CN111801367A - 纤维强化复合材料用树脂组合物及使其的纤维强化复合材料 - Google Patents
纤维强化复合材料用树脂组合物及使其的纤维强化复合材料 Download PDFInfo
- Publication number
- CN111801367A CN111801367A CN201980017130.7A CN201980017130A CN111801367A CN 111801367 A CN111801367 A CN 111801367A CN 201980017130 A CN201980017130 A CN 201980017130A CN 111801367 A CN111801367 A CN 111801367A
- Authority
- CN
- China
- Prior art keywords
- fiber
- reinforced composite
- composite material
- resin composition
- resin
- 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
- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 61
- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- -1 amine compound Chemical class 0.000 claims abstract description 38
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 28
- 229920003986 novolac Polymers 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 11
- 238000000748 compression moulding Methods 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000001721 transfer moulding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005227 gel permeation chromatography Methods 0.000 claims description 4
- 239000004848 polyfunctional curative Substances 0.000 abstract description 11
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 abstract description 6
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 40
- 238000000465 moulding Methods 0.000 description 22
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 15
- 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 11
- 238000012360 testing method Methods 0.000 description 11
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- 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 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DTFQULSULHRJOA-UHFFFAOYSA-N 2,3,5,6-tetrabromobenzene-1,4-diol Chemical compound OC1=C(Br)C(Br)=C(O)C(Br)=C1Br DTFQULSULHRJOA-UHFFFAOYSA-N 0.000 description 2
- GPMCZKILFBRNNY-UHFFFAOYSA-N 2,3-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=C(O)C=CC(O)=C1C(C)(C)CC GPMCZKILFBRNNY-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- 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
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-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
- IFEWMSGMDUQOFZ-UHFFFAOYSA-N 2,3,5-tribromobenzene-1,4-diol Chemical compound OC1=CC(Br)=C(O)C(Br)=C1Br IFEWMSGMDUQOFZ-UHFFFAOYSA-N 0.000 description 1
