CN116829617A - Epoxy resin composition, prepreg, and fiber-reinforced plastic using the same - Google Patents
Epoxy resin composition, prepreg, and fiber-reinforced plastic using the same Download PDFInfo
- Publication number
- CN116829617A CN116829617A CN202280012615.9A CN202280012615A CN116829617A CN 116829617 A CN116829617 A CN 116829617A CN 202280012615 A CN202280012615 A CN 202280012615A CN 116829617 A CN116829617 A CN 116829617A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin composition
- fiber
- reinforcing fibers
- bifunctional
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 145
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 145
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- -1 prepreg Substances 0.000 title claims abstract description 49
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims description 20
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims description 20
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000004593 Epoxy Substances 0.000 claims abstract description 30
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 17
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 238000005452 bending Methods 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- 239000011342 resin composition Substances 0.000 abstract description 3
- 125000000732 arylene group Chemical group 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 30
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 20
- 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 17
- 239000000835 fiber Substances 0.000 description 17
- 229930185605 Bisphenol Natural products 0.000 description 12
- 239000012535 impurity Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 229930182555 Penicillin Natural products 0.000 description 3
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 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 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229940049954 penicillin Drugs 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- OXKVZHIHRSTGAN-UHFFFAOYSA-N naphthalene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 OXKVZHIHRSTGAN-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- ZUZAETTVAMCNTO-UHFFFAOYSA-N 2,3-dibutylbenzene-1,4-diol Chemical compound CCCCC1=C(O)C=CC(O)=C1CCCC ZUZAETTVAMCNTO-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 101100189356 Mus musculus Papolb gene Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 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
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- 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
- 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
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)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an epoxy resin composition for improving the adhesion of thermoplastic epoxy resin to reinforcing fibers. The epoxy resin composition is a resin composition containing a bifunctional phenol compound, a bifunctional epoxy resin and a polymerization catalyst, and is characterized in that the bifunctional epoxy resin contains 50 wt% or more of an epoxy resin (a) represented by the following formula (1), the bifunctional epoxy resin/bifunctional phenol compound (molar ratio) is 1.01-1.05 mol, the epoxy equivalent of a polymer obtained from the epoxy resin composition is 5000-20000 g/eq, the flexural strength is 70MPa or more, and the tetrahydrofuran insoluble content is 10 wt% or less. (A is represented by the formula (2), X is a single bond, alkylene, arylene, O, CO, or the like, Y 1 Is alkyl or aryl. )
Description
Technical Field
The present invention relates to an epoxy resin composition, an epoxy resin composition containing reinforcing fibers, a prepreg, and a fiber-reinforced plastic using the same.
Background
Fiber Reinforced Plastics (FRP) exhibit excellent physical properties such as light weight, high strength, etc., and have been used in many fields. Among them, carbon Fiber Reinforced Plastics (CFRP) obtained by using carbon fibers as reinforcing fibers are known to be particularly excellent in mechanical strength.
Since the price and the balance of physical properties are excellent, an epoxy resin is mainly used as a base resin of FRP. In addition, it is known that epoxy resins also exhibit good mechanical properties as CFRP base resins because they have secondary hydroxyl groups and form good bonding surfaces with reinforcing fibers.
On the other hand, a plastic using a thermoplastic resin as a base resin is called FRTP, and has been developed because of its excellent mass productivity, moldability, and recyclability. As the matrix resin of FRTP, nylon, polypropylene, polycarbonate, and the like are mainly used.
As the problem of FRTP, there is a problem that the 90-degree bending strength of the unidirectional material (UD material) is low because the adhesiveness between the reinforcing fiber and the resin is low. Various methods for cleaning a sizing agent attached to a fiber, modifying the surface of a reinforcing fiber with ozone, acid or the like, and the like have been studied in order to improve the adhesion between the reinforcing fiber and a resin, but all require additional steps and are not simple (non-patent document 1).
An in-situ polymerization type thermoplastic epoxy resin has been proposed as a thermoplastic resin to improve the adhesion to reinforcing fibers. The thermoplastic epoxy resin polymerized in situ is impregnated in the fibers in a low viscosity state before polymerization, so that the impregnation is good, and the proportion of the reinforcing fibers can be increased. In addition, since secondary hydroxyl groups are present in the epoxy resin, good adhesion to the reinforcing fibers can be expected.
In the conventional report on the adhesion between a thermoplastic epoxy resin and carbon fibers, it has been reported that the interfacial shear strength between carbon fibers and a base material is improved when the molecular weight of the thermoplastic epoxy resin is increased (non-patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2006-321897
Non-patent literature
Non-patent document 1: improvement of Bending Strength of Carbon Fiber/Thermoplastic Epoxy Composites (Open Journal of Composite Materials,2017,7,207-217)
Non-patent document 2: japanese society of adhesion VOL.53No.11 (2017) 375-380
Disclosure of Invention
However, according to the studies by the present inventors, it takes a sufficient time for polymerization to sufficiently increase the molecular weight of the thermoplastic epoxy resin in the reinforcing fiber. In addition, if the skeleton volume of the thermoplastic epoxy resin is increased in order to achieve high heat resistance, the steric hindrance of the reaction becomes large, and thus the curing time for polymerization becomes further long, and the productivity is poor. Therefore, there is a need for a method of improving the adhesion of thermoplastic epoxy resin to reinforcing fibers and enhancing the bending strength in the 90-degree direction by a simple method with excellent productivity.
