CN103958560B - Composition epoxy resin, prepreg, fiber reinforced composite material and manufacture method thereof - Google Patents
Composition epoxy resin, prepreg, fiber reinforced composite material and manufacture method thereof Download PDFInfo
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- CN103958560B CN103958560B CN201280058418.7A CN201280058418A CN103958560B CN 103958560 B CN103958560 B CN 103958560B CN 201280058418 A CN201280058418 A CN 201280058418A CN 103958560 B CN103958560 B CN 103958560B
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- 239000000203 mixture Substances 0.000 title claims abstract description 267
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 234
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 233
- 239000000463 material Substances 0.000 title claims description 55
- 229920000311 Fiber-reinforced composite Polymers 0.000 title claims description 37
- 239000003733 fiber-reinforced composite Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- -1 prepreg Polymers 0.000 title description 10
- 150000004693 imidazolium salts Chemical class 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 238000007711 solidification Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims abstract description 12
- 125000000962 organic group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atoms Chemical group C* 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 39
- 230000003014 reinforcing Effects 0.000 claims description 21
- 239000004593 Epoxy Substances 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 12
- 239000003094 microcapsule Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 abstract description 75
- 239000011347 resin Substances 0.000 abstract description 75
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000011159 matrix material Substances 0.000 description 19
- 150000002118 epoxides Chemical class 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 229920005992 thermoplastic resin Polymers 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- 230000000996 additive Effects 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 11
- 238000004017 vitrification Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 229920002725 Thermoplastic elastomer Polymers 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Di(p-aminophenyl)sulphone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 238000005039 chemical industry Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1H-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000001896 cresols Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920002496 poly(ether sulfone) Polymers 0.000 description 4
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2H-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N Diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N Fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000000630 rising Effects 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical group CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-Methylenedianiline Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- ADXDQENDQRQGQZ-UHFFFAOYSA-N C(C1=CC=CC=C1)C=1NC(=C(N=1)C)O Chemical compound C(C1=CC=CC=C1)C=1NC(=C(N=1)C)O ADXDQENDQRQGQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 229920001721 Polyimide Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000051 modifying Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002492 poly(sulfones) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- AXJZCJSXNZZMDU-UHFFFAOYSA-N (5-methyl-1H-imidazol-4-yl)methanol Chemical compound CC=1N=CNC=1CO AXJZCJSXNZZMDU-UHFFFAOYSA-N 0.000 description 1
- 0 *C1=C(*)N=C(*)*1CCO Chemical compound *C1=C(*)N=C(*)*1CCO 0.000 description 1
- ZWOULFZCQXICLZ-UHFFFAOYSA-N 1,3-dimethyl-1-phenylurea Chemical compound CNC(=O)N(C)C1=CC=CC=C1 ZWOULFZCQXICLZ-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-Methylimidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- CIPOCPJRYUFXLL-UHFFFAOYSA-N 2,3,4-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C(CN(C)C)=C1CN(C)C CIPOCPJRYUFXLL-UHFFFAOYSA-N 0.000 description 1
- JJWKKSUCSNDHNJ-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanol Chemical compound CC1=NC=CN1CCO JJWKKSUCSNDHNJ-UHFFFAOYSA-N 0.000 description 1
- WOJMOIOVKUURQZ-UHFFFAOYSA-N 2-(4-phenylbutoxymethyl)oxirane Chemical class C1OC1COCCCCC1=CC=CC=C1 WOJMOIOVKUURQZ-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-Aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- RRTJBIJAUFOAGW-UHFFFAOYSA-N 2-methyl-1H-imidazol-5-ol Chemical compound CC1=NC=C(O)N1 RRTJBIJAUFOAGW-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- AHNGUGDMAGMLGV-UHFFFAOYSA-N 5-benzyl-3-methyl-2-phenylimidazol-4-ol Chemical compound N1=C(C=2C=CC=CC=2)N(C)C(O)=C1CC1=CC=CC=C1 AHNGUGDMAGMLGV-UHFFFAOYSA-N 0.000 description 1
- 206010003694 Atrophy Diseases 0.000 description 1
- MRBNOISZXJXZKE-UHFFFAOYSA-N C1(=CC=C(C=C1)C=1N(C(=C(N1)C)O)C)C Chemical compound C1(=CC=C(C=C1)C=1N(C(=C(N1)C)O)C)C MRBNOISZXJXZKE-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N Cyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N Dirurol Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- 210000000981 Epithelium Anatomy 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 229950000845 Politef Drugs 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002480 Polybenzimidazole fiber Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N cyanoguanidine Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000994 depressed Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000069 poly(p-phenylene sulfide) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011528 polyamide (building material) Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 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
Abstract
The present invention relates to a kind of composition epoxy resin, it is characterized in that, it for not having the composition epoxy resin of the imidazolium compounds shown in the epoxy resin of sulphur atom and composition B: following formula (1), containing the imidazolium compounds shown in composition C: following formula (2) or components D: intramolecular has at least one composition in the epoxy resin of at least 1 sulphur atom containing composition A: intramolecular.According to the present invention it is possible to excellent storage stability under offer room temperature, can have the composition epoxy resin of high-fire resistance by the resin at a lower temperature and after short period internal heating curing, solidification.(in formula (1), R1Represent the alkyl of straight or branched of carbon number 1～5, methylol, R2Represent alkyl or the hydrogen atom of the straight or branched of carbon number 1～5.) (in formula (2), R3Represent the organic group containing more than 1 carbon atom, R4～R6Represent hydrogen atom or methyl or ethyl.)
Description
Technical field
The present invention relates to epoxy resin composition for fiber-reinforced composite material, employ the preimpregnation of this resin combination
Expect, employ fiber reinforced composite material and the manufacture method thereof of this prepreg.Application claims was based on November 29th, 2011
In Japanese Patent Application 2011-260732 and the priority of Japanese Patent Application 2011-260733 of Japan's proposition, its content is quoted
In this.
Background technology
Containing carbon fiber and the carbon fiber-reinforced composite material of matrix resin, due to the mechanics physical property etc. of its excellence and extensive
In aircraft, automobile, industrial applications.In recent years, along with it uses the accumulation of achievement, the application of carbon fiber-reinforced composite material
Scope is gradually extended.For constituting the matrix resin of described composite, mouldability is excellent, the most also
It is requisite for showing high mechanical strength.Matrix resin is used mostly the thermosetting resin of impregnation, excellent heat resistance,
As such thermosetting resin, use phenolic resin, melmac, bimaleimide resin, unsaturated polyester (UP) tree
Fat, epoxy resin etc..Wherein, epoxy resin due to thermostability, mouldability is excellent, use its carbon fibre composite to obtain
Obtain high mechanical strength and be widely used.
As the FRP obtained containing reinforcing fiber and matrix resin, (Fiber Reinforced Plastics, below has
Time also referred to as " fiber reinforced composite material ") concrete grammar, it is known to the method for what patent documentation 1 was recorded use autoclave,
The compression forming method etc. that the method for the use vacuum bag that patent documentation 2 is recorded or patent documentation 3 are recorded.
But, the method that above-mentioned patent documentation 1～3 is recorded needs after prepreg stacking giving target shape,
About 2～6 hours be heating and curing is carried out at a temperature of more than about 160 DEG C.That is, the method that above-mentioned patent documentation 1～3 is recorded needs
Under high temperature and process for a long time.
