JP4901629B2 - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
- Publication number
- JP4901629B2 JP4901629B2 JP2007195106A JP2007195106A JP4901629B2 JP 4901629 B2 JP4901629 B2 JP 4901629B2 JP 2007195106 A JP2007195106 A JP 2007195106A JP 2007195106 A JP2007195106 A JP 2007195106A JP 4901629 B2 JP4901629 B2 JP 4901629B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- parts
- resin composition
- prepreg
- oxazolidone ring
- 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.)
- Active
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- 239000003822 epoxy resin Substances 0.000 title claims description 205
- 229920000647 polyepoxide Polymers 0.000 title claims description 205
- 239000000203 mixture Substances 0.000 title claims description 83
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 claims description 53
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 40
- 239000012783 reinforcing fiber Substances 0.000 claims description 36
- 239000004744 fabric Substances 0.000 claims description 27
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000005060 rubber Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 60
- 230000000052 comparative effect Effects 0.000 description 48
- 239000002966 varnish Substances 0.000 description 45
- -1 isocyanate compound Chemical class 0.000 description 44
- 239000002904 solvent Substances 0.000 description 41
- 230000015572 biosynthetic process Effects 0.000 description 35
- 238000003786 synthesis reaction Methods 0.000 description 35
- 238000005470 impregnation Methods 0.000 description 34
- 229920005989 resin Polymers 0.000 description 31
- 239000011347 resin Substances 0.000 description 31
- 239000002994 raw material Substances 0.000 description 30
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 24
- 239000011342 resin composition Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 20
- 239000004809 Teflon Substances 0.000 description 18
- 229920006362 Teflon® Polymers 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000005266 casting Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 18
- 239000012948 isocyanate Substances 0.000 description 18
- 229920003986 novolac Polymers 0.000 description 17
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 16
- 239000004593 Epoxy Substances 0.000 description 16
- 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 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000000465 moulding Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical group O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 5
- 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 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 150000002357 guanidines Chemical class 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 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 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 3
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011208 reinforced composite material Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-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
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 2
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 125000005628 tolylene group Chemical group 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
- 150000003672 ureas Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OTXHZHQQWQTQMW-UHFFFAOYSA-N (diaminomethylideneamino)azanium;hydrogen carbonate Chemical compound OC([O-])=O.N[NH2+]C(N)=N OTXHZHQQWQTQMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 239000005967 1,4-Dimethylnaphthalene Substances 0.000 description 1
- SIZPGZFVROGOIR-UHFFFAOYSA-N 1,4-diisocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=C(N=C=O)C2=C1 SIZPGZFVROGOIR-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- JVBOHJILWXWANF-UHFFFAOYSA-N 2-cyano-N-(N,N-diethylcarbamimidoyl)acetamide Chemical compound C(C)N(C(NC(CC#N)=O)=N)CC JVBOHJILWXWANF-UHFFFAOYSA-N 0.000 description 1
- LTRMOUYRMDEEOR-UHFFFAOYSA-N 2-cyano-n-(diaminomethylidene)acetamide Chemical compound NC(N)=NC(=O)CC#N LTRMOUYRMDEEOR-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- UJZXMWXPFCLKHA-UHFFFAOYSA-N [P].NC(N)=N Chemical class [P].NC(N)=N UJZXMWXPFCLKHA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HNJBHAKOPNXKPI-UHFFFAOYSA-N butanedioic acid;guanidine Chemical compound NC(N)=N.OC(=O)CCC(O)=O HNJBHAKOPNXKPI-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- OSXWETDBWKSBFH-UHFFFAOYSA-N diphenyl-bis(prop-2-enyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](CC=C)(CC=C)C1=CC=CC=C1 OSXWETDBWKSBFH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- VVZKVJZZDTVKSD-UHFFFAOYSA-N ethyl (ne)-n-[amino-(ethoxycarbonylamino)methylidene]carbamate Chemical compound CCOC(=O)NC(=N)NC(=O)OCC VVZKVJZZDTVKSD-UHFFFAOYSA-N 0.000 description 1
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical compound [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- NGGXACLSAZXJGM-UHFFFAOYSA-N n-(diaminomethylidene)acetamide Chemical compound CC(=O)N=C(N)N NGGXACLSAZXJGM-UHFFFAOYSA-N 0.000 description 1
- MHKWLKXZLMBCNW-UHFFFAOYSA-N n-(diaminomethylidene)propanamide Chemical compound CCC(=O)NC(N)=N MHKWLKXZLMBCNW-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GXYJVHVZCMHHFY-UHFFFAOYSA-N phosphane;tetrabutylphosphanium Chemical class P.CCCC[P+](CCCC)(CCCC)CCCC GXYJVHVZCMHHFY-UHFFFAOYSA-N 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- FWYKRJUVEOBFGH-UHFFFAOYSA-M triphenyl(prop-2-enyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FWYKRJUVEOBFGH-UHFFFAOYSA-M 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、エポキシ樹脂組成物及びこれを用いたプリプレグに関し、特に、プリプレグ取扱い性及び耐熱性のバランスに優れたエポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin composition and a prepreg using the same, and particularly to an epoxy resin composition excellent in the balance between prepreg handling properties and heat resistance.