The present inventors have conducted intensive studies with a view to exhibiting adhesion of thermoplastic epoxy resin to reinforcing fibers, and as a result, found that: the use of a specific epoxy resin composition can improve the adhesion to the reinforcing fibers and enhance the bending strength in the 90-degree direction.
That is, the present invention is an epoxy resin composition comprising a bifunctional phenol compound, a bifunctional epoxy resin and a polymerization catalyst as essential components,
the difunctional epoxy resin contains 50% by weight or more of a difunctional epoxy resin (a) represented by the following formula (1),
1.01 to 1.05 mol of the bifunctional epoxy resin relative to 1 mol of the bifunctional phenol compound,
the polymer obtained from the epoxy resin composition is a thermoplastic epoxy resin, the epoxy equivalent of which is 5000g/eq to 20000g/eq, and the flexural strength of which is 70MPa or more, and when dissolved in tetrahydrofuran, the insoluble content of which is 10% by weight or less of the polymer.
[ chemical formula 1]
Here, a in the formula (1) is represented by the formula (2), n is a repetition number, and the average value thereof is 0 to 5.X is a single bond, a hydrocarbon group having 1 to 13 carbon atoms, -O-, -CO-, -COO-, -S-, -SO 2 -any one of Y 1 Independently represents any one of an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 10 carbon atoms, Y 2 And Y 3 Each independently represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
The present invention also provides an epoxy resin composition or prepreg containing reinforcing fibers, which is obtained by mixing the epoxy resin composition with reinforcing fibers.
The reinforcing fiber is preferably a PAN-based carbon fiber, and is preferably contained in a proportion of 50 to 80% by weight in the resin composition or the prepreg.
The present invention also provides a fiber-reinforced plastic obtained by using the epoxy resin composition containing reinforcing fibers or the prepreg.
According to the present invention, a thermoplastic epoxy resin composition having excellent adhesion to reinforcing fibers can be provided.
The reason why the adhesiveness between the reinforcing fiber and the resin is exhibited is considered to be that: by controlling the composition ratio of the raw materials, an epoxy resin having a low epoxy equivalent weight and a high epoxy group concentration can be obtained, and excellent adhesion is formed between the epoxy resin and the functional groups and sizing agent on the surface of the reinforcing fiber.
Further, since polymerization is not sufficiently performed, the bending strength of the polymer is 70MPa or more, and thus the polymer can exhibit sufficient strength as a composite material. Conventionally, it has been considered that the adhesiveness of an epoxy resin is caused by secondary hydroxyl groups, and the influence of the concentration of epoxy groups of a polymer has not been reported. According to the present invention, the adhesiveness to the reinforcing fibers can be exhibited by a simple method of adjusting the feed ratio of the raw materials.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
The epoxy resin composition of the present invention is a composition containing a bifunctional phenol compound, a bifunctional epoxy resin and a polymerization catalyst as essential components and capable of being polymerized by heating. Additives such as organic solvents, fillers, and flame retardants may be contained.
The difunctional epoxy resin contains 50% by weight or more of the epoxy resin (a) represented by the formula (1) as an essential component. Preferably 66 wt% or more, more preferably 75 wt% or more, and still more preferably 80 wt% or more. The epoxy resin (a) constitutes a part of the difunctional epoxy resin.
The epoxy equivalent of the difunctional epoxy resin is preferably 150 to 350g/eq.
In the formula (1), A is a divalent group represented by the above formula (2). n is a repetition number and its average value is 0 to 5, preferably 0 to 1.
In the formula (2), X is a single bond, a hydrocarbon group having 1 to 13 carbon atoms, -O-, -CO-, -COO-, -S-, -SO 2 -any one of the following.
As the hydrocarbon group having 1 to 13 carbon atoms, an alkylene group having 1 to 9 carbon atoms or an arylene group having 6 to 13 carbon atoms is preferable, and examples thereof include-CH 2 －、－CH(CH 3 )－、－C(CH 3 ) 2 －、－C(CF 3 ) 2 －、－CHPh－、－C(CH 3 ) Ph-, 1-cyclopropylene, 1-cyclobutylene, 1-cyclopentylene, 1-cyclohexylene, 4-methyl-1, 1-cyclohexylene 3, 5-trimethyl-1, 1-cyclohexylene, 1-cyclooctylene, 1-cyclononylene, 1, 2-ethylene, 1, 2-cyclopropylene, 1, 2-cyclobutylene 1, 2-cyclopentylene, 1, 2-cyclohexylene, 1, 2-phenylene, 1, 3-propylene, 1, 3-cyclobutylene, 1, 3-cyclopentylene, 1, 3-cyclohexylene, 1, 3-phenylene, 1, 4-butylene, 1, 4-cyclohexylene, 1, 4-phenylene, 1-fluorenyl, 1, 2-xylylene, 1, 4-phenyleneXylyl, tetrahydrodicyclopentadiene, tetrahydrotricyclopentadienyl, and the like.