On the other hand, high frequency under the High Temperature High Pressure that patent documentation 4 is recorded compressing due to its productivity ratio high, as
Forming method commonly used in mobile applications and it is known that.
During high frequency is compressing, in order to realize a large amount of productions of goods, it is desirable to by a lower temperature, i.e.
About 100～150 DEG C heating several minutes completed solidification to about 30 minutes.
Now, if the vitrification point of the matrix resin after Gu Hua is high, then the molded body after being heating and curing is the most cooled i.e.
During taking-up, molded body is the most indeformable, therefore can shorten molding cycle further.It is therefore desirable to the matrix resin after Gu Hua has
Higher vitrification point.
Additionally, by the vitrification point improving matrix resin, even if improve the temperature of baking application, molded body is the most not
Deformation, therefore can apply wider range of application condition to the molded body after being heating and curing.From such reason, also require that
Matrix resin after solidification has higher vitrification point.
If the vitrification point of matrix resin is high, fiber reinforced composite material can show height the most in high temperature environments
Mechanical strength, this is also known.
When the prepreg with thermosetting resin as matrix being carried out high frequency being compressing, there is the tree due to prepreg
Fat temperature rises and situation that resin viscosity extremely reduces.In this case, according to the difference of the structure of mould, resin sometimes
Can drastically flow out, the surface resin of the products formed that generation is obtained is not enough, i.e. such outward appearance is or not resin atrophy (the withered れ of fat)
Bad in the performances such as good or fiber crawls, or produce owing to resin flows into the push rod (Ejector pin) in mould, air
The bad problem waited in molding of mould operating that valve (Air valve) etc. is caused.Therefore, to thermosetting resin as matrix
Prepreg carry out high frequency compressing time, in order to improve quality and productivity ratio, need a kind of stream to the resin in mould
The dynamic method being adjusted.
Patent Document 5 discloses and use full-bodied epoxy resin as the method for matrix resin, by asphalt mixtures modified by epoxy resin
Fat adds the method that thermoplastic resin adjusts the flowing of resin.
But, for the method using full-bodied epoxy resin that patent documentation 5 is recorded, resin under room temperature (25 DEG C)
Viscosity also uprises.Therefore, the operation under the room temperature such as stacking operation of the operability of prepreg significantly reduces.Additionally, about
The method adding general thermoplastic resin in epoxy resin, due to aforementioned thermoplastic resin dissolubility in the epoxy
Low, to also result in the composition epoxy resin of acquisition vitrification point (is the most also recited as " Tg ".) reduction, solidification
The reduction etc. of speed, therefore, it is difficult to it is compressing to be applicable to high frequency.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 10-128778 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-159613 publication
Patent documentation 3: Japanese Unexamined Patent Publication 10-95048 publication
Patent documentation 4: No. 2004/48435 publication of International Publication
Patent documentation 5: Japanese Unexamined Patent Publication 2005-213352 publication
Summary of the invention
The problem that invention is to be solved
It is an object of the invention to provide: excellent storage stability under room temperature, can at a lower temperature and shorter time
Between internal heating curing, solidification resin there is the composition epoxy resin of high-fire resistance, use that this composition epoxy resin obtains,
The prepreg of the excess flow of resin during heat-pressure curing can be suppressed, use the fiber reinforced composite material that this prepreg obtains
Material.
Additionally, the present invention provides the manufacture method of the large-duty fiber reinforced composite material employing this prepreg.
For the method solving problem
The present inventor etc. conduct in-depth research to solve above-mentioned problem, comprise following composition it was found that utilize
Composition epoxy resin can solve the problem that above-mentioned problem, thus completes the present invention.The i.e. present invention comprises following item.
A kind of composition epoxy resin, it is containing following compositions A and the composition epoxy resin of composition B, containing composition C
With at least one in components D.
Composition A: intramolecular does not have the epoxy resin of sulphur atom
Composition B: there is the imidazolium compounds of the structure of following formula (1)
Composition C: there is the imidazolium compounds of the structure of following formula (2)
Components D: intramolecular has the epoxy resin of at least one sulphur atom
[chemical formula 1]
(in formula, R1Represent alkyl, methylol, R2Represent alkyl or hydrogen atom.)
[chemical formula 2]
(in formula, R3Represent the organic group containing more than 1 carbon atom, R4～R6Represent hydrogen atom or methyl or ethyl.)
That is, the present invention relates to below scheme.
[1] a kind of composition epoxy resin, it is characterised in that it is containing composition A and the epoxy composite of composition B
Thing, containing at least one composition in composition C or components D；
Composition A: intramolecular does not have the epoxy resin of sulphur atom
Imidazolium compounds shown in composition B: following formula (1)
Imidazolium compounds shown in composition C: following formula (2)
Components D: intramolecular has the epoxy resin of at least 1 sulphur atom
[chemical formula 3]
(in formula, R1Represent the alkyl of straight or branched of carbon number 1～5, methylol, R2Represent carbon number 1～5
The alkyl of straight or branched or hydrogen atom.)
[chemical formula 4]
(in formula, R3Represent the organic group containing more than 1 carbon atom, R4～R6Represent hydrogen atom or methyl or ethyl.)
[2] according to composition epoxy resin described in [1], wherein, described composition A for select free bisphenol A type epoxy resin,
Bisphenol f type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin, there is the epoxy resin of naphthalene skeleton, isocyanide
Modified the having of acid estersThe epoxy resin of oxazolidone ring, phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, contracting
Water glycerol amine type epoxy resin, diglycidyl ether type epoxy resin, the modifier of these epoxy resin, brominated epoxy resin form
Group in the above epoxy resin of at least one；
[3] according to the composition epoxy resin described in [1] or [2], wherein, the R of described composition C3Preferably there is-CH2R7
Structure or-CH2OR7Group (wherein, the R of structure7Represent the organic group containing more than 1 carbon atom), or for having-CH2OR8
Group (wherein, the R of structure8Represent the aryl with or without substituent group)；
[4] according to the composition epoxy resin described in any one in [1]～[3], wherein, described composition epoxy resin
Described in the content of composition B be 2～40 mass parts relative to total 100 mass parts of described composition A and described components D；
[5] according to the composition epoxy resin described in any one in [1]～[4], wherein, described composition epoxy resin
Described in the content of composition B be 3～25 mass parts relative to total 100 mass parts of described composition A and described components D；
[6] according to the composition epoxy resin described in any one in [1]～[5], wherein, described composition epoxy resin
Described in the content of composition B be 3～15 mass parts relative to total 100 mass parts of described composition A and described components D；
[7] according to the composition epoxy resin described in any one in [1]～[6], wherein, described composition epoxy resin
Containing composition A, composition B and at least composition C, described composition C is the imidazolium compounds being encapsulated in microcapsule；
[8] according to the composition epoxy resin described in [7], wherein, described in described composition epoxy resin, composition C's contains
Amount is 1～6 mass parts relative to total 100 mass parts of described composition A and described components D；
[9] according to the composition epoxy resin described in [7], wherein, described in described composition epoxy resin, composition C's contains
Amount is 1.5～4 mass parts relative to total 100 mass parts of described composition A and described components D；
[10] according to the composition epoxy resin described in any one in [1]～[9], wherein, described epoxy composite
Thing contains composition A, composition B and at least components D, the mass ratio of composition A described in composition epoxy resin and described components D with
Composition A: components D is calculated as 95:5～10:90；
[11] according to the composition epoxy resin described in any one in [1]～[10], wherein, described epoxy composite
The mass ratio of composition A described in thing and described components D is with composition A: components D is calculated as 80:20～12:88；
[12] according to the composition epoxy resin described in any one in [1]～[11], wherein, described epoxy composite
The mass ratio of composition A described in thing and described components D is with composition A: components D is calculated as 60:40～13:87；
[13] according to the composition epoxy resin described in any one in [10]～[12], wherein, the molecule of described components D
It is contained within the structure shown in following formula (3)；
[chemical formula 5]
[14] according to the composition epoxy resin described in any one in [10]～[13], wherein, under described components D contains
State the structure shown in formula (4)；
[chemical formula 6]
[15] according to the composition epoxy resin described in any one in [10]～[14], wherein, described components D contains ring
Epoxy resins and intramolecular have the product of the amines of at least one sulphur atom；
[16] according to the composition epoxy resin described in any one in [1]～[15], wherein, containing composition C and composition
D；
[17] according to the composition epoxy resin described in any one in [1]～[16], wherein, described epoxy resin group is made
Compound makes prepreg containing being immersed in reinforcing fiber bundle, by be preheated to the mould described prepreg of clamping of 140 DEG C and to add
It is depressed into 1MPa, keeps 5 minutes, become more than 150 DEG C at the G ' Tg of the solidfied material of this described prepreg obtained；
[18] a kind of prepreg, it is for making the composition epoxy resin described in any one in [1]～[17] strong containing being immersed in
Change in fibre bundle and form；
[19] a kind of fiber reinforced composite material, it obtains for making the prepreg described in [18] solidify；
[20] manufacture method of a kind of fiber reinforced composite material, it has make the prepreg described in [18] in mould
The operation of 1～20 minute is kept under conditions of 100～150 DEG C, 1～15MPa.