- ZIIRLFNUZROIBX-UHFFFAOYSA-N 2,3,5-trichlorobenzene-1,4-diol Chemical compound OC1=CC(Cl)=C(O)C(Cl)=C1Cl ZIIRLFNUZROIBX-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- XIWRQEFBSZWJTH-UHFFFAOYSA-N 2,3-dibromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1Br XIWRQEFBSZWJTH-UHFFFAOYSA-N 0.000 description 1
- DBCKMJVEAUXWJJ-UHFFFAOYSA-N 2,3-dichlorobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Cl)=C1Cl DBCKMJVEAUXWJJ-UHFFFAOYSA-N 0.000 description 1
- PKFWNYFJULYNFI-UHFFFAOYSA-N 2,3-diphenylbenzene-1,4-diol Chemical compound C=1C=CC=CC=1C=1C(O)=CC=C(O)C=1C1=CC=CC=C1 PKFWNYFJULYNFI-UHFFFAOYSA-N 0.000 description 1
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 description 1
- FKWOGPPGVRDIRZ-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=CC=C1O FKWOGPPGVRDIRZ-UHFFFAOYSA-N 0.000 description 1
- HIGSPBFIOSHWQG-UHFFFAOYSA-N 2-Isopropyl-1,4-benzenediol Chemical compound CC(C)C1=CC(O)=CC=C1O HIGSPBFIOSHWQG-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- PULOARGYCVHSDH-UHFFFAOYSA-N 2-amino-3,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1OC1CC1=C(CC2OC2)C(N)=C(O)C=C1CC1CO1 PULOARGYCVHSDH-UHFFFAOYSA-N 0.000 description 1
- REFDOIWRJDGBHY-UHFFFAOYSA-N 2-bromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1 REFDOIWRJDGBHY-UHFFFAOYSA-N 0.000 description 1
- XEXCJROIGGFECP-UHFFFAOYSA-N 2-methyl-3-propan-2-ylbenzene-1,4-diol Chemical compound CC(C)C1=C(O)C=CC(O)=C1C XEXCJROIGGFECP-UHFFFAOYSA-N 0.000 description 1
- VIIYYMZOGKODQG-UHFFFAOYSA-N 2-nitrobenzene-1,4-diol Chemical compound OC1=CC=C(O)C([N+]([O-])=O)=C1 VIIYYMZOGKODQG-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-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
- GRWFFFOEIHGUBG-UHFFFAOYSA-N 3,4-Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo-hexanecarboxylate Chemical compound C1C2OC2CC(C)C1C(=O)OCC1CC2OC2CC1C GRWFFFOEIHGUBG-UHFFFAOYSA-N 0.000 description 1
- FLROJJGKUKLCAE-UHFFFAOYSA-N 3-amino-2-methylphenol Chemical compound CC1=C(N)C=CC=C1O FLROJJGKUKLCAE-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000531908 Aramides Species 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Chemical class 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- RPYFJVIASOJLJS-UHFFFAOYSA-N [3-(aminomethyl)-2-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1CC2C(CN)C(CN)C1C2 RPYFJVIASOJLJS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- BXJGUBZTZWCMEX-UHFFFAOYSA-N dimethylhydroquinone Natural products CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SUNVJLYYDZCIIK-UHFFFAOYSA-N durohydroquinone Chemical compound CC1=C(C)C(O)=C(C)C(C)=C1O SUNVJLYYDZCIIK-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PYXKIBGUDPZSBQ-UHFFFAOYSA-N phenol;3,5,5-trimethylcyclohex-2-en-1-one Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.CC1=CC(=O)CC(C)(C)C1 PYXKIBGUDPZSBQ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- STOSPPMGXZPHKP-UHFFFAOYSA-N tetrachlorohydroquinone Chemical compound OC1=C(Cl)C(Cl)=C(O)C(Cl)=C1Cl STOSPPMGXZPHKP-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
本发明的目的在于提供一种无损低粘度性与耐热性,且快速硬化性优异的树脂组合物。一种纤维强化复合材料用树脂组合物及在其中调配强化纤维而获得的纤维强化复合材料,所述纤维强化复合材料用树脂组合物为包括主剂及硬化剂、且主剂与硬化剂的质量比为90:10~70:30的范围的二液硬化型的树脂组合物,所述主剂包含环氧树脂(A),所述硬化剂包含选自降冰片烷二胺或三乙四胺中的胺化合物(B)及酚化合物(C),所述纤维强化复合材料用树脂组合物的特征在于:酚化合物(C)包含具有两个以上的酚性羟基的酚化合物,且在硬化剂中含有5重量%~35重量%。
Description
技术领域
本发明涉及一种粘度低且短时间内的硬化性优异的纤维强化复合材料用的树脂组合物、使用其的纤维强化复合材料及使用其的纤维强化成形体的制造方法。
背景技术
一般而言,纤维强化复合材料包含玻璃纤维、聚芳酰胺(aramide)纤维或碳纤维等强化纤维及不饱和聚酯树脂、乙烯酯树脂、环氧树脂、酚树脂、苯并噁嗪树脂、氰酸酯树脂、双马来酰亚胺树脂等热硬化性基质树脂,就轻量且强度、耐腐蚀性或耐疲劳性等机械物性优异的方面而言,作为飞机、汽车、土木建筑及运动用品等的结构材料而广泛适用。
纤维强化复合材料的制造方法是通过以下方法而实施:使用将热硬化性的基质树脂预先含浸于强化纤维所得的预浸体的高压釜成形法或压制成形法;或包括使液状的基质树脂含浸于强化纤维的步骤及通过热硬化而进行的成形步骤的树脂转注成形法(resintransfer molding method)、液体压缩成形法(liquid compression molding method)、湿敷(wet lay-up)成形法、拉拔成形法或长丝缠绕(filament winding)成形法等。其中,不使用预浸体来进行含浸与成形的树脂转注等成形法中,为使强化纤维快速地含浸,而使用低粘度的基质树脂。
此外,在树脂转注成形法、液体压缩成形法中,为了确保高生产性,在使强化纤维含浸树脂后,要求硬化速度快的基质树脂。进而,在这些成形法中,包括在硬化后将成形物自模具脱模的步骤,为了确保高生产性,要求不仅硬化速度快而且脱模性也优异的基质树脂组合物。
以往,在树脂转注成形法、液体压缩成形法中,一直使用不饱和聚酯树脂、乙烯酯树脂、氨基甲酸酯树脂或环氧树脂等热硬化性树脂。具有自由基聚合性的不饱和聚酯树脂、乙烯酯树脂虽然粘度低且快速硬化性优异,但有成形时的硬化收缩大,成形物的耐热性、强度或韧性等机械物性相对低的课题。氨基甲酸酯树脂虽然可获得快速硬化性优异、强度或韧性高的成形物,但有成形物的耐热性低、吸水率高的课题。环氧树脂虽然可获得耐热性、强度或韧性高的成形物,但有快速硬化性差的课题。
专利文献1中,虽然尝试通过环氧树脂与特定的酚化合物的组合来对树脂组合物赋予快速硬化性,但至凝胶化为止的时间长,快速硬化性不足,耐热性也差。
专利文献2、专利文献3中,尝试通过在包含环氧树脂与聚乙烯多胺的树脂组合物中添加特定的催化剂来赋予快速硬化性。但是,至凝胶化为止的时间长,快速硬化性不足。
专利文献4中,尝试通过环氧树脂与特定的胺化合物、酚化合物的组合来对树脂组合物赋予快速硬化性,但仍然是快速硬化性不足。
关于纤维强化复合材料的基质树脂,为使低粘度性优异且不降低耐热性、进而确保高生产性,期望快速硬化性的进一步提升。
现有技术文献
专利文献
专利文献1:日本专利特开2016-098322号公报
专利文献2:日本专利特表2015-535022号公报
专利文献3:日本专利特表2015-536373号公报
专利文献4:WO2017/179358号公报
发明内容
本发明的目的在于提供一种无损低粘度性与耐热性、且快速硬化性优异的纤维强化复合材料用的树脂组合物。进而,目的在于提供一种可生产性良好地获得纤维强化复合材料及纤维强化成形体的树脂组合物或制造方法。
本发明人等人为解决所述课题而进行研究,结果发现,通过使用包含特定的环氧树脂的主剂、及包含特定的胺化合物与具有酚性羟基的酚化合物的硬化剂,而解决所述课题,从而完成本发明。
即,本发明为一种纤维强化复合材料用树脂组合物,其为包括主剂及硬化剂、且主剂与硬化剂的质量比为90:10~70:30的范围的二液硬化型的树脂组合物,所述主剂包含环氧树脂(A),所述硬化剂包含下述式(1)或式(2)所表示的胺化合物(B)及酚化合物(C),所述纤维强化复合材料用树脂组合物的特征在于:酚化合物(C)包含具有两个以上的酚性羟基的酚化合物,且在硬化剂中含有5重量%~35重量%。
