして樹脂硬化物を得た。この硬化物の靱性
は０．８２ＭＰａ・ｍ-1/2であり、ガラス転移温度は２
０１℃であった。また、昇温速度１．５℃／分とし０．
５９ＭＰａの圧力下、１８０℃で２時間で硬化させたコ
ンポジットの耐衝撃性を測定したところ、１７０ＭＰａ
・ｍｍ-2であった。さらに、ここで用いたプリプレグは
ドレープ性が悪く、取り扱い性に問題があった。結果を
表３に示す。
(比較例３)［Ａ］成分としてＥＬＭ４３４を９０重量部
と、ＹＤ−１２８を１０重量部加え［Ｂ］成分としてエ
ピコート１００４を３重量部、［Ｃ］成分としてスミカ
エクセル５００３Ｐを１５重量部混合し、１５０℃で１
時間加熱撹拌を行い透明な粘稠液を得た。この組成物を
冷却し、温度が７０℃以下になったところで［Ｄ］成分
のかわりに、硬化剤として分子中に芳香族を持たないジ
シアンジアミド３．５重量部とジアミンでない１，３−
ジクロロフェニルジメチルウレア４重量部を加え均一に
拡散させて得た組成物をモールド中で１３０℃で２時間
硬化させ硬化物を得た。このとき硬化物の靱性は０．６
６ＭＰａ・ｍ-1/2であり、ガラス転移温度は１４０℃で
あった。成形温度を１３０℃とした以外、実施例１と同
様にしてコンポジットを作製した。耐衝撃性を測定した
ところ、１６０ＭＰａ・ｍｍ-2であった。結果を表３に
示す。The prepreg is (+ 45 ° / 0 ° / −45 °
(/ 90 °) 3s configuration, 24 sheets are pseudo isotropically stacked, and
It was molded in a autoclave to produce a laminate. This stack
From the body, cut out a test piece measuring 150 mm long × 100 mm wide
The Gardner Impactor according to ASTM D695.
Apply a falling weight impact of 6.7 J / mm to the center of the test piece.
Eh, compressive strength after impact using Instron universal testing machine
I asked.
(Example 1) ELM434 (average molecule) as the component [A]
50 parts by weight of Epicoat 630 (average amount)
Molecular weight 300) and GAN (average molecular weight 250)
25 parts by weight, as an ingredient [B], Epicoat 1004 (flat
10 parts by weight of an average molecular weight of 1800) as a component [C].
Mika Excel 3600P (Terminal chlorine, average molecular weight 160
(00) is mixed with 35 parts by weight and heated and stirred at 150 ° C. for 1 hour.
Then, a transparent viscous liquid was obtained. The composition is cooled and the temperature
When the temperature falls below 70 ° C., as the [D] component 3,
Add 56 parts by weight of 3'-diaminodiphenyl sulfone and mix evenly.
The resulting composition was dispersed in a mold at 180 ° C. for 2
It was cured for a time to obtain a cured product. At this time, the toughness of the cured product is
1.12 MPa · m-1/2And the glass transition temperature is 19
It was 9 ° C. Further, the rate of temperature rise is 1.5 ° C./min and is 0.5
Under a pressure of 9 MPa, the cured product was cured at 180 ° C. for 2 hours.
The impact resistance of Pogit is 240 MPa ・ mm-2Met.
The results are shown in Table 1.
(Example 2) 45 parts by weight of ELM434 as [A] component
Part and Epicoat 630 25 parts by weight, GAN 30 parts by weight
Part, Epicoat 4004P (average molecule as component [B])
1600) in an amount of 10 parts by weight, and as a component [C]
Mix 35 parts by weight of Xcel 3600P and heat at 150 ° C for 1 hour.
While heating and stirring, a transparent viscous liquid was obtained. Cool this composition
However, when the temperature falls below 70 ° C, [D] component
50 parts by weight of 3,3'-diaminodiphenyl sulfone
The composition obtained by uniformly adding
It was cured at 0 ° C. for 2 hours to obtain a cured product. Toughness of this cured product
Is 1.10 MPa · m-1/2And the glass transition temperature is 1
It was 95 ° C. In addition, the temperature rising rate is 1.5 ° C./min and the rate is 0.1.