Invention effect
According to the present invention it is possible to obtain excellent storage stability under room temperature, can at a lower temperature and the short period
Resin after internal heating curing, solidification has the composition epoxy resin of high-fire resistance.
Additionally, the excess flow of resin when the composition epoxy resin of the present invention can suppress heat-pressure curing, so
The matrix resin of fiber reinforced composite material can be suitable for use as.
Accompanying drawing explanation
Figure 1A is the pressure used by fiber reinforced composite material representing and manufacturing the composition epoxy resin employing the present invention
The sectional view of state when mold for forming processed is opened.
Figure 1B is the pressure used by fiber reinforced composite material representing and manufacturing the composition epoxy resin employing the present invention
The sectional view of state when mold for forming processed is closed.
Detailed description of the invention
Hereinafter the preferred embodiment of the present invention is illustrated, but the present invention is not limited only to these modes.
The purport of the present invention is a kind of composition epoxy resin, it is characterised in that it is containing composition A and the ring of composition B
Epoxy resin composition, containing at least one composition in composition C or components D.
Composition A: intramolecular does not have the epoxy resin of sulphur atom
Imidazolium compounds shown in composition B: following formula (1)
Imidazolium compounds shown in composition C: following formula (2)
Components D: intramolecular has the epoxy resin of at least 1 sulphur atom
[chemical formula 7]
(in formula, R1Represent the alkyl of straight or branched of carbon number 1～5, methylol, R2Represent carbon number 1～5
The alkyl of straight or branched or hydrogen atom.)
[chemical formula 8]
(in formula, R3Represent the organic group containing more than 1 carbon atom, R4～R6Represent hydrogen atom or methyl or ethyl.)
In aforesaid ingredients (C), i.e. imidazolium compounds shown in formula (2), R3Preferably there is-CH2R7Structure or-CH2OR7Knot
Group (wherein, the R of structure7Represent the organic group containing more than 1 carbon atom), more preferably there is-CH2OR8The group of structure
(wherein, R8Represent the aryl with or without substituent group).
(composition A)
In the present invention, as composition A, intramolecular is used not have more than a kind in the epoxy resin of sulphur atom.As with
Make the epoxy resin of the composition A of the present invention, such as, in the case of 2 functionality epoxy resin, bisphenol type epoxy tree can be enumerated
Fat, bisphenol f type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin, have naphthalene skeleton epoxy resin,
Or to the most isocyanate-modified the having of epoxy resin obtained by these resin modifiedsThe epoxy resin etc. of oxazolidone ring.Make
Be 3 officials can above multi-functional epoxy resin, such as phenolic resin varnish type epoxy resin, cresol novolak type epoxy tree can be enumerated
Glycidyl amine epoxy tree as fat, four glycidyl group diaminodiphenyl-methane, triglycidyl group amino-phenol
Fat, four (glycidoxypropyl phenyl) ethane, three (glycidoxypropyl phenylmethanes), methylene bis (2-glycidyl epoxide) naphthalene
Such diglycidyl ether type epoxy resin and to the bromide i.e. bromine of epoxy resin, these epoxy resin obtained by they modifications
Change epoxy resin etc., but be not limited only to this.Additionally, as composition A, it is also possible to by two or more group in these epoxy resin
Close and use.
Wherein, particularly preferably use bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin,
Cresol novolak type epoxy resin.Additionally, the molecular weight of these epoxy resin be preferably 200～3000, more preferably 300～
2000.If molecular weight is 200～3000, composition epoxy resin easy to manufacture, so preferably.Here, molecular weight refers to profit
The weight average molecular weight being scaled polystyrene measured with gel permeation chromatography.
Additionally, the epoxide equivalent of the epoxy resin used as composition A be preferably 50～1000g/eq, more preferably 90～
700g/eq.If the epoxide equivalent of the epoxy resin used as composition A is 50～1000g/eq, the cross-linked structure of solidfied material is equal
Even, so preferably.Here, the epoxide equivalent meaning is the molecular weight of epoxy resin of every 1 epoxy radicals.
Using bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin, cresol novolak
When type epoxy resin etc. are as composition A, there is the epoxy resin of high rigid molecular structure as compared with during composition A with using, can
To obtain more preferable effect, described effect is: improves the mechanical strength of products formed, i.e. improve the epoxy resin group containing the present invention
Compound is as the mechanical strength of the fiber reinforced composite material of matrix resin.This is because, make that there is high rigid molecular structure
Epoxy resin solidifies at short notice, when generating highdensity cross-linked structure, easily produce strain in crosslinked eyed structure, and
When using above-mentioned epoxy resin as composition A, the probability that this problem occurs is low.
(composition B)
In the present invention, composition B is the imidazolium compounds shown in following formula (1).
[chemical formula 9]
(in formula, R1Represent the alkyl of straight or branched of carbon number 1～5, methylol, R2Represent carbon number 1～5
The alkyl of straight or branched or hydrogen atom.)
This imidazolium compounds plays the effect of the firming agent of epoxy resin, by coordinating in combination with composition C or components D
In composition epoxy resin, composition epoxy resin can be made to solidify at short notice.