[化1]
所述酚化合物(C)优选为由下述通式(3)所表示,且以在凝胶渗透色谱法的测定中二核体含有率为17面积%以下、三核体含有率为38面积%以上、四核体以上的含有率为45面积%以下的比例构成的苯酚酚醛清漆。
[化2]
(式中,n表示0以上的整数,为0~5)
所述硬化剂的25℃下的粘度优选为2000mPa·s以下。所述粘度可通过E型粘度计进行测定。
本发明的纤维强化复合材料用树脂组合物可为将其在120℃下进行5分钟热处理而硬化成的硬化物的玻璃化温度为110℃以上。
本发明的另一实施例为一种纤维强化复合材料,其特征在于,其是在所述纤维强化复合材料用树脂组合物中调配强化纤维而成。所述情况下,强化纤维的体积含有率优选为45%~70%。
另外,本发明为一种成形体的制造方法,其特征在于,利用树脂转注成形法、或液体压缩成形法将所述纤维强化复合材料成形。
本发明的又一实施例为一种成形体的制造方法,其特征在于包括如下步骤,所述步骤包括:准备所述二液硬化型的纤维强化复合材料用树脂组合物;将所述纤维强化复合材料用树脂组合物的二液与强化纤维混合而制成纤维强化复合材料;继而利用模具将所述纤维强化复合材料加热硬化而成形。
本发明的纤维强化复合材料用树脂组合物的粘度低,具有良好的对强化纤维的含浸性,且显示出短时间内的硬化性。因此,适合作为用以通过树脂转注成形法或液体压缩成形法将纤维强化复合材料制成成形体的纤维强化复合材料用树脂组合物。进而,硬化而得的成形物为自模具的脱模性优异,且玻璃化温度高者。
具体实施方式
以下,对本发明的实施方式进行详细说明。
本发明的纤维强化复合材料用树脂组合物在其中调配强化纤维而形成纤维强化复合材料,且通过将所述纤维强化复合材料硬化或成形而形成硬化物或成形体。以下,也将纤维强化复合材料用树脂组合物称为树脂组合物,也将纤维强化复合材料称为复合材料。
本发明的树脂组合物为包括主剂及硬化剂的二液硬化型的树脂组合物,所述主剂包含环氧树脂(A),所述硬化剂包含所述式(1)或式(2)所表示的胺化合物(B)及酚化合物(C)。此处,也将所述环氧树脂(A)、胺化合物(C)、酚化合物(C)分别称为(A)成分、(B)成分、及(C)成分,或者分别称为环氧树脂、胺化合物、及酚化合物。
用作主剂成分的环氧树脂(A)可优选地使用二官能以上的环氧树脂。具体而言,可使用双酚A型环氧树脂、双酚F型环氧树脂、双酚E型环氧树脂、双酚S型环氧树脂、双酚Z型环氧树脂、异佛尔酮双酚型环氧树脂等双酚型环氧树脂;这些双酚型环氧树脂的卤素、烷基取代物、氢化物等、以及不限于单量体而具有多个重复单元的高分子量体;环氧烷加成物的缩水甘油醚;苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双酚A酚醛清漆型环氧树脂等酚醛清漆型环氧树脂;3,4-环氧基-6-甲基环己基甲基-3,4-环氧基-6-甲基环己烷羧酸酯、3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯、1-环氧基乙基-3,4-环氧基环己烷等脂环式环氧树脂;三羟甲基丙烷聚缩水甘油醚、季戊四醇聚缩水甘油醚、聚氧亚烷基二缩水甘油醚等脂肪族环氧树脂;邻苯二甲酸二缩水甘油酯、四氢邻苯二甲酸二缩水甘油酯、二聚酸缩水甘油酯等缩水甘油酯;四缩水甘油基二氨基二苯基甲烷、四缩水甘油基二氨基二苯基砜、三缩水甘油基氨基苯酚、三缩水甘油基氨基甲酚、四缩水甘油基亚二甲苯二胺等缩水甘油胺类等。这些可单独使用一种,也可组合使用两种以上。
就流动性的观点而言,环氧树脂的25℃下的粘度优选为30000mPa·s以下。再者,本说明书中,只要无特别说明,则粘度是通过E型粘度计进行测定。
用作硬化剂成分的胺化合物(B)为所述式(1)所表示的降冰片烷二胺、或所述式(2)所表示的三乙四胺。通过为这些胺化合物,快速硬化性提升。降冰片烷二胺、三乙四胺可分别单独使用,也可混合使用。
另一用作硬化剂成分的酚化合物(C)为一分子中具有两个以上的酚性羟基作为官能基的酚化合物。通过为两个以上,快速硬化性提升。
作为所述酚化合物的具体例,可列举:双酚A、双酚S、双酚F、联苯酚、双酚芴、2,2-双(4-羟基-3,5-二甲基苯基)丙烷、4,4'-亚甲基双(2,6-二甲基苯酚)、4,4'-亚甲基双(2,6-二-叔丁基苯酚)、双甲酚芴、苯酚酚醛清漆、甲酚酚醛清漆、对苯二酚、甲基对苯二酚、二甲基对苯二酚、三甲基对苯二酚、四甲基对苯二酚、异丙基对苯二酚、甲基-异丙基对苯二酚、单-叔丁基对苯二酚、二-叔丁基对苯二酚、单-叔戊基对苯二酚、二-叔戊基对苯二酚、硝基对苯二酚、苯基对苯二酚、二苯基对苯二酚、氯对苯二酚、二氯对苯二酚、三氯对苯二酚、四氯对苯二酚、溴对苯二酚、二溴对苯二酚、三溴对苯二酚、四溴对苯二酚、儿茶酚、叔丁基儿茶酚、间苯二酚、邻苯三酚、二硝基邻苯三酚、1,2,4-苯三醇等,这些可单独使用一种,也可视需要而使用两种以上。
这些中,尤其是双酚A、双酚F、或苯酚酚醛清漆就快速硬化性与硬化剂的品质稳定性的方面而言优异。
作为所述苯酚酚醛清漆,优选为由所述通式(3)所表示,且以在凝胶渗透色谱法(gel permeation chromatography,GPC)的测定中二核体含有率为17面积%以下、三核体含有率为38面积%以上、四核体以上的含有率为45面积%以下的比例构成的苯酚酚醛清漆。此处,所谓二核体是指通式(3)中n=0的成分,所谓三核体是指通式(3)中n=1的成分,所谓四核体是指通式(3)中n=2的成分。通过以二核体含有率为17面积%以下、三核体含有率为38面积%以上、四核体以上的含有率为45面积%以下的比例包含,硬化剂的粘度不会过高,可无损对纤维的含浸性地显现快速硬化性。