エポキシ樹脂は硬化後の機械的特性、電気的特性や接着性に優れるため、電子材料用封止材、塗料・塗装用材料、接着剤等の分野に広く用いられている。従来、炭素繊維強化複合材料（以下、ＣＦＲＰとも略される）の分野においては、硬化時の低収縮性、成形性、繊維との接着性、硬化物の耐熱性、強度向上などのため、一般にエポキシ樹脂を主成分とした熱硬化性樹脂が広く使用されている。とりわけ、加工性と耐熱性を両立させる観点から、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等の２官能エポキシ樹脂と、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、テトラグリシジルジアミノジフェニルメタン等の多官能エポキシ樹脂、さらにはフェノキシ樹脂等の熱可塑性樹脂を組み合わせた樹脂組成物が幅広く使用されている。 Epoxy resins are widely used in fields such as encapsulants for electronic materials, paints / coating materials, adhesives and the like because they are excellent in mechanical properties, electrical properties and adhesiveness after curing. Conventionally, in the field of carbon fiber reinforced composite materials (hereinafter also abbreviated as CFRP), it is generally used for low shrinkage at the time of curing, moldability, adhesion to fibers, heat resistance of cured products, strength improvement, etc. Thermosetting resins based on epoxy resins are widely used. In particular, from the viewpoint of achieving both workability and heat resistance, bifunctional epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and polyfunctionals such as phenol novolac epoxy resin, cresol novolac epoxy resin, tetraglycidyl diaminodiphenylmethane, etc. Resin compositions that combine thermoplastic resins such as epoxy resins and phenoxy resins are widely used.
また、昨今、ＣＦＲＰへのさらなる強靭化・高耐熱化・軽量化等の高機能化への要請がある。耐熱性と可撓性を両立できるエポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂のトリレンジイソシアネート変性エポキシ樹脂が挙げられる。さらに、架橋密度を高めて耐熱性を上げる場合の欠点である硬化物の脆さを改質するために、樹脂組成物中に固形ゴムや熱可塑性エラストマーを添加して靭性を向上させる方法もとられている。 In recent years, there has been a demand for higher functionality such as further strengthening, higher heat resistance, and weight reduction of CFRP. Examples of the epoxy resin that can achieve both heat resistance and flexibility include a tolylene diisocyanate-modified epoxy resin of bisphenol A type epoxy resin. Furthermore, in order to improve the brittleness of the cured product, which is a drawback when increasing the crosslink density and increasing the heat resistance, a method for improving toughness by adding solid rubber or thermoplastic elastomer to the resin composition It has been.
ビスフェノールＡ型エポキシ樹脂のトリレンジイソシアネート変性エポキシ樹脂を用いる技術として、例えば、特許文献１には、ビスフェノールＡ型エポキシ樹脂と上記記載の変性エポキシ樹脂とを含むエポキシ樹脂組成物が記載されている。また、特許文献２には、添加剤としてアクリロニトリル−ブタジエン共重合体を含むエポキシ樹脂組成物が記載されている。 As a technique using a tolylene diisocyanate-modified epoxy resin of a bisphenol A type epoxy resin, for example, Patent Document 1 describes an epoxy resin composition containing a bisphenol A type epoxy resin and the above-described modified epoxy resin. Patent Document 2 describes an epoxy resin composition containing an acrylonitrile-butadiene copolymer as an additive.
しかしながら、上記特許文献１で使用される変性エポキシ樹脂は、樹脂自身の軟化点が高く、溶融粘度も高い。一方、ＣＦＲＰ用途では、炭素繊維への含浸性やプリプレグのタック性を適度に維持するために、エポキシ樹脂組成物の溶融粘度を適切な粘度範囲に調整することが要求される。使用するエポキシ樹脂の溶融粘度が必要以上に高いと、より粘度の低いエポキシ樹脂、例えばビスフェノールＡ型液状エポキシ樹脂やビスフェノールＦ型液状エポキシ樹脂の配合量を増やして、エポキシ樹脂組成物の粘度を下げる必要があるため、硬化品特性として充分な耐熱性を維持することが困難になる傾向となる。 However, the modified epoxy resin used in Patent Document 1 has a high softening point and a high melt viscosity. On the other hand, in CFRP applications, it is required to adjust the melt viscosity of the epoxy resin composition to an appropriate viscosity range in order to maintain carbon fiber impregnation properties and prepreg tackiness appropriately. When the melt viscosity of the epoxy resin used is higher than necessary, the amount of the epoxy resin having a lower viscosity, for example, bisphenol A type liquid epoxy resin or bisphenol F type liquid epoxy resin is increased to lower the viscosity of the epoxy resin composition. Since it is necessary, it tends to be difficult to maintain sufficient heat resistance as a cured product characteristic.