As the example as the imidazolium compounds shown in the above-mentioned formula (1) of composition B, 2-phenyl-4,5-bis-can be enumerated
Hydroxy methylimidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2-phenyl-4-benzyl-5-hydroxy methylimidazole, 2-p-methylphenyl-
Tolyl-4,5-dihydroxymethyl miaow between tolyl-4-methyl-5-hydroxy methylimidazole, 2-between 4-methyl-5-hydroxy methylimidazole, 2-
The hydrogen of 5 of the 1H-imidazoles such as azoles, 2-p-methylphenyl-4,5-hydroxymethyl-imidazole replaced by methylol and the hydrogen of 2 by phenyl or
The substituted imidazolium compounds of tolyl.Wherein, more preferably 2-phenyl-4,5-hydroxymethyl-imidazole, 2-phenyl-4-methyl-5-hydroxyl
First between tolyl-4-methyl-5-hydroxy methylimidazole, 2-between Methylimidazole., 2-p-methylphenyl-4-methyl-5-hydroxy methylimidazole, 2-
Phenyl-4,5-hydroxymethyl-imidazole, 2-p-methylphenyl-4,5-hydroxymethyl-imidazole.Additionally, as composition B, it is also possible to by these
Two or more in imidazolium compounds is applied in combination.
In the present invention, for the content of composition B in composition epoxy resin, contained by composition epoxy resin
Epoxy resin (composition A, or be components D and the total of composition A when containing components D) 100 mass parts, preferably 2～40 matter
Amount part, more preferably 3～25 mass parts, more preferably 3～15 mass parts.When the content of composition B is more than 2 mass parts,
The curing reaction of composition epoxy resin can be promoted.Additionally, solidification resin has high-fire resistance, so preferably.
Additionally, the imidazolium compounds shown in above-mentioned formula (1) is crystalline solid under the conditions of room temperature (25 DEG C), at 100 DEG C
Time following, dissolubility in the epoxy is low.Accordingly, as composition B, it is however preferred to have below 100 μm, particularly 20 μm with
Under the powder body of volume average particle size.If the volume average particle size of composition B is below 100 μm, epoxy can be well dispersed within
In resin combination thus promote curing reaction, so preferably.
(composition C)
Composition C in the present invention is the imidazolium compounds shown in following formula (2).
[chemical formula 10]
(in formula, R3Represent the organic group containing more than 1 carbon atom, R4～R6Represent hydrogen atom or methyl or ethyl.)
Wherein, R3Preferably there is-CH2R7Structure or-CH2OR7Group (wherein, the R of structure7Represent containing more than 1 carbon
The organic group of atom), particularly preferably there is-CH2OR8Group (wherein, the R of structure8Represent with or without substituent group
Aryl).
This imidazolium compounds plays the effect of the low temperature curing agent of epoxy resin, by coordinating in combination at ring with composition B
In epoxy resin composition, composition epoxy resin can be made to solidify at short notice.Additionally, be typically pressed into carrying out high frequency
During type, along with the rising of the resin temperature of prepreg, resin viscosity reduces.Therefore, according to the difference of the structure of mould, sometimes set
Fat drastically can be flowed out by mould.But, the composition epoxy resin of the present invention containing composition C at low temperatures, i.e. 70～110
DEG C begin to curing reaction, in the uphill process of the resin temperature of prepreg, i.e. from the resin temperature of prepreg the most about 70
～the state of 110 DEG C rises, the cross-linking reaction of composition epoxy resin is the most quickly carried out, and therefore inhibits the reduction of resin viscosity,
Resin can be suppressed by the outflow of mould.
As the example as the imidazolium compounds shown in the above-mentioned formula (2) of composition C, 1-(2-hydroxyl-3-benzene can be enumerated
Epoxide propyl group)-2-methylimidazole, make diglycidyl ether type epoxy resin and 2-methylimidazole react obtain adduct.Wherein,
Make arylolycidyl ethers type epoxy resin and 2-methylimidazole react the adduct obtained and can make the epoxy resin of the present invention
The physical properties excellent of the solidfied material of compositions, so preferably.Additionally, as composition C, it is also possible to by 2 in these imidazolium compoundss
Plant combination of the above to use.
Composition C preferably has the performance making composition epoxy resin solidify below 100 DEG C and is endowed hot potentiality
Material.Here, " hot potentiality " refers to following character: do not had the reactivity with epoxy resin before implementing thermal process,
After implementing the thermal process of more than more than specified temp and special time, though the most also performance and epoxy resin
High response.
In the present invention, composition C is preferably encapsulated in microcapsule and disperses potentiality firming agent in the epoxy, enters
The epithelium of one step more preferably microcapsule is made up of cross-linked polymer.Here, as the epoxy resin for dispersion component C, both may be used
Identical with the composition A or components D with the present invention, it is also possible to different.As such epoxy resin, from the stability of microcapsule
Viewpoint is set out, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin.
As the method that composition C is encapsulated in microcapsule, it is not particularly limited, from the sight of the uniformity of microcapsule shell
Point sets out, and interfacial polymerization, situ aggregation method or from the phase separation method such method of organic solution system are preferably used.
About composition C curing performance, can be so that the temperature of epoxy resin composition, can be according to following steps
Judge.First, by liquid bisphenol A type epoxy resin (such as Mitsubishi Chemical's (strain) that epoxide equivalent is 184～194g/eq
Society jER828) 100 mass parts and composition C7 mass parts uniformly mix, the modulation composition epoxy resin containing composition C.So
After, utilize means of differential scanning calorimetry device (being denoted as " DSC " below) to make aforementioned epoxy resins with the programming rate condition of 10 DEG C/min
Compositions solidifies, and measures heat release behavior.In the DSC figure of aforementioned epoxy resins compositions, exotherm away from baseline, first
When the temperature (Exotherm Onset Temperature) of the tangent line of flex point and the intersection point of baseline is less than 100 DEG C, it can be determined that this composition C has
The curing performance of less than 100 DEG C.Similarly, on DSC figure, exotherm is less than 90 DEG C away from baseline, Exotherm Onset Temperature
Time, it can be determined that this composition C has the curing performance of less than 90 DEG C.
In the present invention, more preferably use the low temperature curing agent of the curing performance with less than 90 DEG C as composition C.
As can be suitable for making composition C be contained in composition epoxy resin, composition C be encapsulated in microcapsule and point
Dissipate in the epoxy, the firming agent masterbatch with the curing performance of less than 100 DEG C, Asahi Chemical Industry E-can be enumerated
Firming agent masterbatch i.e. Novacure HX3721, HX3722, HX3742, HX3748 etc. of materials society, but the most only limit
In this.
In the present invention, in composition epoxy resin, the content of composition C is preferably relative to the ring in composition epoxy resin
Epoxy resins (composition A, or be components D and the total of composition A when containing components D) 100 mass parts are 1～6 mass parts, more excellent
Elect 1.5～4 mass parts as.If the content of composition C is more than 1 mass parts, the curing reaction speed of composition epoxy resin is fast, can
With the outflow of resin during suppression solidification, so preferably.
(components D)
In the present invention, components D is the epoxy resin that intramolecular has at least one sulphur atom.Have at least as intramolecular
The epoxy resin of one sulphur atom, has bisphenol-s epoxy resin, has the epoxy resin of sulfur skeleton, it is possible to use they conducts
The components D of the present invention.Additionally, as components D, it is also possible to use the epoxy resin containing structure shown in following formula (3).As this
The epoxy resin of sample, the reaction that can enumerate the amines that such as epoxy resin has at least one sulphur atom with intramolecular is produced
Thing.That is, as components D, can produce containing the reaction of the amines that epoxy resin and intramolecular have at least one sulphur atom
Thing.