本发明的树脂组合物为主剂与硬化剂的二液硬化型,包含所述胺化合物与酚化合物的硬化剂可视需要而包含其他硬化剂成分、硬化促进剂、或硬化催化剂。
另外,在主剂及硬化剂中,也可适当调配塑化剂、染料、有机颜料或无机填充剂、高分子化合物、偶合剂、表面活性剂及溶剂等作为其他成分。另外,也可调配其他硬化性树脂。作为此种硬化性树脂,可列举不饱和聚酯树脂、硬化性丙烯酸树脂、硬化性氨基树脂、硬化性三聚氰胺树脂、硬化性脲树脂、硬化性氰酸酯树脂、硬化性氨基甲酸酯树脂、硬化性氧杂环丁烷树脂、硬化性环氧基/氧杂环丁烷复合树脂等,但并不限定于这些。
这些可考虑与主剂及硬化剂中所含的成分的反应性或粘度等而调配于任一者中。避免与主剂或硬化剂中所含的成分反应地进行调配。另外,溶剂会使成形体的生产性下降,故理想的是不含或为少量。
作为所述其他硬化剂成分或硬化促进剂、硬化催化剂,例如可列举:三级胺、羧酸、磺酸、路易斯酸络合物、鎓盐、咪唑、醇类、或苯酚、甲酚、丙烯酚(allyl phenol)、硝基酚、对氨基酚、间氨基酚、单-叔丁基酚、二-叔丁基酚等具有一个酚性羟基的化合物等。这些可使用一种或两种以上。
硬化剂中理想的是以5质量%~35质量%的范围包含酚化合物(C)。若含有率过低,则快速硬化性无法充分显现。另一方面,若含有率过高,则硬化剂的粘度变得过高,此外耐热性也下降。
胺化合物(B)的含有率理想的是以65%~95%的范围包含。
硬化剂的25℃下的粘度优选为2000mPa·s以下。若粘度超过2000mPa·s,则难以在强化纤维中充分含浸。粘度的下限并无特别限制,粘度越低,成形时的组合物的注入含浸越容易而优选。
本发明的树脂组合物为主剂与硬化剂的二液硬化型,通过将这些以规定的比例混合,而能够加热硬化。所述主剂与硬化剂的混合比率是根据主剂中的环氧树脂成分与硬化剂中的硬化剂成分的种类而决定。具体而言,计算所有环氧树脂成分中所含的环氧基的摩尔数及硬化剂成分中所含的活性氢的摩尔数的比率而加以调整,摩尔比为90:10~70:30的范围。若为所述范围,则所得的树脂硬化物的耐热性或弹性系数优异。
本发明的树脂组合物的在120℃下加热5分钟而成为硬化物时的玻璃化温度(Tg)优选为100℃以上,更优选为110℃以上。在Tg低于100℃的情况下,当将所得的纤维强化复合材料的硬化物或成形体自模具脱模时容易变形。
作为本发明的纤维强化复合材料中使用的强化纤维,选自玻璃纤维、聚芳酰胺纤维、碳纤维、硼纤维等中,但为了获得强度优异的纤维强化复合材料,优选为使用碳纤维。
本发明的纤维强化复合材料包含所述树脂组合物及强化纤维。纤维强化复合材料中的强化纤维的体积含有率优选为45%~70%,更优选为48%~62%的范围。通过设为所述范围,可获得空隙少且强化纤维的体积含有率高的成形体,因而可获得强度优异的成形材料。
纤维强化复合材料的硬化可优选地通过以下方式来进行:将主剂以50℃~90℃的范围、将硬化剂以20℃~60℃的范围的温度注入至预先配置有纤维的模具等中,以90℃~160℃的温度、优选为100℃~140℃加热硬化15秒~360秒的时间、优选为25秒~150秒。主剂与硬化剂可同时注入至模具中,为了提高均匀性,理想的是之前混合后进行注入。但是,也可不进行混合而注入至模具中,并在纤维的存在下进行混合。作为混合方式,冲突混合、静态混合器方式等并无特别限制,优选为短时间内完成均匀混合的冲突混合方式。
若注入温度低,则流动性下降,从而导致对成形模具及纤维的填充不良而欠佳。另外,若注入温度高,则产生飞边,或在注入时树脂开始硬化而槽内或成形模具内的树脂硬化,产生填充不良,因而欠佳。另外,若成形时间过短,则无法充分填充,若过长,则模具内的树脂硬化而导致成形不良,并且导致生产性的下降,因而欠佳。本发明的纤维强化复合材料中所含的树脂组合物可获得能够在如所述那样的较低注入温度下注入、含浸于成形模具,另外以短的硬化时间完成自模具的脱模的硬化物。
由本发明的树脂组合物来制作纤维强化复合材料或成形体的方法并无特别限定,适宜为树脂转注成形(resin transfer molding,RTM)法或液体压缩成形(liquidcompression molding,LCM)法。所谓RTM法,是指将包含强化纤维的纤维基材或预成形体设置于成形模具内,在所述成形模具内注入液状的纤维强化复合材料用树脂组合物而使强化纤维含浸,制成纤维强化复合材料,其后进行加热而使纤维强化复合材料硬化,从而获得成形体的方法。硬化条件适宜为所述纤维强化复合材料用树脂组合物的硬化中所说明的条件。所谓LCM法,是指将包含预先融合有树脂的强化纤维的纤维基材或预成形体,在释放了成形压力的状态下设置于成形模具内,并将成形模具合模,由此而同时进行含浸与成形,并在制成纤维强化复合材料后将模具加热而使纤维强化复合材料硬化,从而获得成形体的方法。LCM法的硬化条件也适宜为所述纤维强化复合材料用树脂组合物的硬化中所说明的条件。
实施例
其次,基于实施例对本发明进行具体的说明,但本发明只要不超过其主旨,则并不限定于以下的实施例。表示调配量的份只要无特别说明则为质量份。
实施例及比较例中使用的各成分的简称如下所述。
YD-128:双酚A型环氧树脂(新日铁住金化学公司制造)
YDF-170:双酚F型环氧树脂(新日铁住金化学公司制造)
TETA:三乙四胺
NBDA:双(氨基甲基)降冰片烷
1,3-BAC:1,3-双氨基甲基环己烷
BPA:双酚A
BPF:双酚F
4tBP:4-叔丁基苯酚
合成例1