また、上記特許文献２のエポキシ樹脂組成物のように、固形ゴムや熱可塑性エラストマーを添加剤として併用すると、例えエポキシ樹脂と相溶したとしても、樹脂組成物の溶融粘度上昇が大きくなり、流動性が損なわれて、樹脂が均一に含浸したプリプレグを製造することが困難になる傾向となる。プリプレグに樹脂が均一に含浸されていないと、半硬化させる際にボイドが生じ、結果として、得られる半硬化物の外観不良や他のプリプレグとの接着性の低下を引き起こし、硬化品の強度面においても充分とは言えず、未だ改善の余地がある。 Moreover, like the epoxy resin composition of the said patent document 2, when solid rubber and thermoplastic elastomer are used together as an additive, even if it is compatible with an epoxy resin, the melt viscosity rise of a resin composition will become large, and it will flow The properties tend to be impaired, making it difficult to produce a prepreg impregnated uniformly with a resin. If the resin is not uniformly impregnated in the prepreg, voids are generated when it is semi-cured, resulting in poor appearance of the resulting semi-cured product and reduced adhesion to other prepregs. However, there is still room for improvement.
本発明は、かかる課題に鑑みなされたものであり、プリプレグ取り扱い性及び耐熱性のバランスに優れたエポキシ樹脂組成物を提供することを目的とする。 This invention is made | formed in view of this subject, and it aims at providing the epoxy resin composition excellent in the balance of prepreg handleability and heat resistance.
本発明者は、上記課題を解決するために、エポキシ樹脂の種類、及び変性に用いるイソシアネート化合物の種類、並びに変性して得られる変性エポキシ樹脂の性状、及び硬化物特性の関係に着目して鋭意研究を重ねた結果、特定のオキサゾリドン環を有するエポキシ樹脂を含むエポキシ樹脂組成物が、従来のエポキシ樹脂組成物に比して低粘度であるためプリプレグへの含浸性に優れ、また、硬化物の耐熱性にも優れることを見出し、本発明をなすに至った。 In order to solve the above problems, the inventor has earnestly focused on the relationship between the type of epoxy resin, the type of isocyanate compound used for modification, the properties of the modified epoxy resin obtained by modification, and the properties of the cured product. As a result of repeated research, an epoxy resin composition containing an epoxy resin having a specific oxazolidone ring has a lower viscosity than a conventional epoxy resin composition, and thus has excellent prepreg impregnation properties. The inventors have found that the heat resistance is also excellent and have come to make the present invention.
すなわち、本発明は、以下のとおりである。
［１］
（Ａ）オキサゾリドン環を有するエポキシ樹脂と、
（Ｂ）硬化剤と、を含み、
前記（Ａ）が下記一般式（１）で表される構造を有するエポキシ樹脂である、エポキシ樹脂組成物；
［２］
（Ｃ）ビスフェノールＡ型エポキシ樹脂及び／又はビスフェノールＦ型エポキシ樹脂をさらに含む、［１］記載のエポキシ樹脂組成物。
［３］
（Ｄ）熱可塑性エラストマー成分及び／又は架橋ゴム成分をさらに含む、［１］又は［２］のいずれかに記載のエポキシ樹脂組成物。
［４］
（Ｅ）フィラーをさらに含む、［１］〜［３］のいずれかに記載のエポキシ樹脂組成物。
［５］
前記（Ｂ）硬化剤がグアニジン誘導体である、［１］〜［４］のいずれかに記載のエポキシ樹脂組成物。
［６］
粘度が６０℃において３００〜３０００Ｐａ・ｓであることを特徴とする［１］〜［５］のいずれかに記載のエポキシ樹脂組成物。
［７］
［１］〜［６］のいずれかに記載のエポキシ樹脂組成物を強化繊維シートに含浸してなるプリプレグ。
［８］
前記強化繊維シートがカーボン繊維布である、［７］記載のプリプレグ。
That is, the present invention is as follows.
[1]
(A) an epoxy resin having an oxazolidone ring;
(B) a curing agent,
An epoxy resin composition in which (A) is an epoxy resin having a structure represented by the following general formula (1);
[2]
(C) The epoxy resin composition according to [1], further comprising a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin.
[3]
(D) The epoxy resin composition according to any one of [1] or [2], further comprising a thermoplastic elastomer component and / or a crosslinked rubber component.
[4]
(E) The epoxy resin composition according to any one of [1] to [3], further including a filler.
[5]
The epoxy resin composition according to any one of [1] to [4], wherein the (B) curing agent is a guanidine derivative.
[6]
The epoxy resin composition according to any one of [1] to [5], wherein the viscosity is 300 to 3000 Pa · s at 60 ° C.
[7]
A prepreg obtained by impregnating a reinforcing fiber sheet with the epoxy resin composition according to any one of [1] to [6].
[8]
The prepreg according to [7], wherein the reinforcing fiber sheet is a carbon fiber cloth.
本発明によれば、プリプレグ取り扱い性及び耐熱性のバランスに優れたエポキシ樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition excellent in the balance of prepreg handleability and heat resistance can be provided.
以下、本発明を実施するための最良の形態（以下、発明の実施の形態）について詳細に説明する。なお、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
本実施の形態のエポキシ樹脂組成物は、（Ａ）オキサゾリドン環を有するエポキシ樹脂及び（Ｂ）硬化剤を含み、前記（Ａ）が上記一般式（１）で表される構造を有するエポキシ樹脂である。 The epoxy resin composition of the present embodiment includes (A) an epoxy resin having an oxazolidone ring and (B) a curing agent, and (A) is an epoxy resin having a structure represented by the general formula (1). is there.