[chemical formula 11]
There is as intramolecular the amines of at least one sulphur atom, such as 4 can be enumerated, 4 '-diamino-diphenyl
Sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfide, double (4-(4-amino-benzene oxygen) phenyl) sulfone, double (4-
(3-amino-benzene oxygen) phenyl) sulfone, 4,4 '-diamino diphenyl sulfide and their derivant etc..Wherein, from solidification tree
From the viewpoint of the thermostability of fat, diamino diphenyl sulfone is preferably used, more preferably uses 4,4 '-diamino diphenyl sulfone.
As the epoxy resin reacted with amine compound, can be identical with composition A, it is also possible to different.
The method with intramolecular as acquisition epoxy resin with the product of the amines of at least one sulphur atom,
Can enumerate following method: epoxy resin and intramolecular are had at least one sulphur atom amines, such as have aforementioned
The amines of structure shown in formula (3) is according to the ratio mixing of 100:3～100:30, preferably 100:5～100:20,130
～200 DEG C, preferably react 140～170 DEG C of heating.When using the method, remained unreacted sometimes in product
Epoxy resin, amine compound, but need not specially remove these residues.
In the present invention, produce by having the reaction of the amines of at least one sulphur atom containing epoxy resin and intramolecular
Thing, as components D, can adjust the viscosity of the composition epoxy resin of the present invention, so preferably.That is, by adjustment ring epoxy resins
There is with intramolecular the reaction condition of the amines of at least one sulphur atom, the viscosity of the product obtained can be carried out
Control, such as: by being set to high temperature, long-time, the viscosity that can make the product of acquisition is high；By being set to low temperature, in short-term
Between, the viscosity that can make the product of acquisition is low.Therefore, by by the ring containing the previous reaction product with desired viscosity
Epoxy resins is coupled in composition epoxy resin as components D, can be with the viscosity of adjustment ring epoxy resin composition.
Additionally, as components D, it is also possible to use as intramolecular have at least one sulphur atom epoxy resin, contain
There is the epoxy resin of structure shown in following formula (4).
[chemical formula 12]
As such epoxy resin, such as bisphenol A type epoxy resin can be enumerated and have at least one in previous molecular
The product of the amines of individual sulphur atom.
When in the composition epoxy resin of the present invention containing components D, its content is in terms of the mass ratio of composition A and components D
It is preferably 95:5～10:90, more preferably 80:20～12:88, more preferably 60:40～13:87.If composition A and composition
The mass ratio of D is 95:5～10:90, and the thermostability of the resin after solidification improves, so preferably.
About the total content of composition A and components D in the composition epoxy resin of the present invention, relative to epoxy composite
Thing 100 mass parts, preferably 70～98 mass parts, more preferably 80～98 mass parts.If composition A in composition epoxy resin
Content is 70～98 mass parts, generates the cross-linked structure of densification in solidfied material, so preferably.
(auxiliary curing agent)
In the present invention, in order to improve firming agent, i.e. composition B or the curing activity of composition C, the Ke Yi used in the present invention
Do not damage and in the range of spirit of the invention, combine suitable auxiliary curing agent.By by composition B or composition C and auxiliary curing agent group
Close, composition epoxy resin can be made to solidify in shorter time.On the other hand, when the addition of auxiliary curing agent is too much, Gu
The storage stability of the resin combination after the thermostability reduction of the resin combination after change or solidification is deteriorated, it is therefore desirable to control
It is made as adding on a small quantity.
As the example of auxiliary curing agent, 3-phenyl-1,1-dimethyl urea, 3-(3,4-Dichlorobenzene base)-1,1-can be enumerated
Double (the 3,3-dimethyl urea groups) toluene of dimethyl urea (DCMU), 3-(3-chloro-4-aminomethyl phenyl)-1,1-dimethyl urea, 2,4-this
The amine coordination compounies such as the urea derivative of sample, tertiary amine, Boron Trifluoride Ethylamine, boron chloride-amine coordination compound.
(other firming agent)
Additionally, in the composition epoxy resin of the present invention, it is also possible to do not damaging group in the range of spirit of the invention
Conjunction had both been not belonging to composition B and had also been not belonging to " other firming agent " of composition C.Generally, " other solidification that the curable under low temperature is excellent
Agent " need to control to add for a small amount of, this be due to its can shorten composition epoxy resin and the life-span of prepreg, i.e. shortening can
The state of cohesiveness and flexibility to keep prepreg carries out the time limit preserved.
(additive)
Additionally, in the composition epoxy resin of the present invention, it is also possible to add choosing free thermoplastic resin, thermoplastic elastomer (TPE)
With elastomer group in groups in more than a kind resin as additive.Such additive not only changes composition epoxy resin
Viscoelasticity thus improve viscosity, storage modulus and thixotropy, also there is the toughness of the solidfied material improving composition epoxy resin
Effect.More than in thermoplastic resin, thermoplastic elastomer (TPE) and elastomer the a kind resin used as additive is the most permissible
It is used alone, it is also possible to and use two or more.Additionally, should be selected from a kind in thermoplastic resin, thermoplastic elastomer (TPE) and elastomer
Above resin both can exist with the state being dissolved in epoxy resin ingredient, it is also possible to microgranule, long fibre, chopped fiber, knits
The shapes such as thing, non-woven fabrics, net, pulpous state are arranged in the top layer of prepreg.When will be selected from thermoplastic resin, thermoplastic with such state
When more than a kind resin in property elastomer and elastomer is arranged in the top layer of prepreg, can suppress to make aforementioned prepreg solidify
Obtained by the splitting of fiber reinforced composite material.
In the present invention, about the addition of aforementioned additive in composition epoxy resin, relative to composition epoxy resin
In epoxy resin (composition A, or in composition epoxy resin containing components D time be components D and the total of composition A) 100
Mass parts, preferably 1～15 mass parts, more preferably 2～10 mass parts.If the addition of additive is 1～15 mass parts, then
It is prone in composition epoxy resin add, so preferably.In the present invention, and during with two or more additive, preferably with
The total amount of additive mode within the above range is adjusted.
In the present invention, as thermoplastic resin, main chain is preferably used there is choosing free carbon-carbon bond, amido link, acid imide
Key in the group of key, ester bond, ehter bond, carbonic acid ester bond, ammonia ester bond, urea bond, thioether bond, sulfone linkage, imidazoles key and carbonyl bond composition
Thermoplastic resin.Among them, more preferably use and be selected from polyacrylate, polyamide, Nomex, polyester, poly-carbonic acid
Ester, polyphenylene sulfide, polybenzimidazoles, polyimides, Polyetherimide, polysulfones and polyether sulfone are such belongs to the one of engineering plastics
Group thermoplastic resin.Wherein, polyimides, Polyetherimide, polysulfones and polyether sulfone etc. are particularly preferably used.By using these
Additive, the thermostability of the solidification resin of composition epoxy resin improves, so preferably.Additionally, from improving epoxy composite
The toughness of the solidfied material of thing and maintain solidification resin environment resistant from the viewpoint of, preferably these thermoplastic resins have with heat
The reactive functional groups of thermosetting resin reaction.As such functional group, carboxyl, amino and hydroxyl etc. can be enumerated.
Manufacture method ＞ of ＜ composition epoxy resin
The composition epoxy resin of the present invention can be by existing known method manufacture.For example, it is preferable to use glass to burn
Bottle, kneader, planetary stirring machine, general agitating heating still, stirring pressurized, heated still etc. manufacture.