The resin cured at 180 ° C. for 2 hours under the pressure of 59 MPa.
The impact resistance of the deposit was measured to be 240 MPa
・ Mm-2Met. The results are shown in Table 1. Also, this resin
Under 1 hour at 100 ° C and 3 hours at 180 ° C.
Toughness was 1.10 MPa · m-1/2And
And the glass transition temperature was 196 ° C. Furthermore, the temperature rise
100 at a speed of 1.5 ° C./min and a pressure of 0.59 MPa
Composite cured at ℃ for 1 hour and 180 ℃ for 3 hours
Impact resistance of 240MPa mm-2And the curing conditions
No deterioration of mechanical properties was observed.
(Example 3) ELM434 and Epicor as the component [A]
50 parts by weight each of 630 and 630 as the [B] component.
3 parts by weight of PICOAT 1004, Sumika as [C] component
Excel 5200P (Terminal chlorine, average molecular weight 3500
30 parts by weight of 0) are mixed and heated and stirred at 150 ° C. for 1 hour.
A transparent viscous liquid was obtained. The composition is cooled and the temperature is
When the temperature falls below 70 ° C., 3,3′-di of the [D] component
Disperses 34.6 parts by weight of aminodiphenyl sulfone uniformly
The resulting composition is cured in a mold at 180 ° C for 2 hours
To obtain a cured product. The toughness of this cured product is 1.08 MPa
・ M-1 / 2The glass transition temperature is 204 ° C.
It was In addition, the rate of temperature rise is 1.5 ° C./min and 0.59 MPa
Of a composite cured under pressure at 180 ° C for 2 hours
When the impact resistance was measured, it was 235 MPa · mm-2And
It was. The results are shown in Table 1.
(Example 4) 50 parts by weight of ELM434 as [A] component
And Epicoat 630 25 parts by weight, GAN 25 parts by weight
Part, Epicoat 4007P (average molecule as component [B])
Amount 4000) 10 parts by weight, and as a component [C]
Mix 35 parts by weight of Xcel 3600P and heat at 150 ° C for 1 hour.
While heating and stirring, a transparent viscous liquid was obtained. Cool this composition
However, when the temperature falls below 70 ° C, [D] component
56 parts by weight of 3,3'-diaminodiphenyl sulfone
The composition obtained by uniformly adding
It was cured at 0 ° C. for 2 hours to obtain a cured product. Toughness of this cured product
Is 1.08 MPa · m-1/2And the glass transition temperature is
It was 200 ° C. Also, the heating rate is 1.5 ° C./min.
Cure at 180 ° C for 2 hours under 0.59MPa pressure
When the impact resistance of the composite was measured, it was 235M.
Pa · mm-2Met. The results are shown in Table 1.
(Example 5) 50 parts by weight of ELM434 as the component [A]
And Epicoat 630 25 parts by weight, GAN 25 parts by weight
Part, [B] component, Epicoat YL6616 (average
10 parts by weight of 1000), Sumika as [C] component
Mix 35 parts by weight of Excel 3600P and mix at 150 ° C for 1
The mixture was heated and stirred for an hour to obtain a transparent viscous liquid. This composition
After cooling, when the temperature falls below 70 ° C, the component [D]
As 3,3'-diaminodiphenyl sulfone 57.2
Add parts by weight and spread uniformly to obtain a composition
And cured at 180 ° C. for 2 hours to obtain a cured product. This cured product
Has a toughness of 1.06 MPa · m-1/2And the glass transition temperature
The degree was 209 ° C. In addition, the heating rate is 1.5 ° C / min.
Cured at 180 ° C for 2 hours under a pressure of 0.59 MPa.
The impact resistance of the composite was measured and found to be 235
MPa · mm-2Met. The results are shown in Table 1.
(Example 6) 90 parts by weight of ELM434 as [A] component
And Epototo YD-128 (average molecular weight 350)
Add 10 parts by weight of Epicoat 1004 as a component [B]
3 parts by weight, Sumika Excel 5003P as [C] component
35 parts by weight of (terminal hydroxyl group, average molecular weight 30000)
And stir for 1 hour at 150 ° C to form a clear viscous liquid.