在具备搅拌机、温度调节装置、回流冷却器、完全冷凝器、减压装置等的搅拌槽型反应机中,加入100份的作为双酚F且二核体量为90面积%的双酚F、及600份的苯酚,升温至80℃后,添加1.55份的草酸二水合物,搅拌10分钟而溶解后,历时30分钟滴加115份的37.5%福马林。其后,将反应温度维持为92℃,继续反应3小时。反应结束后,将温度提高至110℃,进行脱水后,将残存的苯酚在150℃、60mmHg的回收条件下回收约90%后,在160℃、5mmHg的回收条件下回收,之后进而在160℃、80mmHg的条件下历时90分钟滴加水10份而将残存的苯酚去除,获得粗苯酚酚醛清漆树脂。所得的粗苯酚酚醛清漆树脂的组成为:二核体量为55.1面积%、三核体量为24.9面积%、四核体量为11.1面积%、五核体量为5.0面积%、六核体以上的含量为3.9面积%,Mw为339,分散度(Mw/Mn)为1.190。
将以上所得的粗苯酚酚醛清漆树脂以21kg/小时向将转子转数设为250rpm、以3mmHg~5mmHg的真空度运转的离心薄膜蒸发器中连续地供给1小时,将蒸发成分及苯酚酚醛清漆树脂连续地抽出。离心薄膜蒸发器带有套管,加热传导面为0.21m2且在套管中流动260℃的热介质。另外,离心薄膜蒸发器具有外部冷凝器,冷却传导面为1.3m2且流动120℃的加温水,使蒸发成分的总量冷凝而抽出。
所得的苯酚酚醛清漆树脂的组成为:二核体量为9.1面积%、三核体量为48.9面积%、四核体量为22.9面积%、五核体量为10.4面积%、六核体以上的含量为8.7面积%,Mw为423,分散度(Mw/Mn)为1.122。蒸发成分的二核体量为97.9面积%,三核体量为2.1面积%,Mw为203,分散度(Mw/Mn)为1.006。所得的苯酚酚醛清漆树脂中未确认到着色。将所述苯酚酚醛清漆的名称称为PN-1。
各物性的测定或试验方法如下所述。
(分子量分布的测定)
使用在凝胶渗透色谱仪(gel permeation chromatograph,GPC)的本体(东曹股份有限公司制造的HLC-8220GPC)上串联地具有管柱(东曹股份有限公司制造的TSKgelG4000HXL、TSKgelG3000HXL、TSKgelG2000HXL)者,将管柱温度设为40℃,洗脱液使用四氢呋喃,流速设为1ml/分钟,检测器使用折射率(refractive index,RI)(示差折射计)检测器来进行测定,根据峰值的面积%而求出二核体含有率、三核体含有率、及n=1体含有率。
(硬化剂粘度的测定)
使用锥板型E型粘度计(东机产业股份有限公司:RE80H),在25℃下测定。将自测定开始经过60秒后的值设为粘度的值。
(凝胶时间的测定)
在预先加热至120℃的凝胶化试验机(日新科学制造)的板上添加二液硬化型树脂组合物,使用氟树脂棒以一秒钟转两下的速度搅拌,将树脂组合物发生硬化直至失去塑化性所需的时间设为凝胶化时间。
(玻璃化温度的测定)
使用动态粘弹性试验机,在升温速度5℃/分钟、弯曲模式、测定频率10Hz的条件下对玻璃化温度测定用试验片进行测定,将损失弹性系数(E”)的最大值设为玻璃化温度。
(碳纤维强化塑料(Carbon Fiber Reinforced Plastics,CFRP)的弯曲试验)
使用自奥特古拉夫(Autograph)AGS-X(岛津制作所制造),通过依据日本工业标准(Japanese Industrial Standards,JIS)K-7074的方法来对CFRP弯曲试验片进行测定,测定弯曲弹性系数(GPa)与最大弯曲应力(MPa)。
实施例1
使用100份的作为(A)成分的YD-128、13.3份的作为(B)成分的TETA3.3份的作为(C)成分的BPA,将这些放入150mL的塑料容器中,使用真空混合器,一边在室温下搅拌5分钟一边混合而获得树脂组合物。
将所述树脂组合物流入挖通为平板形状且设置有4mm厚的间隔件的纵60mm×横80mm且加热至120℃的模具中,进行5分钟硬化后,使用台式带锯将所得的硬化物切削为50mm×10mm的大小而获得试验片,将其用于玻璃化温度(Tg)的测定。
通过手糊(hand lay-up)成形而使碳纤维织物(纤维单位面积重量为300g/m2、0°构成、6ply(股))含浸以上所得的树脂组合物,制成CFRP基材。继而,将CFRP基材载置于加热至120℃的模具,将模具闭合,硬化5分钟,获得2mm厚的CFRP试验板。对所述CFRP试验板进行切削加工,制作100mm×15mm×厚2mm的CFRP弯曲试验片。将其用于CFRP的弯曲试验的评价中。
实施例2~实施例8、比较例1~比较例6
以表1及表2所记载的组成(份)使用各原料来作为(A)成分~(C)成分,除此以外,以与实施例1相同的混合条件制作树脂组合物及试验片。
将实施例1~实施例8的调配、试验结果示于表1中,将比较例1~比较例6的调配、试验结果示于表2中。调配量的数字为质量份。
[表1]
[表2]
CFRP的弯曲强度等大致相同,但实施例的成形性或快速硬化性优异,因而生产性高,而且耐热性优异。
Claims (9)
3.根据权利要求1所述的纤维强化复合材料用树脂组合物,其特征在于,硬化剂的通过E型粘度计而测定的25℃下的粘度为2000mPa·s以下。
4.根据权利要求1所述的纤维强化复合材料用树脂组合物,其特征在于,将纤维强化复合材料用树脂组合物在120℃下进行5分钟热处理而硬化成的硬化物的玻璃化温度显示为110℃以上。
5.一种纤维强化复合材料,其特征在于,是在如权利要求1至4中任一项所述的纤维强化复合材料用树脂组合物中调配强化纤维而成。
6.根据权利要求5所述的纤维强化复合材料,其中强化纤维的体积含有率为45%~70%。
7.一种硬化物,为如权利要求5所述的纤维强化复合材料的硬化物。
8.一种成形体的制造方法,其特征在于,利用树脂转注成形法、或液体压缩成形法将如权利要求5所述的纤维强化复合材料成形。
9.一种成形体的制造方法,其特征在于包括如下步骤,所述步骤包括:
准备如权利要求1所述的二液硬化型的纤维强化复合材料用树脂组合物;