The composition epoxy resin of the present invention is preferably manufactured by the manufacture method such as with following operation.
Operation (1): by epoxy resin (composition A, or be components D and the total of composition A when containing components D) and
The additives such as thermoplastic resin are put in dissolution vessel, add hot mixing 1～6 hours at 70～150 DEG C, thus obtain epoxy resin
The operation of host.
Operation (2): after aforementioned epoxy resins host is cooled to 50～70 DEG C, adding ingredient B and/or composition C, other
Firming agent, auxiliary curing agent, mix 0.5～2 hour at 50～70 DEG C, thus obtain the operation of composition epoxy resin.
The manufacture ＞ of ＜ prepreg
The composition epoxy resin of the present invention can be impregnated in reinforcing fiber bundle thus manufacture prepreg.The system of prepreg
The method of making is not particularly limited, even if the composition epoxy resin of the present invention is being heated to about 60～100 DEG C and viscosity declines
Time, the most also it is stable, therefore goes for what the hot melt (hot-melt) by not using solvent was carried out
The manufacture of prepreg.In addition it is possible to use following method: the composition epoxy resin of the present invention is coated on used stripping
Making thin film on paper even load sheet, appropriateness Pressurized-heated, i.e. heats together with reinforcing fiber bundle, the sheet that formed by reinforcing fiber bundle
To 80～120 DEG C and clamp with mip rolls and pressurize, so that it is impregnated in reinforcing fiber bundle, it is possible to use following method:
On the sheet composition epoxy resin of the present invention is coated directly onto reinforcing fiber bundle, being formed by reinforcing fiber bundle, similarly add
Pressure is heated, so that it is impregnated in reinforcing fiber bundle.
Make the composition epoxy resin of the present invention containing being immersed in the preservation at room temperature of the prepreg in reinforcing fiber bundle
Excellent in stability, additionally, have the viscosity of appropriateness, i.e. has prepreg and prepreg or prepreg and molding die surface
Cohesiveness and the easiness of stripping, it is possible to be applicable to make the fiber reinforced composite material of the shape of complexity.
(reinforcing fiber)
The reinforcing fiber combined with the composition epoxy resin of the present invention is not particularly limited, can be by carbon fiber, graphite
Fiber, glass fibre, organic fiber, boron fibre, steel fibre etc. are with shapes such as fibre bundle, cloth, chopped strand, delustring fabrics (mat)
State uses.
In these reinforcing fibers, carbon fiber, graphite fibre specific modulus good, i.e. machine direction elastic modelling quantity is 200GPa
Above, it is recognized that the lightweight for fiber reinforced composite material has remarkable result, so preferably.Additionally, according to purposes not
With, it is possible to use the carbon fiber of all kinds or graphite fibre.
＜ fiber reinforced composite material ＞
The composition epoxy resin of the present invention is adapted as the matrix resin of fiber reinforced composite material.
The manufacture method of the fiber reinforced composite material of the composition epoxy resin employing the present invention is limited the most especially
Fixed, can be manufactured by following method: make matrix resin composition inject and contain to be immersed in the parison comprising reinforcing fiber also
The RTM method (Resin Transfer Molding) of solidification or VaRTM method (Vacuum assisted Resin Transfer
Molding), by the sheet overlap of the sheet comprising reinforcing fiber bundle and the matrix resin of the composition epoxy resin comprising the present invention also
Heating under vacuum decompression state is so that aforementioned substrates resin impregnated is in the sheet comprising reinforcing fiber bundle and the RFI method that solidifies
(Resin Film Infusion), uses the molding of the prepreg being impregnated with aforementioned substrates resin in reinforcing fiber bundle and obtain
Method etc..
As the method for forming using prepreg, it is possible to use autoclave molding, vacuum-bag process, compressing etc. arbitrary
From effectively utilizing the feature of composition epoxy resin of the present invention, the method for forming, obtains that productivity ratio is high, the fibre strengthening of high-quality
From the viewpoint of composite, it is preferably laminated to type method.When making fiber reinforced composite material by compressing legal system, preferably
Including following operation: the composition epoxy resin of the present invention will be made containing being immersed in the prepreg in reinforcing fiber bundle or making aforementioned
The parison pre-adjusting that prepreg is laminated clamps to the mould of solidification temperature and heats pressurization.
Time compressing, the temperature in mould is preferably 100～150 DEG C.Furthermore it is preferred that it is solid under conditions of 1～15MPa
Change 1～20 minute.
At the composition epoxy resin utilizing the compressing method manufacture of aforementioned condition to contain the present invention as matrix resin
Fiber reinforced composite material time, in order to avoid by mould take out compressing after fiber reinforced composite material time occur do not wish
The deformation hoped, the vitrification point of the fibrous composite after preferred consolidation, especially as storage shear modulus (property
Rate) start the temperature that reduces and the G ' Tg that determines higher than the temperature of mould during molding.That is, as the alternate manner of the present invention, excellent
Choosing, by clamping and make composition epoxy resin contain to be immersed in and obtain in reinforcing fiber bundle being preheated to the mould of 140 DEG C
Prepreg is also forced into 1MPa, solidification 5 minutes, becomes more than 150 DEG C at the G ' Tg of this fiber reinforced composite material obtained.
The most preferably, make the composition epoxy resin of the present invention containing being immersed in reinforcing fiber bundle, by be preheated to the mould of 140 DEG C
Clamp and be forced into 1MPa, solidification 5 minutes, become more than 150 DEG C at the G ' Tg of this solidfied material obtained.Here, G ' Tg is
Refer to utilize the temperature dependency of the storage shear modulus (G ') obtained by the Measurement of Dynamic Viscoelasticity of solidfied material, by aftermentioned method
The vitrification point determined.
Additionally, the purposes employing the fiber reinforced composite material of the composition epoxy resin of the present invention limits the most especially
Fixed, headed by aircraft structural material, it is also possible to for mobile applications, marine purposes, Sport Utility and windmill, roller etc.
As industrial applications.
Embodiment
By the following examples the present invention is specifically illustrated, but the present invention is not by any restriction of these embodiments.
(embodiment 1)
(1) modulation of composition epoxy resin
Using bisphenol A type epoxy resin (epoxide equivalent 189g/eq, Mitsubishi Chemical's (strain) system, trade name as composition A
JER828) (table 1 is denoted as " A-1 ") 50 mass parts, as components D bisphenol-s epoxy resin (epoxide equivalent 300g/eq,
DIC (strain) system, trade name EXA-1514) (being denoted as " D-1 " in table 1) 50 mass parts, polyether sulfone (the equal molecule of matter as additive
Amount 32,000, BASF (strain) system, trade name Ultrason E2020P) (being denoted as " Z-2 " in table 1) 5 parts put in glass flask,
Add hot mixing at 100 DEG C, thus obtain uniform epoxy resin host.Then, the epoxy resin host of acquisition is cooled to 60
Below DEG C, it is then added as 2 phenyl 4 methyl 5 hydroxy methylimidazole (four countries' chemical conversion industry (strain) system, the commodity of composition B
Name 2P4MHZ-PW) (being denoted as " B-1 " in table 1) 10 mass parts, HX3722 (curing agent component content 35%, the rising sun as composition C
Chemical conversion E-materials (strain) system, trade name Novacure HX3722) (being denoted as " C-1 " in table 1) 5 mass parts, mix at 60 DEG C
Close so that it is dispersed, it is thus achieved that composition epoxy resin.