Of these, preferred are single bonds, -O-, -CO-, -COO-, -S-, -SO 2 －、－CH 2 －、－CH(CH 3 )－、－C(CH 3 ) 2 －、－CHPh－、－C(CH 3 ) Ph-, 1-cyclohexylene, 4-methyl-1, 1-cyclohexylene, 3, 5-trimethyl-1, 1-cyclohexylene, 1, 4-phenylene, 1-fluorenyl, more preferably a single bond, -O-, -CO-, -COO-, -S-, -SO 2 －、－CH 2 －、－CH(CH 3 )－、－C(CH 3 ) 2 －、－C(CH 3 ) Ph-, 1-cyclohexylene, 3, 5-trimethyl-1, 1-cyclohexylene, 1-fluorenyl.
Here, ph represents phenyl. Alkylene is meant to include alkylidene.
Y 1 Independently represents any one of an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 10 carbon atoms.
Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, an ethylphenyl group, a xylyl group, an n-propylphenyl group, an isopropylphenyl group, a mesityl group, and a naphthyl group.
Among them, methyl, ethyl, n-propyl, n-butyl, t-butyl, phenyl, tolyl, xylyl, or naphthyl is preferable, and methyl, ethyl, n-propyl, n-butyl, t-butyl, phenyl, or tolyl is more preferable.
Y 2 Independently, any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms is preferable, and a group other than a hydrogen atom is preferable. Examples of alkyl and aryl groups are those described above for Y 1 The same is true for the groups exemplified in (a). Preferred Y 2 And Y is equal to 1 Likewise, the same is true.
Y 3 Independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon atomAny one of aryl groups having a number of 6 to 10. As examples of alkyl and aryl, with Y 1 The same is true for the groups exemplified in (a). Preferred Y 3 Is a hydrogen atom or is combined with Y 1 The same is true for the groups exemplified in (a).
Examples of the bifunctional epoxy resin (a) include tetramethyl bisphenol F-type epoxy resin (for example, YSLV-80XY (manufactured by Mitsubishi chemical corporation), tetramethyl bisphenol type epoxy resin (for example, YX-4000 (manufactured by Mitsubishi chemical corporation)), and xylenol fluorene type epoxy resin (for example, OGSOL CG-500 (manufactured by Osaka gas chemical corporation)).
In addition, the epoxy resin other than the epoxy resin (a) may be used in combination with a bifunctional epoxy resin, and the purity thereof is preferably 95% or more. Further, as long as the purity as the difunctional epoxy resin is high, positional isomers and oligomers may be contained. Examples of the epoxy resin that can be used in combination with the epoxy resin (a) include bisphenol-type epoxy resins such as bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol acetophenone-type epoxy resin, diphenyl sulfide-type epoxy resin, diphenyl ether-type epoxy resin, bisphenol fluorene-type epoxy resin, and the like; bisphenol type epoxy resin, diphenyl dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, dihydroxynaphthalene type epoxy resin, dihydroxybenzene type epoxy resin, and the like, but are not limited thereto.
The difunctional epoxy resin which may be used in combination with the epoxy resin (a) is preferably less than 50% by weight, desirably less than 30% by weight, of all the epoxy resins. If the amount is more than 50% by weight, the component which is hardly dissolved in the solvent is produced by gelation, and thus the re-forming may be deteriorated.
In the case where the monofunctional impurities are contained in the difunctional epoxy resin, there is a possibility that the molecular weight after polymerization does not increase, and thus the mechanical properties of the resulting thermoplastic resin product may be deteriorated. Therefore, the monofunctional impurities are preferably 2% by weight or less relative to the difunctional epoxy resin.
When the trifunctional or higher-functional impurities are contained, a crosslinked structure is easily formed from the impurities, and therefore, there is a possibility that the dispersion of the polymer increases and gelation proceeds to impair the thermoplasticity. Therefore, the content of the trifunctional or higher-functional impurities is preferably 1 wt% or less relative to the bifunctional epoxy resin.
It should be noted that, even if the amount of impurities which do not have an active group which reacts with either one of the epoxy resin and the phenolic hydroxyl group and which do not inhibit the polymerization reaction in the monomer is increased, the molecular weight after the polymerization may be decreased. Therefore, it is preferably 2% by weight or less relative to the difunctional epoxy resin.
The bifunctional phenol compound used in the epoxy resin composition of the present invention is a compound having 2 phenolic hydroxyl groups in 1 molecule, and the purity thereof is preferably 95% by weight or more. Further, as long as the purity as a bifunctional phenol compound is high, a positional isomer may be contained.