将所述纤维强化复合材料用树脂组合物的二液与强化纤维混合而制成纤维强化复合材料;
继而利用模具将所述纤维强化复合材料加热硬化而成形。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-042807 | 2018-03-09 | ||
JP2018042807 | 2018-03-09 | ||
PCT/JP2019/006955 WO2019171991A1 (ja) | 2018-03-09 | 2019-02-25 | 繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111801367A true CN111801367A (zh) | 2020-10-20 |
Family
ID=67847300
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980017130.7A Pending CN111801367A (zh) | 2018-03-09 | 2019-02-25 | 纤维强化复合材料用树脂组合物及使其的纤维强化复合材料 |
Country Status (6)
Country | Link |
---|---|
US (1) | US11390708B2 (zh) |
EP (1) | EP3763765A4 (zh) |
JP (1) | JP7307050B2 (zh) |
CN (1) | CN111801367A (zh) |
TW (1) | TWI803586B (zh) |
WO (1) | WO2019171991A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023089997A1 (ja) * | 2021-11-16 | 2023-05-25 | Dic株式会社 | 硬化性組成物、硬化物、繊維強化複合材料、及び繊維強化樹脂成形品 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080145667A1 (en) * | 2006-12-15 | 2008-06-19 | Barker Michael J | Low odor, fast cure, toughened epoxy adhesive |
CN105377937A (zh) * | 2013-07-18 | 2016-03-02 | 喜利得股份公司 | 基于环氧化物-胺的多组分灰浆料的用途 |
CN109843968A (zh) * | 2016-10-14 | 2019-06-04 | 日铁化学材料株式会社 | 纤维强化复合材料用树脂组合物和使用它的纤维强化复合材料 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0557999A3 (en) * | 1992-02-27 | 1995-09-06 | Mitsui Toatsu Chemicals | Method for simultaneous preparation of bisphenol f and novolak phenol resins |
JPH06100665A (ja) * | 1992-09-18 | 1994-04-12 | Mitsui Toatsu Chem Inc | エポキシ樹脂組成物 |
JPH06287270A (ja) * | 1993-03-31 | 1994-10-11 | Sanyo Chem Ind Ltd | 繊維強化樹脂成形用樹脂組成物および成形体 |
JPH07207125A (ja) * | 1994-01-20 | 1995-08-08 | Mitsui Toatsu Chem Inc | フェノール系樹脂組成物 |
JP2009102563A (ja) | 2007-10-25 | 2009-05-14 | Toray Ind Inc | エポキシ樹脂組成物およびそれを用いた繊維強化複合材料 |
JP2009242719A (ja) * | 2008-03-31 | 2009-10-22 | Sumitomo Bakelite Co Ltd | フェノールノボラック樹脂、エポキシ樹脂組成物及びその硬化物、並びに半導体装置 |
SG179001A1 (en) * | 2009-09-16 | 2012-04-27 | Sumitomo Bakelite Co | Adhesive film, multilayer circuit board, electronic component and semiconductor device |
KR20140097103A (ko) | 2011-10-31 | 2014-08-06 | 도레이 카부시키가이샤 | 섬유 강화 복합 재료용 2액형 에폭시 수지 조성물 및 섬유 강화 복합 재료 |
CN104781303B (zh) | 2012-11-13 | 2017-11-10 | 陶氏环球技术有限责任公司 | 用于树脂传递模塑方法的含多亚乙基四胺的环氧树脂体系 |
KR102131214B1 (ko) | 2012-11-13 | 2020-07-08 | 다우 글로벌 테크놀로지스 엘엘씨 | 수지 이송 성형 공정을 위한 폴리에틸렌 테트라아민 및 트라이에틸렌 다이아민 촉매를 함유하는 에폭시 수지 시스템 |
JP6593620B2 (ja) | 2014-11-21 | 2019-10-23 | Dic株式会社 | エポキシ樹脂組成物、硬化物、繊維強化複合材料、繊維強化樹脂成形品、及び繊維強化樹脂成形品の製造方法 |