(2) making of resin plate is solidified
The composition epoxy resin of acquisition is injected into the politef sept that 2 pieces of 4mm are thick, be clamped with 2mm thickness
Glass plate between, under conditions of the temperature of glass surface is 140 DEG C with heated air circulation type constant temperature oven heat 10 minutes, then
Cooling, it is thus achieved that solidification resin plate.
(3) manufacture of prepreg
With comma coater with resin weight per unit area as 133g/m2By equal for the composition epoxy resin of acquisition in (1)
It is coated in release paper evenly, forms resin bed.It follows that paste Rhizoma Sparganii beautiful sun (strain) 3K processed plain weave carbon on aforementioned resin layer
After fiber cloth TR3110M, utilize (the rising sun fibre machinery industry of hot melt adhesive machine with the condition of temperature 80 DEG C, setting pressure 0.4MPa
(strain) system, JR-600S, treated length 1340mm, set pressure as drum pressure) carry out heating and pressurizeing, make epoxy resin group
Compound is impregnated with in the carbon fibers, and making fiber weight per unit area is 200g/m2, resin containing ratio be being pressed into of 40 mass %
Type prepreg.
(4) manufacture of fiber reinforced composite material
The compressing prepreg obtained in (3) is cut into long 298mm × 298mm, prepares 5 pieces of prepregs according to vertical
The machine direction of silk is alternately parison (thickness 1.1mm, the layer volume 97.7cm that the mode of 0 ° and 90 ° is laminated3, one side
Surface area 888cm2)。
Compressing mould uses the mould 1 illustrated in Figure 1A, Figure 1B.The face contacted with parison of the lower mold 3 of mould 1
The surface area of (not including the face that the caliper portion with fiber reinforced composite material contacts) is 900cm2。
First, upper mold 2 and the lower mold 3 of mould 1 are previously heated to 140 DEG C, lower mold 3 configure aforementioned parison, immediately
Making upper mold 2 decline thus close mould 1, the heating pressurization that the pressure of applying 10MPa is carried out 5 minutes makes it solidify.Then, from mould
Tool 1 taking-up article shaped, it is thus achieved that fiber reinforced composite material.
Calculate by following formula from the resin discharge rate of mould trimming (shear edge).
Resin discharge rate (%)=(W1-W2)/W1 × 100
Wherein, W1: the quality (g) of the parison before solidification
The quality (g) of W2: article shaped (after deburring)
(5) mensuration of thermostability (vitrification point: G ' Tg)
The fiber reinforced composite material obtained in the resin plate obtained in (2), (4) is processed into test film (length 55mm
× width 12.5mm), use TA Instruments society flow graph ARES-RDA, mensuration frequency 1Hz, programming rate 5 DEG C/
Under minute, logG ' is mapped relative to temperature, the district that the near linear of the flat site of record logG ' and logG ' drastically reduce
The temperature of the intersection point of the near linear in territory, as vitrification point (G ' Tg).
(6) evaluation in the life-span of prepreg
(3) life-span of the prepreg obtained in is evaluated as follows: by prepreg in temperature 23 ± 2 DEG C, the reality of humidity 50 ± 5%
Test indoor standing after 3 weeks, tested by the sense of touch of finger tip, be evaluated according to following judgment standard.
A: cohesiveness, flexibility are the most appropriate, therefore show easily to operate.
B: viscosity is weak or lacks flexibility, therefore shows to be difficult to operation.
C: cohesiveness, flexibility are excessively poor, therefore show to be difficult to operate.
(embodiment 1～28, comparative example 1～25)
About embodiment 1～28 and comparative example 1～25, except the composition of composition epoxy resin being changed to table 1～4 institute
Beyond the content recorded, all manufacture fiber reinforced composite material according to operation same as in Example 1 and carry out this fibre strengthening
The physical property measurement of composite.In table 1～table 4, " content of composition B " refers to the total amount of composition B in composition epoxy resin.
Additionally, " content of composition C " refers to the total amount of composition C in composition epoxy resin.Composition C is used to be encapsulated in microcapsule
During masterbatch type curing agent, the use level of aforementioned masterbatch type curing agent is multiplied by curing agent component content (%) and the value that calculates
Total amount is recited as the content of composition C.
Abbreviation in table 1～table 4 is as follows.
Composition A: intramolecular does not have the epoxy resin of sulphur atom
A-1: bisphenol A type epoxy resin (epoxide equivalent 189g/eq, Mitsubishi Chemical's (strain) system, trade name: jER828)
A-2: bisphenol A type epoxy resin (epoxide equivalent 475g/eq, Mitsubishi Chemical's (strain) system, trade name: jER1001)
A-3: dicyclopentadiene-type epoxy resin (epoxide equivalent 265g/eq, DIC (strain) system, trade name: HP7200)
A-4: tris-phenol type epoxy resin (epoxide equivalent 169g/eq, Mitsubishi Chemical's (strain) system, trade name:
jER1032)
A-5: diaminodiphenyl-methane type epoxy resin (epoxide equivalent 120g/eq, Mitsubishi Chemical's (strain) system, trade name:
jER604)
A-6: liquid phenolic resin varnish type epoxy resin (epoxide equivalent 177g/eq, Mitsubishi Chemical's (strain) system, trade name:
jER152)
A-7: bisphenol f type epoxy resin (epoxide equivalent 168g/eq, Mitsubishi Chemical's (strain) system, trade name: jER807)
A-8: naphthalene skeletal epoxy resin (epoxide equivalent 150g/eq, DIC (strain) system, trade name: HP4032)
A-9: haveEpoxy resin (epoxide equivalent 189g/eq, the Asahi Chemical Industry E-materials (strain) of oxazolidone ring
System, trade name: AER4152)
Imidazolium compounds shown in composition B: formula (1)
B-1:2-phenyl-4-methyl-5-hydroxy methylimidazole (four countries' chemical conversion industry (strain) system, trade name: 2P4MHZ-PW)
B-2:2-phenyl-4,5-hydroxymethyl-imidazole (four countries' chemical conversion industry (strain) system, trade name: 2PHZ-PW)
Imidazolium compounds shown in composition C: formula (2)
Use the following masterbatch type curing agent containing the composition C being encapsulated in microcapsule.