［（Ａ）成分］
（Ａ）成分であるオキサドリドン環を有するエポキシ樹脂は、上記一般式（１）で表される構造を有する樹脂であり、該構造を有することにより、これを含むエポキシ樹脂組成物の粘度が低下するので、プリプレグへの優れた含浸性が実現され得、さらに、得られる硬化物に優れた耐熱性を付与することが可能となり得る。
[(A) component]
The epoxy resin having an oxadoridone ring as the component (A) is a resin having a structure represented by the above general formula (1), and the viscosity of the epoxy resin composition containing the epoxy resin composition is reduced by having the structure. Therefore, the excellent impregnation property to a prepreg can be implement | achieved, and also it becomes possible to provide the outstanding heat resistance to the hardened | cured material obtained.
一般式（１）において、Ｒ１〜Ｒ８で示されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子等が挙げられる。 In the general formula (1), examples of the halogen atom represented by R 1 to R 8 include a fluorine atom, a chlorine atom, and a bromine atom.
一般式（１）において、Ｒ１〜Ｒ８で示される炭素数１〜４のアルキル基としては、炭素数が１〜４の直鎖状又は分岐鎖状のアルキル基を示し、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等が挙げられる。 In the general formula (1), the alkyl group having 1 to 4 carbon atoms represented by R 1 to R 8 represents a linear or branched alkyl group having 1 to 4 carbon atoms, for example, a methyl group , Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
Ｒ１〜Ｒ８としては、直鎖状よりも分岐鎖状の方が高耐熱性である傾向にあるため、好ましくはイソプロピル基、イソブチル基であり、より好ましくはｔｅｒｔ−ブチル基である。 R 1 to R 8 are preferably an isopropyl group and an isobutyl group, and more preferably a tert-butyl group, because a branched chain tends to have higher heat resistance than a straight chain.
一般式（２）において、Ｒ’１〜Ｒ’６で示される炭素数１〜４のアルキル基としては、上記で例示したものと同様なものが挙げられる。 In the general formula (2), examples of the alkyl group having 1 to 4 carbon atoms represented by R ′ 1 to R ′ 6 include the same as those exemplified above.
Ｒ’１〜Ｒ’６としては、直鎖状よりも分岐鎖状の方が高耐熱性である傾向にあるため、好ましくはイソプロピル基、イソブチル基であり、より好ましくはｔｅｒｔ−ブチル基である。 R ′ 1 to R ′ 6 are preferably an isopropyl group and an isobutyl group, more preferably a tert-butyl group, because a branched chain tends to have higher heat resistance than a straight chain. .
Ｒ１〜Ｒ８及びＲ’１〜Ｒ’６示される炭素数１〜４のアルキル基は、置換可能な位置に、１又は２以上の置換基で置換されていてもよい。かかる置換基としては、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子）、炭素数１〜６のアルキル基（例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基）、アリール基（例えば、フェニル基、ナフチル基）、アラルキル基（例えば、ベンジル基、フェネチル基）、アルコキシ基（例えば、メトキシ基、エトキシ基）などが挙げられる。 The alkyl group having 1 to 4 carbon atoms represented by R 1 to R 8 and R ′ 1 to R ′ 6 may be substituted with one or more substituents at substitutable positions. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group), aryl group (for example, phenyl group, naphthyl group), aralkyl group (for example, benzyl group, phenethyl group), alkoxy group (for example, methoxy group, ethoxy group) Group).
（Ａ）成分は、少なくとも、０．５〜５モル／ｋｇのオキサゾリドン環を有するものであることが好ましく、０．５〜２．５モル／ｋｇのオキサゾリドン環を有するものであることがより好ましい。０．５モル／ｋｇ以上のオキサゾリドン環を有することは、硬化物の強靭性及び硬化物の耐熱性をより一層向上させる観点から好適である。一方、５モル／ｋｇ以下のオキサゾリドン環を有することは、硬化物の耐水性をより一層向上させる観点から好適である。 The component (A) preferably has at least 0.5 to 5 mol / kg oxazolidone ring, more preferably 0.5 to 2.5 mol / kg oxazolidone ring. . Having an oxazolidone ring of 0.5 mol / kg or more is preferable from the viewpoint of further improving the toughness of the cured product and the heat resistance of the cured product. On the other hand, having an oxazolidone ring of 5 mol / kg or less is suitable from the viewpoint of further improving the water resistance of the cured product.
（Ａ）成分は、エポキシ当量が、１９０〜５０００ｇ／ｅｑであることが好ましく、２００〜２５００ｇ／ｅｑであることがより好ましく、２００〜１０００ｇ／ｅｑであることがさらに好ましい。エポキシ当量が５０００ｇ／ｅｑ以下とすることは、硬化物の耐水性及び硬化物の耐熱性をより一層向上させる観点から好適である。一方、１９０ｇ／ｅｑ以上とすることは、硬化物の強靭性をより一層向上させる観点から好適である。 The component (A) preferably has an epoxy equivalent of 190 to 5000 g / eq, more preferably 200 to 2500 g / eq, and still more preferably 200 to 1000 g / eq. An epoxy equivalent of 5000 g / eq or less is preferable from the viewpoint of further improving the water resistance of the cured product and the heat resistance of the cured product. On the other hand, it is suitable to set it as 190 g / eq or more from a viewpoint of improving the toughness of hardened | cured material further.