US10767001B2 (en) | 2016-04-12 | 2020-09-08 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin curing agent, epoxy resin composition, and carbon fiber-reinforced composite material |
-
2019
- 2019-02-25 CN CN201980017130.7A patent/CN111801367A/zh active Pending
- 2019-02-25 WO PCT/JP2019/006955 patent/WO2019171991A1/ja active Application Filing
- 2019-02-25 US US16/978,944 patent/US11390708B2/en active Active
- 2019-02-25 JP JP2020504926A patent/JP7307050B2/ja active Active
- 2019-02-25 EP EP19765045.0A patent/EP3763765A4/en active Pending
- 2019-03-06 TW TW108107349A patent/TWI803586B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080145667A1 (en) * | 2006-12-15 | 2008-06-19 | Barker Michael J | Low odor, fast cure, toughened epoxy adhesive |
CN105377937A (zh) * | 2013-07-18 | 2016-03-02 | 喜利得股份公司 | 基于环氧化物-胺的多组分灰浆料的用途 |
CN109843968A (zh) * | 2016-10-14 | 2019-06-04 | 日铁化学材料株式会社 | 纤维强化复合材料用树脂组合物和使用它的纤维强化复合材料 |
Also Published As
Publication number | Publication date |
---|---|
US11390708B2 (en) | 2022-07-19 |
TWI803586B (zh) | 2023-06-01 |
TW201938628A (zh) | 2019-10-01 |
JPWO2019171991A1 (ja) | 2021-03-25 |
EP3763765A4 (en) | 2021-11-17 |
US20210054137A1 (en) | 2021-02-25 |
WO2019171991A1 (ja) | 2019-09-12 |
JP7307050B2 (ja) | 2023-07-11 |
EP3763765A1 (en) | 2021-01-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6617559B2 (ja) | 繊維強化複合材料用2液型エポキシ樹脂組成物および繊維強化複合材料 | |
JP7221871B2 (ja) | 繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 | |
JP7186711B2 (ja) | 硬化性樹脂組成物、及びそれを用いたトゥプリプレグ | |
KR102399500B1 (ko) | 섬유 강화 복합 재료용 수지 조성물 및 그것을 이용한 섬유 강화 복합 재료 | |
JP6995779B2 (ja) | 硬化性エポキシ樹脂組成物、及びそれを用いた繊維強化複合材料 | |
CN111801367A (zh) | 纤维强化复合材料用树脂组合物及使其的纤维强化复合材料 | |
JP2016138205A (ja) | プリプレグ及び繊維強化複合材料 | |
JP2016147926A (ja) | 繊維強化複合材料用エポキシ樹脂組成物、エポキシ樹脂硬化物および繊維強化複合材料 | |
JP2018135496A (ja) | 繊維強化複合材料用2液型エポキシ樹脂組成物および繊維強化複合材料 | |
JP7161482B2 (ja) | 硬化性エポキシ樹脂組成物、及びそれを用いた繊維強化複合材料 | |
JP7424990B2 (ja) | 繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 | |
JP2019167443A (ja) | エポキシ樹脂組成物および繊維強化複合材料用プリプレグ | |
JP2022102349A (ja) | 繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 | |
JP2022156912A (ja) | 硬化性樹脂組成物、およびこれを用いた繊維強化複合材料 | |
JP2024064038A (ja) | 硬化性エポキシ樹脂組成物、及びそれを用いた繊維強化複合材料 | |
JP2023149614A (ja) | エポキシ樹脂組成物、繊維強化複合材料及び成形体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20240315 |
|
AD01 | Patent right deemed abandoned |