Obtained. The composition was cooled and the temperature dropped below 70 ° C.
By the way, as the [D] component, 4,4'-diaminodiphe
A set obtained by adding 44 parts by weight of nil sulfone and uniformly diffusing it.
The cured product is cured in a mold at 180 ° C for 2 hours.
Obtained. At this time, the toughness of the cured product is 1.05 MPa · m-1/2
And the glass transition temperature was 208 ° C. Also rise
18 at a temperature rate of 1.5 ° C./min and a pressure of 0.59 MPa
Measures the impact resistance of composites cured at 0 ° C for 2 hours
When determined, 230 MPa ・ mm-2Met. The result
It shows in Table 2.
(Example 7) 50 parts of Epicoat 630 as the component [A]
Add 50 parts by weight of GAN and 50 parts by weight of GAN as the component [B].
3 parts by weight of PICOAT 1004, Ult as [C] component
em1010 (terminal acid anhydride and terminal amino group, flat
38.5 parts by weight of an average molecular weight of 32,000 are mixed to obtain 150
The mixture was heated and stirred at ℃ for 1 hour to obtain a transparent viscous liquid. This group
When the product is cooled and the temperature drops below 70 ° C,
3,3'-diaminodiphenylsulfo as component [D]
54 parts by weight of the composition and uniformly dispersed to obtain a composition.
A cured product was obtained by curing at 180 ° C. for 2 hours in a cold oven. this
When the toughness of the cured product is 1.60 MPa · m-1/2And
The Lath transition temperature was 190 ° C. In addition, the heating rate 1.
5 ° C./min, under pressure of 0.59 MPa, 180 ° C. at 2:00
The impact resistance of the composite cured between
R, 220 MPa ・ mm -2Met. The results are shown in Table 2.
You
(Comparative Example 1) ELM434 and Epicor as the component [A]
50 parts by weight of 806 (average molecular weight 350),
25 weight of Sumika Excel 5003P as [C] component
Mixed and heated and stirred at 150 ° C for 1 hour to give a transparent viscous
A liquid was obtained. The composition is cooled until the temperature drops below 70 ° C.
By the way, 4,4'-diaminodiene as the component [D]
Add 44.3 parts by weight of phenyl sulfone and spread evenly.
The resulting composition was cured in a mold at 180 ° C for 2 hours.
A cured product was obtained. At this time, the toughness of the cured product is 0.66MP
a ・ m-1/2Met. The glass transition temperature of this cured product is 1
It was 92 ° C. Temperature rising rate is 1.5 ° C / min and 0.59M
The component was cured under a pressure of Pa at 180 ° C for 2 hours.
When the impact resistance of the jig was measured, it was 165 MPa · m
m-2Met. The results are shown in Table 3. 1 hour at 100 ℃,
Toughness when cured at 180 ° C for 3 hours
Is 0.80 MPa · m-1/2And the glass transition temperature is 2
It was 02 ° C. The rate of temperature rise is 1.5 ° C / min and is 0.5
1 hour at 100 ° C in an autoclave under a pressure of 9 MPa
Impact resistance of composites cured at 180 ° C for 3 hours
Hammerability is 175 MPa · mm-2And depending on the curing conditions
Changes in the physical properties of fat were observed.
(Comparative Example 2) Corresponding to the component [B] in the raw materials of Example 1.
Instead of Epikote 1004, Epikote 1256
Implemented except that 3 parts by weight of (average molecular weight 50,000) was added.
A resin cured product was obtained in the same manner as in Example 1. Toughness of this cured product
Is 0.82 MPa · m-1/2And the glass transition temperature is 2
It was 01 ° C. In addition, the temperature rising rate is 1.5 ° C./min and the rate is 0.1.
The resin cured at 180 ° C. for 2 hours under the pressure of 59 MPa.
The impact resistance of the deposit was measured to be 170 MPa
・ Mm-2Met. Furthermore, the prepreg used here is
Drapability was poor and there was a problem in handling. The result
It shows in Table 3.
(Comparative Example 3) 90 parts by weight of ELM434 as component [A]
And 10 parts by weight of YD-128 is added as the component [B].