When the monofunctional impurity is contained, the molecular weight after polymerization does not increase, and therefore there is a possibility that the mechanical properties of the thermoplastic resin to be produced will be deteriorated. Therefore, the monofunctional impurities are preferably 2% by weight or less relative to the bifunctional phenol compound.
When the trifunctional or higher-functional impurities are contained, a crosslinked structure is easily formed from the impurities, and therefore, there is a possibility that the dispersion of the polymer increases and gelation proceeds to impair the thermoplasticity. Therefore, the content of the trifunctional or higher impurity is preferably 1 wt% or less relative to the bifunctional phenol compound.
It should be noted that, even if the amount of impurities which do not have an active group which reacts with either one of the epoxy resin and the phenolic hydroxyl group and which do not inhibit the polymerization reaction in the monomer is increased, the molecular weight after the polymerization may be decreased. Therefore, it is preferably 2% by weight or less relative to the bifunctional phenol compound.
The difunctional phenol compound is preferably a bisphenol compound or a bisphenol compound. Examples of bisphenol compounds include bisphenol A, bisphenol F (manufactured by Nitro chemical Co., ltd.), bisphenol fluorene (manufactured by Osaka gas chemical Co., ltd.), bis-E, bis-Z, bisOC-FL, bisP-AP, bisP-CDE, bisP-HTG, bisP-MIBK, bisP-3MZ, S-BOC (manufactured by Nitro chemical Co., ltd.), bisphenol S, and the like. Examples of the diphenol compound include diphenol, dimethyl diphenol, and tetramethyl diphenol. Examples of the other bifunctional phenol compounds include benzenediol such as hydroquinone, methyl hydroquinone, dibutyl hydroquinone, resorcinol, methyl resorcinol, catechol, methyl catechol, and naphthalene diphenol such as naphthalene diphenol. Among these, bisphenol compounds or bisphenol compounds are preferable.
The proportion of the bifunctional epoxy resin contained in the epoxy resin composition of the present invention is 1.01 to 1.05 mol, preferably 1.02 to 1.03 mol, relative to 1 mol of the bifunctional phenol compound. In the case of a thermoplastic epoxy resin, the epoxy resin and the phenol compound are sequentially reacted to obtain a linear structure, thereby exhibiting thermoplastic properties. If the epoxy resin is excessive, it becomes an epoxy group terminal, and if the phenol compound is excessive, it becomes a phenol group terminal to terminate the reaction.
When the proportion of the epoxy resin is less than 1.01 mol, the polymer tends to become a phenolic terminal, and there is a possibility that the adhesion to the reinforcing fiber cannot be exhibited.
When the proportion of the epoxy resin is more than 1.05 mol, there is a possibility that the strength of the resin may be adversely affected by the presence of unreacted epoxy resin components in the resin after termination of the polymerization reaction.
In the epoxy resin composition, if the phenol compound is present in the epoxy resin in a crystalline state, the molar ratio deviates from design upon microscopic observation. If the reaction is initiated in this state, the polymerization may not proceed sufficiently. In order to sufficiently carry out the polymerization, an epoxy resin composition in which a phenol compound and an epoxy resin are uniformly dissolved (compatible) with each other is preferable.
Further, it is preferable that the epoxy resin composition before blending the reinforcing fiber or the like is completely dissolved or made into a uniform liquid, for example, when the haze value in the thickness direction is measured by adding the molten mixture to a glass culture dish in a state free from bubbles so that the thickness is 2mm, if the haze value in the thickness direction is less than 30%, it is judged that the liquid is dissolved or made into a uniform liquid to a level that does not affect the polymerization reaction. The haze value is more preferably less than 20%, and still more preferably less than 10%.
The polymerization catalyst used in the epoxy resin composition is not limited, and a known polymerization catalyst can be used. Specifically, phosphorus-based polymerization catalysts such as triphenylphosphine, tris (p-tolyl) phosphine, tris (o-tolyl) phosphine, and tris (p-methoxyphenyl) phosphine can be exemplified. Examples of the other polymerization catalysts include imidazole compounds such as 1B2MZ, 1B2PZ, and TBZ (manufactured by the four-country chemical industry).
The polymerization catalyst is preferably 0.05 to 5% by weight based on the total amount of the resin composition composed of the bifunctional epoxy resin and the bifunctional phenol compound. In the case of less than 0.05% by weight, time is consumed in-situ polymerization, so that productivity may be lowered, and furthermore, there is a possibility that the polymerization may be deactivated for some reason before the target molecular weight is reached. If the amount is more than 5% by weight, the polymerization reaction proceeds rapidly, and on the other hand, the storage stability may be impaired, which may cause problems in process suitability, and the composition may be a component which participates in the reaction but is not incorporated into the skeleton, and may impair the physical properties after the polymerization, and may be simply expensive, which may be economically disadvantageous.