さらに、（Ａ）成分に含まれる加水分解性塩素量は、好ましくは５００ｐｐｍ以下であり、より好ましくは２００ｐｐｍ以下であり、更に好ましくは１００ｐｐｍ以下であり、特に好ましくは５０ｐｐｍ以下である。
ここで、加水分解性塩素量とは、試料としての（Ａ）成分３ｇを２５ｍｌのトルエンに溶解し、これに０．１規定のＫＯＨ−メタノール溶液２０ｍｌを加えて１５分間煮沸した後に硝酸銀で滴定して得られる値から、同じく試料をトルエンに溶解し、そのまま硝酸銀で滴定して得られる無機塩素量の値を差し引いて求めた値である。この加水分解性塩素量を５００ｐｐｍ以下とすることにより、耐湿性の低下を抑制することが可能となる。
Furthermore, the amount of hydrolyzable chlorine contained in the component (A) is preferably 500 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less, and particularly preferably 50 ppm or less.
Here, the amount of hydrolyzable chlorine is obtained by dissolving 3 g of the component (A) as a sample in 25 ml of toluene, adding 20 ml of a 0.1 N KOH-methanol solution and boiling for 15 minutes, and titrating with silver nitrate. The value obtained by subtracting the value of the amount of inorganic chlorine obtained by dissolving the sample in toluene and titrating with silver nitrate as it is. By making the amount of hydrolyzable chlorine 500 ppm or less, it becomes possible to suppress a decrease in moisture resistance.
加えて、（Ａ）成分は、赤外分光光度測定によるイソシアヌレート環由来の波数１，７１０ｃｍ−１の吸光度が、オキサゾリドン環由来の波数１，７５０ｃｍ−１の吸光度に対して０．３以下のものであることが好ましい。この赤外分光光度測定強度比を０．３以下とすることは、ワニスやプリプレグの保存安定性及び硬化物の耐水性の低下を抑制する観点から好適である。 In addition, the component (A) has an absorbance of wave number 1,710 cm −1 derived from an isocyanurate ring by infrared spectrophotometry, which is 0.3 or less than the absorbance of wave number 1,750 cm −1 derived from an oxazolidone ring. It is preferable. Setting the infrared spectrophotometric intensity ratio to 0.3 or less is preferable from the viewpoint of suppressing the storage stability of the varnish or prepreg and the water resistance of the cured product.
（Ａ）成分の軟化点は、好ましくは６０〜９５℃であり、より好ましくは６０〜８０℃である。軟化点を９５℃以下とすることは、プリプレグ作成時の樹脂の十分な含浸を実現する観点から好適である。一方、６０℃以上とすることは、成型時の樹脂フローを抑制し、適正な樹脂含有を実現する観点から好適である。 The softening point of (A) component becomes like this. Preferably it is 60-95 degreeC, More preferably, it is 60-80 degreeC. Setting the softening point to 95 ° C. or lower is preferable from the viewpoint of realizing sufficient impregnation of the resin at the time of preparing the prepreg. On the other hand, setting it to 60 ° C. or higher is preferable from the viewpoint of suppressing resin flow during molding and realizing proper resin content.
（Ａ）成分の１００℃における溶融粘度は、好ましくは５〜５００Ｐａ・ｓであり、より好ましくは５〜１００Ｐａ・ｓである。溶融粘度を、５００Ｐａ・ｓ以下とすることは、プリプレグ作成時の樹脂の含浸を十分に実現する観点から好適である。一方、５Ｐａ・ｓ以上とすることは、成型時の樹脂フローを抑制して適正な樹脂含有を実現する観点から好適である。 (A) The melt viscosity in 100 degreeC of a component becomes like this. Preferably it is 5-500 Pa.s, More preferably, it is 5-100 Pa.s. Setting the melt viscosity to 500 Pa · s or less is preferable from the viewpoint of sufficiently realizing the impregnation of the resin at the time of preparing the prepreg. On the other hand, setting it to 5 Pa · s or more is preferable from the viewpoint of suppressing the resin flow during molding and realizing proper resin content.
（Ａ）成分の製造方法としては、特に限定されるものではなく、例えば、イソシアネート化合物とグリシジル化合物とを、オキサゾリドン環形成触媒の存在下で反応させることにより、ほぼ理論量で得ることができる。イソシアネート化合物とグリシジル化合物は、当量比１：２〜１：１０の範囲で反応させることが好ましく、この場合、硬化物の耐熱性及び硬化物の耐水性をより一層向上させることが可能となる。 The method for producing the component (A) is not particularly limited, and for example, it can be obtained in a substantially theoretical amount by reacting an isocyanate compound and a glycidyl compound in the presence of an oxazolidone ring-forming catalyst. The isocyanate compound and the glycidyl compound are preferably reacted in an equivalent ratio of 1: 2 to 1:10. In this case, the heat resistance of the cured product and the water resistance of the cured product can be further improved.