3 parts by weight of PICOAT 1004, Sumika as [C] component
Mix 15 parts by weight of Excel 5003P and mix at 150 ° C for 1
The mixture was heated and stirred for an hour to obtain a transparent viscous liquid. This composition
After cooling, when the temperature falls below 70 ° C, the component [D]
Instead of diazo, which has no aromatic group in its molecule as a curing agent.
Cyandiamide 3.5 parts by weight and not diamine 1,3-
Add 4 parts by weight of dichlorophenyldimethylurea to homogenize
The composition obtained by diffusion is placed in a mold at 130 ° C. for 2 hours.
A cured product was obtained by curing. At this time, the toughness of the cured product is 0.6.
6 MPa · m-1/2And the glass transition temperature is 140 ° C.
there were. Same as Example 1 except that the molding temperature was 130 ° C.
In this way, a composite was prepared. Impact resistance was measured
By the way, 160 MPa ・ mm-2Met. The results are shown in Table 3.
Show.
【００８１】[0081]
【表１】 [Table 1]
【００８２】[0082]
【表２】 [Table 2]
【００８３】[0083]
【表３】 [Table 3]
【００８４】[0084]
【発明の効果】本発明のエポキシ樹脂組成物はプロセス
性に優れ、高い靭性を有し、かつ耐熱性に優れた硬化物
を与える。また、該エポキシ樹脂組成物と強化繊維から
なるプリプレグは取り扱い性に優れたものとなる。さら
に、該エポキシ樹脂組成物の硬化物と強化繊維からなる
ことを特徴とする繊維強化複合材料は耐衝撃性、耐熱性
に優れる。本発明の繊維強化複合材料は、航空宇宙用
途、海洋船舶用途、一般産業用途などに使用できる。The epoxy resin composition of the present invention gives a cured product having excellent processability, high toughness and heat resistance. Further, the prepreg comprising the epoxy resin composition and the reinforcing fiber has excellent handleability. Furthermore, a fiber-reinforced composite material characterized by comprising a cured product of the epoxy resin composition and a reinforcing fiber is excellent in impact resistance and heat resistance. The fiber-reinforced composite material of the present invention can be used for aerospace applications, marine vessel applications, general industrial applications and the like.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F072 AA07 AB10 AD23 AD46 AL02 AL04 4J002 CD041 CD051 CD052 CM043 CN013 CN033 EN076 EV246 FD146 GC00 GN00 4J036 AA05 AB09 AC05 AD07 AD08 AF06 DC03 DC10 FB15 JA08 JA11 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4F072 AA07 AB10 AD23 AD46 AL02 AL04 4J002 CD041 CD051 CD052 CM043 CN013 CN033 EN076 EV246 FD146 GC00 GN00 4J036 AA05 AB09 AC05 AD07 AD08 AF06 DC03 DC10 FB15 JA08 JA11
Claims (8)
の成分を含んでなるエポキシ樹脂組成物。 ［Ａ］分子中に少なくとも２個以上のエポキシ基を有
し、かつ平均分子量Ｍａが１５０以上８００以下である
エポキシ樹脂 ［Ｂ］分子中に２個のエポキシ基を有し、平均分子量Ｍ
ｂが９００以上５０００以下であるエポキシ樹脂 ［Ｃ］熱可塑性樹脂であって、その平均分子量Ｍｃが
［Ｂ］のエポキシ樹脂成分の平均分子量Ｍｂに対して、
３≦Ｍｃ／Ｍｂ≦１００を満たす熱可塑性樹脂 ［Ｄ］分子内に芳香族環を有するジアミン硬化剤1. The following [A], [B], [C] and [D]:
An epoxy resin composition comprising the above component. [A] Epoxy resin having at least two epoxy groups in the molecule and having an average molecular weight Ma of 150 or more and 800 or less [B] Having two epoxy groups in the molecule and having an average molecular weight M
b is 900 or more and 5,000 or less, and is an epoxy resin [C] thermoplastic resin, and its average molecular weight Mc is [B] with respect to the average molecular weight Mb of the epoxy resin component,
Thermoplastic resin [D] satisfying 3 ≦ Mc / Mb ≦ 100 A diamine curing agent having an aromatic ring in the molecule
重量部に対して、［Ｂ］成分が０．２〜２５重量部、
［Ｃ］成分が１２〜６０重量部および［Ｄ］成分が２５
〜７０重量部含まれてなることを特徴とする請求項１に
記載のエポキシ樹脂組成物。2. A component [A] 100 in an epoxy resin composition.