The epoxy resin composition may contain an organic solvent for the polymerization catalyst or adjust the viscosity. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction between the epoxy resin and the phenol compound, but hydrocarbon-based, ketone-based, and ether-based are preferable from the viewpoint of easy availability. Specifically, toluene, xylene, acetone, methyl ethyl ketone, isobutyl ketone, cyclopentanone, cyclohexanone, diethylene glycol dimethyl ether, and the like can be mentioned. However, if a large amount of organic solvent is present in the reaction, the polymerization reaction is hindered. In addition, if an organic solvent remains in the polymer, the mechanical properties and heat resistance are deteriorated. Therefore, the proportion of the organic solvent is preferably 5% by weight or less relative to the total weight of the epoxy resin composition.
The progress of polymerization of the epoxy resin composition can be judged by a change in the epoxy equivalent of the polymer. If the heating is performed for less than 1 hour, the epoxy equivalent tends to increase, and there is a possibility that the polymerization does not proceed sufficiently. When the heating was performed for 1 hour or more, the epoxy equivalent did not increase substantially from the value at the time of 1 hour, and it was judged that the polymerization was sufficiently performed. Thus, the polymerization conditions for obtaining the polymer from the epoxy resin composition were heating at 160℃for 1 hour. In the present invention, the polymer used for measuring Tetrahydrofuran (THF) -insoluble matter refers to a polymer obtained by polymerization under such conditions.
The progress of polymerization of the epoxy resin composition containing the reinforcing fiber and the prepreg was also judged by the change in the epoxy equivalent as in the case of confirming the progress of the polymer. If the heating is performed for less than 4 hours, the epoxy equivalent tends to increase, and there is a possibility that the polymerization does not proceed sufficiently. When the heating was performed for 4 hours or more, the epoxy equivalent did not increase substantially from the value at the time of 4 hours, and it was judged that the polymerization was sufficiently performed. In the case of an epoxy resin composition obtained by compounding fibers, the heating time was set to 4 times the epoxy resin composition monomer to obtain a substantially equivalent epoxy equivalent. This is thought to be due to inhibition of the reaction in the fiber. Thus, the curing conditions for obtaining a fiber reinforced plastic from an epoxy resin composition or prepreg containing reinforcing fibers were heating at 160 ℃ for 4 hours.
It is important that the flexural strength of the polymer obtained by polymerizing the epoxy resin composition of the present invention in the absence of fillers and additives such as reinforcing fibers is 70MPa or more. If the flexural strength of the polymer is not more than the lower limit of the range, the mechanical strength as a fiber reinforced plastic cannot be sufficiently exhibited. The higher the strength, the better the mechanical strength as a fiber-reinforced plastic, so that an upper limit value need not be specified.
The epoxy equivalent of the polymer obtained by polymerizing the epoxy resin composition of the present invention is 5000g/eq to 20000g/eq. When the epoxy equivalent of the polymer is less than the lower limit of the range, there is a possibility that the mechanical strength may be deteriorated by containing a large amount of epoxy resin which is not sufficiently polymerized. When the epoxy equivalent of the polymer exceeds the upper limit of the range, the terminal group becomes a phenol group, and therefore, there is a possibility that the adhesiveness of the reinforcing fiber is deteriorated.
The epoxy resin composition of the present invention may contain additives. Examples of the additive include a filler such as fumed silica, a flame retardant such as aluminum hydroxide or red phosphorus, and a modifier such as core-shell rubber. From the viewpoint of stabilizing the polymerization reaction, it is preferable that the additive is blended with a substance different from the resin, but a plasticizer and a compatible flame retardant may be contained within a range that does not affect the reaction.
The epoxy resin composition of the present invention can be polymerized to form a thermoplastic epoxy resin. The thermoplastic epoxy resin is excellent as a resin component of a fiber-reinforced plastic.
The epoxy resin composition containing reinforcing fibers of the present invention is obtained by mixing or impregnating the epoxy resin composition with reinforcing fibers. The prepreg can be obtained as follows.
The epoxy resin composition film of the present invention can be obtained by coating the epoxy resin composition of the present invention on a release-treated paper or plastic film, and imparting a release-treated cover film as required. The release paper, the release plastic film, and the cover film may be made of known materials, and are not particularly limited. The thickness of the epoxy resin composition film is determined according to the design thickness of the prepreg and the resin ratio, and is generally 1 μm to 300 μm. If the particle size is less than 1. Mu.m, the reinforcing fibers are not completely defibrated, and if the particle size is more than 300. Mu.m, the reinforcing fibers are difficult to uniformly impregnate. Preferably 5 μm to 150 μm, more preferably 10 μm to 100 μm.
The reinforcing fibers used in the present invention are materials for reinforcing plastics such as carbon fibers, aramid fibers, and cellulose fibers, and are not particularly limited. Examples of the form of the fibers include UD sheets, woven fabrics, tows, staple fibers, nonwoven fabrics, and paper sheets, in which the fibers are arranged, and the like, without being particularly limited. However, from the viewpoint of impregnation properties, the thickness of each fiber bundle is 1mm or less, preferably 0.5mm or less, and more preferably 0.2mm or less.