（Ａ）成分を得るための原料となるグリシジル化合物（以下、「原料グリシジル化合物」とも称される）の具体例としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、ビスフェノールＳ、テトラメチルビスフェノールＡ、テトラメチルビスフェノールＦ、テトラメチルビスフェノールＡＤ、テトラメチルビスフェノールＳ、テトラブロモビスフェノールＡ、ビフェノール、等の２価フェノール類をグリシジル化した化合物；１，１，１−トリス（４−ヒドロキシフェニル）メタン、１，１，１−（４−ヒドロキシフェニル）エタン、４，４−〔１−〔４−〔１−（４−ヒドロキシフェニル）−１−メチルエチル〕フェニル〕エチリデン〕ビスフェノール等のトリス（グリシジルオキシフェニル）アルカン類、等をグリシジル化した化合物；フェノールノボラック、クレゾールノボラック、ビスフェノールＡノボラック、等のノボラックをグリシジル化した化合物等が挙げられるが、これらに特に限定されるものではない。尚、上記の原料グリシジル化合物は、１種を単独で或いは２種以上を組み合わせて用いることができる。 Specific examples of the glycidyl compound (hereinafter also referred to as “raw material glycidyl compound”) as a raw material for obtaining the component (A) include, for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and tetramethylbisphenol A. , A compound obtained by glycidylation of dihydric phenols such as tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, and biphenol; 1,1,1-tris (4-hydroxyphenyl) methane, Tris (glycidyloxy) such as 1,1,1- (4-hydroxyphenyl) ethane, 4,4- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol Phenyl) alkanes, etc. Rishijiru of the compound; phenol novolac, cresol novolac, bisphenol A novolac, although compounds novolak was glycidylated etc., etc., are not particularly limited thereto. In addition, said raw material glycidyl compound can be used individually by 1 type or in combination of 2 or more types.
本実施の形態においては、（Ａ）成分の樹脂を得るための原料となるイソシアネート化合物（以下、「原料イソシアネート化合物」とも称される）として、下記一般式（３）で表される化合物を用いる。 In the present embodiment, a compound represented by the following general formula (3) is used as an isocyanate compound (hereinafter also referred to as “raw material isocyanate compound”) which is a raw material for obtaining the resin of component (A). .
原料イソシアネート化合物の具体例としては、例えば、ω，ω′−１，４−ジメチルナフタレンジイソシアネート、ω，ω′−１，５−ジメチルナフタレンジイソシアネート、ナフタレン−１，４−ジイソシアネート、ナフタレン−１，５−ジイソシアネート、等が挙げられ、中でも、耐熱性の点から、ナフタレン−１，５−ジイソシアネートが好ましい。なお、原料イソシアネート化合物は、１種を単独で或いは２種以上を組み合わせて用いることができる。 Specific examples of the raw material isocyanate compound include, for example, ω, ω′-1,4-dimethylnaphthalene diisocyanate, ω, ω′-1,5-dimethylnaphthalene diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5. -Diisocyanate etc. are mentioned, Naphthalene-1,5-diisocyanate is especially preferable from a heat resistant point. In addition, a raw material isocyanate compound can be used individually by 1 type or in combination of 2 or more types.
上記（Ａ）成分の製造の際に用いるオキサゾリドン環形成触媒は、原料グリシジル化合物と原料イソシアネート化合物との反応において、オキサゾリドン環を選択的に生成する触媒であることが好ましい。
このようなオキサゾリドン環を生成する触媒の具体例としては、例えば、塩化リチウム、ブトキシリチウム等のリチウム化合物、３フッ化ホウ素等の錯塩；
テトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、テトラメチルアンモニウムヨーダイド、テトラブチルアンモニウムブロマイド等の４級アンモニウム塩；
ジメチルアミノエタノール、トリエチルアミン、トリブチルアミン、ベンジルジメチルアミン、Ｎ−メチルモルホリン等の３級アミン；
トリフェニルホスフィン等のホスフィン類；
アリルトリフェニルホスホニウムブロマイド、ジアリルジフェニルホスホニウムブロマイド、エチルトリフェニルホスホニウムクロライド、エチルトリフェニルホスホニウムヨーダイド、テトラブチルホスホニウムアセテート・酢酸錯体、テトラブチルホスホニウムアセテート、テトラブチルホスホニウムクロライド、テトラブチルホスホニウムブロマイド、テトラブチルホスホニウムヨーダイド等のホスホニウム化合物；
トリフェニルアンチモン及びヨウ素の組み合わせ；
２−フェニルイミダゾール、２−メチルイミダゾール等のイミダゾール類、
等が挙げられる。なお、これらに特に限定されるものではない。また、これらの触媒は、１種を単独で或いは２種以上を組み合わせて用いることができる。
The oxazolidone ring forming catalyst used in the production of the component (A) is preferably a catalyst that selectively generates an oxazolidone ring in the reaction of the raw material glycidyl compound and the raw material isocyanate compound.
Specific examples of such a catalyst that forms an oxazolidone ring include, for example, lithium compounds such as lithium chloride and butoxylithium, and complex salts such as boron trifluoride;
Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetrabutylammonium bromide;
Tertiary amines such as dimethylaminoethanol, triethylamine, tributylamine, benzyldimethylamine, N-methylmorpholine;
Phosphines such as triphenylphosphine;
Allyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, tetrabutylphosphonium acetate / acetic acid complex, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium Phosphonium compounds such as iodide;
A combination of triphenylantimony and iodine;
Imidazoles such as 2-phenylimidazole and 2-methylimidazole,
Etc. In addition, it is not specifically limited to these. Moreover, these catalysts can be used individually by 1 type or in combination of 2 or more types.