0.2 to 25 parts by weight of the component [B] with respect to parts by weight,
12 to 60 parts by weight of the component [C] and 25 parts of the component [D]
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is contained in an amount of about 70 parts by weight.
Ｍｃ≦１０００００を満たす熱可塑性樹脂であることを
特徴とする請求項１または２に記載のエポキシ樹脂組成
物。3. The [C] component has an average molecular weight Mc of 5000 ≦.
The epoxy resin composition according to claim 1, which is a thermoplastic resin satisfying Mc ≦ 100,000.
スルホン、ポリフェニルスルホン、ポリスルホン、ポリ
エーテルエーテルスルホン、ポリエーテルイミドより選
ばれる少なくとも１種であることを特徴とする請求項１
〜３のいずれかに記載のエポキシ樹脂組成物。4. The thermoplastic resin as component [C] is at least one selected from polyether sulfone, polyphenyl sulfone, polysulfone, polyether ether sulfone, and polyetherimide.
The epoxy resin composition according to any one of 1 to 3.
樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型
エポキシ樹脂より選ばれる少なくとも１種であることを
特徴とする請求項１〜４のいずれかに記載のエポキシ樹
脂組成物。5. The component [B] is at least one selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a biphenyl type epoxy resin, according to any one of claims 1 to 4. Epoxy resin composition.
樹脂組成物と強化繊維からなることを特徴とするプリプ
レグ。6. A prepreg comprising the epoxy resin composition according to claim 1 and a reinforcing fiber.
物を硬化してなる樹脂硬化物。7. A cured resin product obtained by curing the resin composition according to claim 1.
を含んでなることを特徴とする繊維強化複合材料。8. A fiber-reinforced composite material comprising the resin cured product according to claim 7 and a reinforcing fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002036352A JP2003238657A (en) | 2002-02-14 | 2002-02-14 | Epoxy resin composition, cured resin, prepreg and fiber reinforced composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002036352A JP2003238657A (en) | 2002-02-14 | 2002-02-14 | Epoxy resin composition, cured resin, prepreg and fiber reinforced composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003238657A true JP2003238657A (en) | 2003-08-27 |
Family
ID=27778257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002036352A Pending JP2003238657A (en) | 2002-02-14 | 2002-02-14 | Epoxy resin composition, cured resin, prepreg and fiber reinforced composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003238657A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005232313A (en) * | 2004-02-19 | 2005-09-02 | Mitsubishi Electric Corp | Thermally conductive resin sheet and power module using the same |
| JP2006117865A (en) * | 2004-10-25 | 2006-05-11 | Nitto Boseki Co Ltd | FIBER-REINFORCED RESIN LINEAR AND METHOD FOR PRODUCING THE SAME |
| JP2006291092A (en) * | 2005-04-13 | 2006-10-26 | Yokohama Rubber Co Ltd:The | Epoxy resin composition for fiber reinforced composite materials |
| WO2007125926A1 (en) * | 2006-04-25 | 2007-11-08 | The Yokohama Rubber Co., Ltd. | Epoxy resin composition for fiber-reinforced composite material |
| JP2008101227A (en) * | 2007-12-27 | 2008-05-01 | Mitsubishi Electric Corp | Thermally conductive resin sheet and power module using the same |
| JP2008156486A (en) * | 2006-12-25 | 2008-07-10 | Yokohama Rubber Co Ltd:The | Epoxy resin composition for fiber-reinforced composite material |
| JP2009292976A (en) * | 2008-06-06 | 2009-12-17 | Mitsubishi Rayon Co Ltd | Prepreg for press molding, and manufacturing method of molded article |
| JP2010126702A (en) * | 2008-12-01 | 2010-06-10 | Toray Ind Inc | Epoxy resin composition, fiber-reinforced composite material, and methods for producing them |
| CN101608050B (en) * | 2008-06-20 | 2011-06-08 | 中国科学院化学研究所 | Epoxy resin modified material with three-layer structure and preparation method thereof |