The epoxy resin composition or prepreg containing reinforcing fibers of the present invention is obtained from reinforcing fibers and the epoxy resin composition and/or the epoxy resin composition film.
The ratio of reinforcing fiber to epoxy resin composition is preferably 5: 5-8: 2. if the ratio of the reinforcing fibers is too small, the strength required for the fiber-reinforced material may not be sufficiently satisfied, and if the ratio of the reinforcing fibers is too large, defects such as voids may be generated.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" means parts by weight and "%" means% by weight.
The raw materials, catalyst, solvent and reinforcing fibers used in the examples are as follows.
[ epoxy resin ]
A1: tetramethyl biphenol type epoxy resin (YX-4000, epoxy equivalent 188, manufactured by Mitsubishi chemical Co., ltd.)
A2: bisphenol A type epoxy resin (YD-8125, epoxy equivalent 173, manufactured by Nissan chemical materials Co., ltd.)
[ phenol Compounds ]
B1: bisphenol A (hydroxy equivalent 114, manufactured by Nissan chemical materials Co., ltd.)
B2:4,4' -bis (3, 5-trimethylcyclohexylidene) bisphenol (BisP-HTG, hydroxyl equivalent 155, manufactured by Benzhou chemical industry Co., ltd.)
[ polymerization catalyst ]
C1: tris (p-methoxyphenyl) phosphine (TPAP, manufactured by North chemical industry Co., ltd.)
C2:2, 3-dihydro-1H-pyrrole- [1,2-a ] benzimidazole (TBZ, manufactured by Sichuang chemical industry Co., ltd.)
[ solvent ]
D1: cyclohexanone
[ reinforcing fiber ]
E: PAN carbon fiber (Toray Co., ltd., T700-12K-50C)
The evaluation method of the examples is as follows.
Epoxy equivalent:
the measurement was performed in accordance with the Japanese Industrial Standard JIS K7236 standard, and the unit is expressed as "g/eq".
The polymer was directly measured, and the resin component was extracted from the fiber-reinforced plastic in the following order, and then the obtained resin component was used for measurement.
About 4g of the sample was weighed into a 110mL penicillin bottle, 100mL of Tetrahydrofuran (THF) was added thereto, ultrasonic diffusion was performed at room temperature for 1 hour, and then the sample was allowed to stand at room temperature for 23 hours or more to dissolve. The resulting THF solution was filtered with a 5 μm filter paper under reduced pressure, and the filtrate was recovered. The recovered filtrate was dried in a silica bath at 20℃for 24 hours or more and then dried in an oven set at 110℃for 5 hours or more, whereby a resin component after film formation was obtained.
Hydroxyl equivalent:
the measurement was performed according to JIS K0070 standard, and the unit is expressed as "g/eq". The hydroxyl equivalent of the phenolic resin means a phenolic hydroxyl equivalent unless otherwise specified.
Uniformity:
whether the phenol compound is uniformly melted in the epoxy resin is judged by the haze value. The haze value was evaluated on five scales of "less than 5% (< 5)", "less than 10% (< 10)", "less than 20% (< 20)", "less than 30% (< 30)", "30% or more (30.ltoreq.) by referring to a haze value standard plate made by color technical research on villages by adding the epoxy resin composition to a colorless transparent glass culture dish to a thickness of 2 mm. If the haze value is less than 30%, it is judged that the phenol compound is uniformly dissolved in the epoxy resin, and if it is 30% or more, it is judged that the phenol compound is not uniformly dissolved, and it is marked as x.
Gel fraction:
about 1g of the sample was precisely weighed in a 100mL penicillin bottle, 50mL of tetrahydrofuran was added thereto, ultrasonic diffusion was performed at room temperature for 1 hour, and then the sample was left standing at room temperature for 23 hours or more to dissolve. In addition, the 325 mesh wire gauze was dried in an oven at 100℃for 1 hour, and its weight was measured. The metal mesh was folded into a funnel shape, and the whole sample solution was poured onto the funnel. The sample is washed with tetrahydrofuran until no insoluble matter remains in the penicillin bottle, poured into a funnel, further washed with tetrahydrofuran, and dried in an oven at 100 ℃ for more than 4 hours. The dry weight of the metal mesh was subtracted from the weight of the dried sample and the metal mesh, and divided by the weight of the sample to determine the gel fraction in wt% and evaluate the gel fraction. The gel fraction is equal to the weight% of THF insoluble matter.
Bending test:
the flexural strength of the polymer was measured in accordance with JIS K7171. The test was performed at a test speed of 1mm/min using an Autograph AGS-X (Shimadzu corporation) with a sample size of 4mm in thickness, 100mm in length, 15mm in width and 70mm in bending span.
The 90-degree-direction bending strength of the unidirectional fiber-reinforced plastic was measured in accordance with JIS K7074. The test was performed at a test speed of 1mm/min using an Autograph AGS-X (Shimadzu corporation) with a sample size of 2mm in thickness, 100mm in length, 15mm in width and 70mm in bending span.