オキサゾリドン環形成触媒の使用量は、特に限定されるものではなく、通常は原料に対し５ｐｐｍ〜２ｗｔ％（「ｗｔ％」と「質量％」とは同義である）程度の範囲で使用され、好ましくは１０ｐｐｍ〜１ｗｔ％、より好ましくは２０〜５０００ｐｐｍ、さらに好ましくは２０〜１０００ｐｐｍの範囲である。触媒の使用量を２ｗｔ％以下とすることにより、耐湿性の低下を抑制することが可能となり、一方、５ｐｐｍ以上とすることにより、生産効率を向上させることが可能となる。 The amount of the oxazolidone ring-forming catalyst is not particularly limited, and is usually used in the range of about 5 ppm to 2 wt% (“wt%” and “mass%” are synonymous) with respect to the raw material, preferably Is in the range of 10 ppm to 1 wt%, more preferably 20 to 5000 ppm, still more preferably 20 to 1000 ppm. When the amount of the catalyst used is 2 wt% or less, it is possible to suppress a decrease in moisture resistance. On the other hand, when the amount is 5 ppm or more, production efficiency can be improved.
（Ａ）成分の製造は、原料グリシジル化合物や原料イソシアネート化合物等を溶解又は分散可能な溶剤の存在下においても実施することができる。ここで用いる溶剤の具体例としては、特に限定されるものではないが、例えば、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシド、メチルエチルケトン、キシレン、トルエン、メチルセロソルブ、テトラヒドロフラン等の不活性溶剤が好ましい。これらは、１種を単独で或いは２種以上を組み合わせて用いることができる。 The production of the component (A) can also be carried out in the presence of a solvent capable of dissolving or dispersing the raw material glycidyl compound, the raw material isocyanate compound and the like. Specific examples of the solvent used here are not particularly limited. For example, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methyl ethyl ketone, xylene, Inert solvents such as toluene, methyl cellosolve and tetrahydrofuran are preferred. These can be used singly or in combination of two or more.
以下、（Ａ）成分の好ましい製造プロセスについて説明する。
まず、原料グリシジル化合物を反応器内に所定量投入した後、加熱して所定温度に調整し、その後、オキサゾリドン環形成触媒を投入する。触媒の投入は、水又は溶剤に触媒を添加した溶液を投入することによって実施してもよい。触媒投入時の反応器内の温度は、２０〜２００℃の範囲であることが好ましく、８０〜２００℃であることがより好ましく、１１０〜１８０℃であることがさらに好ましい。２０℃以上で触媒を投入することにより、所定の反応温度に到達するまでの間、エポキシ基と分子内２級アルコール性基との反応を防いで、エポキシ基濃度の低下を抑制でき、一方、２００℃以下で触媒を投入することにより、反応の暴走を抑制することができる。
Hereinafter, the preferable manufacturing process of (A) component is demonstrated.
First, a predetermined amount of a raw material glycidyl compound is charged into a reactor, and then heated to adjust the temperature to a predetermined temperature, and then an oxazolidone ring-forming catalyst is charged. The catalyst may be charged by adding a solution obtained by adding a catalyst to water or a solvent. The temperature in the reactor when the catalyst is charged is preferably in the range of 20 to 200 ° C, more preferably 80 to 200 ° C, and even more preferably 110 to 180 ° C. By introducing the catalyst at 20 ° C. or higher, the reaction between the epoxy group and the intramolecular secondary alcohol group can be prevented until the predetermined reaction temperature is reached, and the decrease in the epoxy group concentration can be suppressed, By introducing the catalyst at 200 ° C. or lower, the runaway reaction can be suppressed.
次に、原料イソシアネート化合物を反応器に所定量投入する。ここで、原料イソシアネート化合物を、０．５〜１０時間、好ましくは２〜５時間かけて、１回又は数回に分け段階的又は連続的に滴下することが望ましい。滴下時間を０．５時間以上とすることにより、所望しないイソシアヌレート環の生成が抑制され、一方、１０時間以下とすることにより、エポキシ基濃度の低下が抑制され、いずれの場合も、得られる（Ａ）成分性能の劣化を抑制することができる。 Next, a predetermined amount of the raw material isocyanate compound is charged into the reactor. Here, it is desirable to drop the raw material isocyanate compound stepwise or continuously in one or several times over 0.5 to 10 hours, preferably 2 to 5 hours. By setting the dropping time to 0.5 hours or longer, generation of an undesired isocyanurate ring is suppressed, while by setting it to 10 hours or shorter, a decrease in the epoxy group concentration is suppressed, and in any case, it is obtained. (A) Deterioration of component performance can be suppressed.