C-1:HX3722 (curing agent component content 35%, Asahi Chemical Industry E-materials (strain) system, trade name: Novacure
HX3722)
C-2:HX3748 (curing agent component content 35%, Asahi Chemical Industry E-materials (strain) system, trade name: Novacure
HX3748)
Components D: intramolecular has the epoxy resin of at least one sulphur atom
D-1: bisphenol-s epoxy resin (epoxide equivalent 300g/eq, DIC (strain) system, trade name: EXA-1514)
The product of D-2:A-1 and 4,4 '-diamino diphenyl sulfone:
By A-1 and 4,4 '-diamino diphenyl sulfone (Wakayama refine industry (strain) system, trade name: SeikacureS) press
Mass ratio according to A-1/4,4 '-diamino diphenyl sulfone=100/9 is reacting obtained by 150 DEG C of Hybrid Heating after mixed at room temperature
Product, is product the mixing as main component of the amines with epoxy resin and intramolecular with at least one sulphur atom
Compound (epoxide equivalent 266g/eq)
Auxiliary curing agent (X):
X-1:3-phenyl-1,1-dimethyl urea (PTI Japan (strain) system, trade name: Omicure94)
X-2:1,1 '-(4-methyl isophthalic acid, 3-phenylene) double (3,3-dimethyl urea) (PTI Japan (strain) system, trade name:
Omicure24)
X-3:4,4 '-methylene bis (phenyl dimethyl urea) (PTI Japan (strain) system, trade name: Omicure52)
Other firming agent (Y):
(the four countries' chemical conversion industry of Y-1:2,4-diaminourea-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine
(strain) system, trade name: C11Z-A)
Y-2:2,4-diaminourea-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine isocyanuric acid adduct (four countries
Chemical conversion industry (strain) system, trade name: 2MA-OK)
Y-3: dicyandiamide (Mitsubishi Chemical's (strain) system, trade name: DICY15)
Y-4:2-Methylimidazole. (four countries' chemical conversion industry (strain) system, trade name: 2MZ-H)
Y-5:1,2-methylimidazole (four countries' chemical conversion industry (strain) system, trade name: 1,2DMZ)
Y-6:2,4-diaminourea-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine (four countries' chemical conversion industry (strain) system,
Trade name: 2MZ-A)
Y-7:N-benzyl-2-methylimidazole (Tokyo chemical conversion industry (strain) system)
Y-8:1-(2-hydroxyethyl)-2-methylimidazole (Japan's synthetic chemical industry (strain) system)
Y-9: isophthalic dihydrazide (big chemistry (strain) system, trade name: IDH-S)
The thermoplastic resin (Z) used as additive:
Z-1: phenoxy resin (Nippon Steel chemistry (strain) system, trade name Phenotote YP-50S, matter average molecular weight 50,
000～70,000)
Z-2: polyether sulfone (BASF (strain) system, trade name Ultrason E2020P, matter average molecular weight 32,000)
3K flat carbon fabric cloth: the beautiful sun of Rhizoma Sparganii (strain) system, trade name TR3110M
[table 1]
[table 2]
[table 3]
[table 4]
From table 1～4, embodiment 1～16 excellent storage stability of the prepreg obtained respectively.Additionally, this is real
Executing example 1～16 and show high G ' Tg, thus can also know, the fibre strengthening using the composition epoxy resin of the present invention to manufacture is multiple
Condensation material has high-fire resistance.
On the other hand, in the comparative example 1 low for G ' Tg of the fiber reinforced composite material after solidification, during the demoulding, products formed is firm
Property is low, and therefore in stripping operation, products formed deforms.Therefore, in comparative example 1, in order to obtain good products formed, it is necessary to
Cool down before the products formed demoulding, it is difficult to carry out the molding of fiber reinforced composite material with high frequency.
Additionally, in the comparative example 1,12 and 18～20 that all do not contains of composition C and components D, thermostability (G ' Tg) is low, in addition than
In relatively example 1,2, too much resin during heat-pressure curing, is had to flow out.Additionally, do not contain the comparative example 4～11,21～25 of composition B
In, thermostability is low.And then, do not contain in the comparative example 7,8 of composition C yet, during heat-pressure curing, have too much resin to flow.?
In comparative example 3,13～17, owing to the addition of other firming agent, auxiliary curing agent is many, therefore the storage stability of prepreg is poor.
On the other hand, compared with embodiment 27,28, the thermostability of embodiment 26 and 17 is high, wherein, and embodiment 17 heat-resisting
Property is the highest.In addition understanding, compared with comparative example 24, the thermostability of embodiment 18 is higher.It follows that in composition epoxy resin
The addition of composition B is preferably relative to epoxy resin 100 mass parts (containing during components D being components D and the total amount of composition A
100 mass parts) it is 2～40 mass parts.
Compared with embodiment 14, the resin discharge of embodiment 6 is few, is 0.9%, from but preferably, the tree of embodiment 3
Fat discharge is less, is 0.8%, from but preferably.Additionally, compared with embodiment 14, the resin discharge of embodiment 8 is few,
Be 1.2%, from but preferably.From these experimental results, the content of composition C is preferably relative to epoxy resin 100 matter
Amount part (total amount 100 mass parts containing during components D being components D and composition A) is 1～6 mass parts.
Compared with embodiment 25, the thermostability of embodiment 23 is high, from but preferably, the thermostability of embodiment 17 is higher,
From but preferably.Additionally, compared with embodiment 20, the thermostability of embodiment 12 is preferred.From these experimental results,
The addition of components D is preferably 95:5～10:90 in terms of the mass ratio of composition A: components D.
Industrial applicability
The composition epoxy resin of the present invention can suppress the excess flow of resin during heat-pressure curing, therefore can fit
In the matrix resin as fiber reinforced composite material.
Description of reference numerals
1 mould
2 upper molds
3 lower molds
4 female cross cutting edge
5 androtype trimming portions
6 moulding materials
Claims (4)
1. a composition epoxy resin, it is characterised in that it is containing composition A, composition B and the epoxy composite of composition C
Thing,
Composition A: intramolecular does not have the epoxy resin of sulphur atom,
Imidazolium compounds shown in composition B: following formula (1),
Imidazolium compounds shown in composition C: following formula (2),
In formula (1), R1Represent the alkyl of straight or branched of carbon number 1～5, methylol, R2Represent the straight of carbon number 1～5
Chain or the alkyl of side chain or hydrogen atom,
In formula (2), R3Represent the organic group containing more than 1 carbon atom, R4～R6Represent hydrogen atom or methyl or ethyl,
Described composition C is the imidazolium compounds being encapsulated in microcapsule,
The content of described composition B is 2～40 mass parts relative to epoxy resin 100 mass parts contained by composition epoxy resin,
The content of described composition C is 1～6 mass parts relative to epoxy resin 100 mass parts in composition epoxy resin.
2. a prepreg, it is to make the composition epoxy resin described in claim 1 form containing being immersed in reinforcing fiber bundle.
3. a fiber reinforced composite material, it is to make the prepreg solidification described in claim 2 obtain.
4. a manufacture method for fiber reinforced composite material, its have make the prepreg described in claim 2 in mould
The operation of 1～20 minute is kept under conditions of 100～150 DEG C, 1～15MPa.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510816527.6A CN105254848B (en) | 2011-11-29 | 2012-11-29 | Composition epoxy resin, prepreg, fiber reinforced composite material and its manufacturing method |
| CN201610294024.1A CN105949716B (en) | 2011-11-29 | 2012-11-29 | Composition epoxy resin, prepreg and fiber reinforced composite material |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-260733 | 2011-11-29 | ||
| JP2011-260732 | 2011-11-29 | ||
| JP2011260733 | 2011-11-29 | ||
| JP2011260732 | 2011-11-29 | ||
| PCT/JP2012/080956 WO2013081060A1 (en) | 2011-11-29 | 2012-11-29 | Epoxy resin composition, prepreg, fiber-reinforced composite material, and method for producing same |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510816527.6A Division CN105254848B (en) | 2011-11-29 | 2012-11-29 | Composition epoxy resin, prepreg, fiber reinforced composite material and its manufacturing method |
| CN201610294024.1A Division CN105949716B (en) | 2011-11-29 | 2012-11-29 | Composition epoxy resin, prepreg and fiber reinforced composite material |
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| Publication Number | Publication Date |
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| CN103958560A CN103958560A (en) | 2014-07-30 |
| CN103958560B true CN103958560B (en) | 2016-11-30 |
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