Resin adhesion amount:
the cross section of the fiber reinforced plastic after the bending test was observed by SEM (JSM-7900F, manufactured by Japanese electric Co., ltd.), and the resin adhesion amount on the fiber was confirmed. If the adhesion between the fibers and the resin is good, it is confirmed that the resin adheres well to the fiber surface of the fracture surface. 10 fibers were observed by SEM, and the number of fibers having 80% or more of the resin attached to the surface of the fibers was evaluated.
More than 9: and (c) 8 or less: x-shaped glass tube
Example 1
A1 2913 part, B1 1000 part and B2 1000 part were separately pulverized and mixed by a Henschel mixer. Next, the mixture was melt-mixed using an S1KRC kneader (manufactured by Castanea Corp., inc.) preheated to 170℃at a barrel temperature, and the whole amount was collected in a metal tank and cooled with stirring to obtain a precursor mixture (F1) of an epoxy resin composition.
5 parts of C1 (polymerization catalyst) are dissolved in 5 parts of D1 (organic solvent) in advance. The precursor mixture (F1) was placed in a planetary mixer set at 60℃and mixed with the polymerization catalyst solution before the addition. After mixing, the mixture was rapidly withdrawn and immediately cooled to 40℃or lower to obtain an epoxy resin composition (G1).
The obtained epoxy resin composition (G1) was heated to about 70℃and stirred, poured into an iron chromium plating metal mold container having a gap of 4mm in advance, and thermally polymerized in a hot air circulation oven at 160℃for 60 minutes to obtain a polymer.
The epoxy equivalent of the obtained polymer was measured and found to be 9900g/eq.
The flexural strength of the obtained polymer was measured and found to be 87MPa.
The gel fraction of the obtained polymer was measured and found to be 1%.
Examples 2 to 3 and comparative examples 1 to 4
An epoxy resin composition and a polymer were obtained in the same manner as in example 1 under the conditions described in table 1. The epoxy equivalent, flexural strength and gel fraction of the obtained polymer were measured in the same manner as in example 1, and the evaluation results thereof are shown in table 1.
In comparative examples 3 and 4, the pulverization and mixing using a henschel mixer were replaced by the stirring and mixing in a planetary stirrer set at 60 ℃.
For comparative example 3, the barrel temperature at the time of melt mixing was set at 80 ℃. At this time, the haze value of the obtained epoxy resin composition was 30% or more, and the melted state of the phenol compound was determined to be x.
In addition, the gel fraction of the polymer of comparative example 4 was 95%, and the measurement of the epoxy equivalent amount was not performed because the polymer could not be dissolved in the solvent.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| A1 | 2947 | 2947 | 2920 | 2804 | 3148 | ||
| A2 | 2277 | 2713 | |||||
| B1 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | |
| B2 | 1000 | 1000 | 1000 | 1000 | 1000 | 2000 | 1000 |
| C1 | 5.0 | 4.9 | 4.3 | 4.8 | |||
| C2 | 5.0 | 2.4 | 2.5 | ||||
| D1 | 5.0 | 5.0 | 2.4 | 4.9 | 2.5 | 4.3 | 4.8 |
| Molar ratio of | 1.03 | 1.03 | 1.02 | 0.98 | 1.10 | 1.02 | 1.03 |
| Epoxy resin composition | G1 | G2 | G3 | G4 | G5 | G6 | G7 |
| Uniformity of | ○ | ○ | ○ | ○ | ○ | × | ○ |
| Gel fraction (%) | 1 | 3 | 2 | 2 | 0 | 0 | 95 |
| Epoxy equivalent (g/eq.) | 9900 | 11000 | 14000 | 120000 | 2500 | 3000 | - |
| Resin strength (MPa) | 99 | 100 | 98 | 100 | 50 | 29 | 103 |
Example 4
The release paper after the release treatment was fixed with the release face facing upward on a hot plate preheated to 70 ℃, the epoxy resin composition (G1) obtained in example 1 was placed on the release paper, and then coating was performed with a bar coater preheated to 70 ℃ to give an area weight of the resin of 79G/m 2 . Immediately after the coating, the resulting sheet was removed from the hot plate and air-cooled to obtain an epoxy resin composition sheet.
Next, the epoxy tree is obtainedThe weight of the fat composition sheet was 153g/m as the area of the fiber 2 The carbon fiber (E) was bonded to the surface of the prepreg at a surface pressure of 0.5MPa by using a hot press preheated to 90 ℃, and the prepreg was removed after 1 minute and air-cooled to obtain rc=34%.
Further, the obtained prepreg was laminated with 13 sheets so that the orientation direction of the fibers was the same, and then sandwiched with a release film, and a unidirectional fiber-reinforced plastic was obtained by vacuum compression. The conditions for vacuum pressing were 160℃and 0.1MPa for 240 minutes.
The 90-degree bending strength of the obtained unidirectional fiber-reinforced plastic was measured and found to be 86MPa. The epoxy equivalent was measured on the resin component of the obtained unidirectional fiber-reinforced plastic, and found to be 9800g/eq.