| EP2011826A4 (en) * | 2006-04-25 | 2012-02-29 | Yokohama Rubber Co Ltd | Epoxy resin composition for fiber-reinforced composite material |
| EP2017296A4 (en) * | 2006-04-25 | 2012-02-29 | Yokohama Rubber Co Ltd | Epoxy resin composition for fiber-reinforced composite material |
| JP2012048230A (en) * | 2010-07-29 | 2012-03-08 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal one-drop-fill process and liquid crystal display element |
| EP2627710A2 (en) | 2010-10-12 | 2013-08-21 | Hexcel Corporation | Improving solvent resistance of epoxy resins toughened with polyethersulfone |
| JP2014058692A (en) * | 2014-01-06 | 2014-04-03 | Mitsubishi Rayon Co Ltd | Prepreg for press molding and method of manufacturing molded article |
| JP2016148050A (en) * | 2010-06-14 | 2016-08-18 | ヘクセル コンポジッツ、リミテッド | Improvements in composite materials |
| CN111825951A (en) * | 2020-07-28 | 2020-10-27 | 惠柏新材料科技（上海）股份有限公司 | A kind of epoxy resin composition with toughening property and synthesis method |
| US11319406B2 (en) * | 2017-11-14 | 2022-05-03 | Eneos Corporation | Prepreg, fiber-reinforced composite material, and molded article |
| WO2022113976A1 (en) | 2020-11-27 | 2022-06-02 | 東レ株式会社 | Prepreg and method for producing prepreg |
-
2002
- 2002-02-14 JP JP2002036352A patent/JP2003238657A/en active Pending
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7602051B2 (en) | 2004-02-19 | 2009-10-13 | Mitsubishi Denki Kabushiki Kaisha | Thermally conductive resin sheet and power module using the same |
| JP2005232313A (en) * | 2004-02-19 | 2005-09-02 | Mitsubishi Electric Corp | Thermally conductive resin sheet and power module using the same |
| JP2006117865A (en) * | 2004-10-25 | 2006-05-11 | Nitto Boseki Co Ltd | FIBER-REINFORCED RESIN LINEAR AND METHOD FOR PRODUCING THE SAME |
| JP2006291092A (en) * | 2005-04-13 | 2006-10-26 | Yokohama Rubber Co Ltd:The | Epoxy resin composition for fiber reinforced composite materials |
| WO2007125926A1 (en) * | 2006-04-25 | 2007-11-08 | The Yokohama Rubber Co., Ltd. | Epoxy resin composition for fiber-reinforced composite material |
| EP2011826A4 (en) * | 2006-04-25 | 2012-02-29 | Yokohama Rubber Co Ltd | Epoxy resin composition for fiber-reinforced composite material |
| EP2017296A4 (en) * | 2006-04-25 | 2012-02-29 | Yokohama Rubber Co Ltd | Epoxy resin composition for fiber-reinforced composite material |
| US8137786B2 (en) | 2006-04-25 | 2012-03-20 | The Yokohama Rubber Co., Ltd. | Epoxy resin composition for fiber-reinforced composite material |
| JP2008156486A (en) * | 2006-12-25 | 2008-07-10 | Yokohama Rubber Co Ltd:The | Epoxy resin composition for fiber-reinforced composite material |
| JP2008101227A (en) * | 2007-12-27 | 2008-05-01 | Mitsubishi Electric Corp | Thermally conductive resin sheet and power module using the same |
| JP2009292976A (en) * | 2008-06-06 | 2009-12-17 | Mitsubishi Rayon Co Ltd | Prepreg for press molding, and manufacturing method of molded article |
| CN101608050B (en) * | 2008-06-20 | 2011-06-08 | 中国科学院化学研究所 | Epoxy resin modified material with three-layer structure and preparation method thereof |
| JP2010126702A (en) * | 2008-12-01 | 2010-06-10 | Toray Ind Inc | Epoxy resin composition, fiber-reinforced composite material, and methods for producing them |
| JP2016148050A (en) * | 2010-06-14 | 2016-08-18 | ヘクセル コンポジッツ、リミテッド | Improvements in composite materials |
| JP2012048230A (en) * | 2010-07-29 | 2012-03-08 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal one-drop-fill process and liquid crystal display element |
| EP2627710A2 (en) | 2010-10-12 | 2013-08-21 | Hexcel Corporation | Improving solvent resistance of epoxy resins toughened with polyethersulfone |