With respect to examples 5 to 6 and comparative examples 5 to 8, unidirectional fiber-reinforced plastics were obtained in the same manner as in example 4. In comparative example 8, since many insoluble matters were generated at the time of measuring the epoxy equivalent, the measurement of the epoxy equivalent was not performed.
TABLE 2
| Example 4 | Example 5 | Example 6 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Epoxy resin composition | G1 | G2 | G3 | G4 | G5 | G6 | G7 |
| Epoxy equivalent (g/eq.) | 9800 | 12000 | 15000 | 110000 | 2500 | 2800 | - |
| Intensity (MPa) | 86 | 95 | 88 | 46 | 51 | 21 | 47 |
| Resin adhesion amount | ○ | ○ | ○ | × | ○ | ○ | ○ |
From tables 1,2, it can be confirmed that: if the epoxy equivalent of the polymer is 5000g/eq to 20000g/eq and the resin strength is 70MPa or more, the 90-degree bending strength of the reinforced fiber plastic is 80MPa or more.
From comparative example 5 (comparative example 1), it can be confirmed that: if the epoxy equivalent of the polymer is high, the fiber-resin bond is weak and cannot sufficiently exhibit 90-degree bending strength.
From comparative examples 6 and 7 (comparative examples 2 and 3), it was confirmed that: if the resin strength of the polymer is not strong enough, 90 degree bending strength cannot be sufficiently exhibited.
From comparative example 8 (comparative example 4), it can be confirmed that: if the insoluble content in the polymer is large, 90-degree bending strength cannot be sufficiently exhibited. It is considered that the lowest melt viscosity of the resin containing many gel components tends to be high during polymerization, and voids are liable to remain as CFRP molded products, which adversely affects the 90-degree bending strength.
Claims (7)
1. An epoxy resin composition comprising a bifunctional phenol compound, a bifunctional epoxy resin and a polymerization catalyst as essential components,
the difunctional epoxy resin contains 50% by weight or more of a difunctional epoxy resin a represented by the following formula (1),
the mixing ratio of the bifunctional phenol compound to the bifunctional epoxy resin is 1.01 to 1.05 mol relative to 1 mol of the bifunctional phenol compound,
the polymer obtained from the epoxy resin composition is a thermoplastic epoxy resin, the epoxy equivalent is 5000g/eq to 20000g/eq, the bending strength is more than 70MPa, when dissolved in tetrahydrofuran, the insoluble component is less than 10 wt%,
here, A is a divalent group represented by the formula (2), n is a repetition number, wherein the average value is 0 to 5, X is a single bond, a hydrocarbon group of 1 to 13 carbon atoms, -O-, -CO-, -COO-, -S-, or-SO 2 －，Y 1 Independently is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, Y 2 And Y 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
2. An epoxy resin composition containing reinforcing fibers, comprising the epoxy resin composition according to claim 1 and reinforcing fibers.
3. The epoxy resin composition containing reinforcing fibers according to claim 2, wherein the PAN-based carbon fibers are contained as reinforcing fibers in a proportion of 50 to 80% by weight.
4. A prepreg comprising a mixture of the epoxy resin composition of claim 1 and reinforcing fibers.
5. The prepreg according to claim 4, wherein the PAN-based carbon fiber is contained as a reinforcing fiber in an amount of 50 to 80% by weight.
6. A fiber-reinforced plastic obtained by using the prepreg according to claim 4 or 5.
7. A fiber-reinforced plastic obtained by using the epoxy resin composition containing reinforcing fibers according to claim 2 or 3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-057494 | 2021-03-30 | ||
| JP2021057494 | 2021-03-30 | ||
| PCT/JP2022/010714 WO2022209715A1 (en) | 2021-03-30 | 2022-03-10 | Epoxy resin composition, prepreg, and fiber-reinforced plastic obtained using these |
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| CN116829617A true CN116829617A (en) | 2023-09-29 |
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| JP (1) | JPWO2022209715A1 (en) |
| CN (1) | CN116829617A (en) |
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| WO2008018364A1 (en) * | 2006-08-07 | 2008-02-14 | Nippon Steel Chemical Co., Ltd. | Prepreg, laminate and printed wiring board |
| JP5660783B2 (en) * | 2010-01-18 | 2015-01-28 | 新日鉄住金化学株式会社 | Sulfone group-containing polyhydroxy polyether resin, resin composition containing the resin, curable resin composition containing the resin, and film obtained therefrom |
| JP6022230B2 (en) * | 2012-06-22 | 2016-11-09 | 新日鉄住金化学株式会社 | High molecular weight epoxy resin, resin composition and cured product using the same |
| US10961363B2 (en) * | 2015-12-01 | 2021-03-30 | Nippon Steel Chemical & Material Co., Ltd. | In-situ polymerized type thermoplastic prepreg, thermoplastic composite, and methods of manufacturing the same |
| JP7185383B2 (en) * | 2019-04-17 | 2022-12-07 | 日本化薬株式会社 | Curable resin composition and its cured product |
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