| JP2013538932A (en) * | 2010-10-12 | 2013-10-17 | ヘクセル コーポレイション | Improvement of solvent resistance of epoxy resin toughened with polyethersulfone |
| US8686069B2 (en) | 2010-10-12 | 2014-04-01 | Hexcel Corporation | Solvent resistance of epoxy resins toughened with polyethersulfone |
| EP2627710B1 (en) * | 2010-10-12 | 2023-11-22 | Hexcel Corporation | Improving solvent resistance of epoxy resins toughened with polyethersulfone |
| JP2014058692A (en) * | 2014-01-06 | 2014-04-03 | Mitsubishi Rayon Co Ltd | Prepreg for press molding and method of manufacturing molded article |
| US11319406B2 (en) * | 2017-11-14 | 2022-05-03 | Eneos Corporation | Prepreg, fiber-reinforced composite material, and molded article |
| CN111825951A (en) * | 2020-07-28 | 2020-10-27 | 惠柏新材料科技（上海）股份有限公司 | A kind of epoxy resin composition with toughening property and synthesis method |
| WO2022113976A1 (en) | 2020-11-27 | 2022-06-02 | 東レ株式会社 | Prepreg and method for producing prepreg |
| US12528925B2 (en) | 2020-11-27 | 2026-01-20 | Toray Industries, Inc. | Prepreg and method for producing prepreg |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103270109B (en) | Epoxy resin composition for fiber-reinforced composite material, prepreg and fibre reinforced composites | |
| CN104870511B (en) | Epoxy resin composition, prepreg, and carbon-fiber-reinforced composite material | |
| TWI435887B (en) | Epoxy resin composition, prepreg and fiber-reinforced composite material | |
| US7005185B2 (en) | Quick cure carbon fiber reinforced epoxy resin | |
| US7208228B2 (en) | Epoxy resin for fiber reinforced composite materials | |
| JP2003238657A (en) | Epoxy resin composition, cured resin, prepreg and fiber reinforced composite material | |
| JP6497027B2 (en) | Epoxy resin composition, cured resin, prepreg and fiber reinforced composite material | |
| US20130217805A1 (en) | Epoxy resin composition, prepreg and fiber-reinforced composite materials | |
| KR20140048340A (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
| JP2010059225A (en) | Epoxy resin composition for carbon fiber-reinforced composite material, prepreg, and carbon fiber-reinforced composite material | |
| CN108026251B (en) | Composition epoxy resin, prepreg and fibre reinforced composites | |
| JP2008144110A (en) | Epoxy resin composition for fiber-reinforced composite material | |
| WO2016204173A1 (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
| JP2005298713A (en) | Epoxy resin composition for fiber reinforced composite material, prepreg and fiber reinforced composite material | |
| JP6555006B2 (en) | Epoxy resin composition, cured resin, prepreg and fiber reinforced composite material | |
| JP2019038939A (en) | Prepreg and fiber-reinforced composite material | |
| JP2011079983A (en) | Epoxy resin composition for carbon fiber-reinforced composite material, prepreg and carbon fiber-reinforced composite material | |
| JP2016132709A (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
| JP2007154160A (en) | Epoxy resin composition, prepreg and fiber-reinforced composite material | |
| JP2014156582A (en) | Prepreg and fiber-reinforced composite material | |
| JP4655329B2 (en) | Unidirectional prepreg and fiber reinforced composites | |
| JP2011057851A (en) | Epoxy resin composition, prepreg and fiber-reinforced composite material | |
| JPH04249544A (en) | Resin composition, prepreg and production of prepreg | |
| JP2011074353A (en) | Epoxy resin composition for carbon fiber-reinforced composite material, prepreg, and carbon fiber-reinforced composite material | |
| JP7775710B2 (en) | Epoxy resin composition, prepreg and fiber-reinforced composite material |