原料エポキシ化合物と原料イソシアネート化合物との反応温度は、通常２０〜３００℃の範囲であり、好ましくは６０〜２５０℃、より好ましくは１２０〜２３０℃、さらに好ましくは１４０〜２２０℃、特に好ましくは１４０〜２００℃の範囲である。反応温度を３００℃以下とすることにより、得られる（Ａ）成分の性能劣化が抑制され、２０℃以上とすることにより、所望しないトリイソシアヌレート環の生成が抑制され、いずれの場合も、得られる（Ａ）成分の硬化物の耐水性の低下を抑制することができる。 The reaction temperature of the raw material epoxy compound and the raw material isocyanate compound is usually in the range of 20 to 300 ° C, preferably 60 to 250 ° C, more preferably 120 to 230 ° C, still more preferably 140 to 220 ° C, and particularly preferably 140. It is the range of -200 degreeC. By setting the reaction temperature to 300 ° C. or lower, performance deterioration of the obtained component (A) is suppressed, and by setting it to 20 ° C. or higher, generation of an undesired triisocyanurate ring is suppressed. It is possible to suppress a decrease in water resistance of the cured product (A).
また、原料グリシジル化合物と原料イソシアネート化合物により（Ａ）成分を製造する際は、フェノール化合物を添加することが好ましい。
ここで添加するフェノール化合物の具体例としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、ビスフェノールＳ、テトラメチルビスフェノールＡ、テトラメチルビスフェノールＦ、テトラメチルビスフェノールＡＤ、テトラメチルビスフェノールＳ、テトラブロモビスフェノールＡ、ビフェノール、ジヒドロキシナフタレン、１，１，１−トリス（４−ヒドロキシフェニル）メタン、１，１，１−（４−ヒドロキシフェニル）エタン、４，４−〔１−〔４−〔１−（４−ヒドロキシフェニル）−１−メチルエチル〕フェニル〕エチリデン〕ビスフェノール等のトリス（グリシジルオキシフェニル）アルカン類、アミノフェノール、フェノールノボラック、クレゾールノボラック、ビスフェノールＡノボラック、ナフトールノボラック等が挙げられるが、これらに特に限定されるものではない。これらは、１種を単独で或いは２種以上を組み合わせて用いることができる。
Moreover, when manufacturing (A) component with a raw material glycidyl compound and a raw material isocyanate compound, it is preferable to add a phenol compound.
Specific examples of the phenol compound added here include, for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A. , Biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1- (4-hydroxyphenyl) ethane, 4,4- [1- [4- [1- (4 -Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, tris (glycidyloxyphenyl) alkanes, aminophenol, phenol novolak, cresol novolak, bisphenol A novolak, Off tall novolac and the like, but not particularly limited thereto. These can be used singly or in combination of two or more.
なお、本実施の形態のエポキシ樹脂組成物は、（Ａ）成分を１種含むものであれば、例えば、（Ａ）成分を２種以上含むものであっても、（Ａ）成分以外のエポキシ樹脂を１種或いは２種以上含むものであってもよい。この場合、エポキシ樹脂の総量に対し、（Ａ）成分が８０質量％以上含まれることが好ましく、９０質量％以上含まれることがより好ましく、１００質量％含まれていてもよい。（Ａ）成分が８０質量％以上であると、プリプレグの取扱い性と、硬化物の耐熱性を向上させることができるため好ましい。 In addition, if the epoxy resin composition of this Embodiment contains 1 type of (A) component, for example, even if it contains 2 or more types of (A) components, epoxy other than (A) component One type or two or more types of resins may be included. In this case, it is preferable that 80 mass% or more of (A) component is contained with respect to the total amount of an epoxy resin, it is more preferable that 90 mass% or more is contained, and 100 mass% may be contained. It is preferable for the component (A) to be 80% by mass or more because the prepreg handleability and the heat resistance of the cured product can be improved.
また、（Ａ）成分が、本実施の形態のエポキシ樹脂組成物中に占める割合としては、好ましくは５０質量％以上、より好ましくは６０質量％以上、更に好ましくは７０質量％以上、特に好ましくは８０質量％以上である。上限としては、好ましくは９５質量％以下、より好ましくは９０質量％以下である。 Moreover, as a ratio for which (A) component accounts in the epoxy resin composition of this Embodiment, Preferably it is 50 mass% or more, More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more, Most preferably 80% by mass or more. As an upper limit, Preferably it is 95 mass% or less, More preferably, it is 90 mass% or less.
［（Ｂ）硬化剤］
（Ｂ）成分としては、特に限定されるものではなく、各種公知のものを適宜選択して用いることができるが、硬化時の反応速度の観点から、ウレア系化合物（分子内にウレア結合を有する化合物を示す）、グアニジン誘導体、芳香族アミン化合物及びノボラック型フェノール樹脂よりなる群から選択される少なくとも１種であることが好ましい。これらウレア系化合物、グアニジン誘導体、芳香族アミン化合物及びノボラック型フェノール樹脂は、１種を単独で或いは２種以上を組み合わせて用いることができる。
[(B) Curing agent]
The component (B) is not particularly limited, and various known compounds can be appropriately selected and used. From the viewpoint of the reaction rate during curing, a urea compound (having a urea bond in the molecule). Compound), at least one selected from the group consisting of guanidine derivatives, aromatic amine compounds and novolac-type phenol resins. These urea compounds, guanidine derivatives, aromatic amine compounds and novolac type phenol resins can be used singly or in combination of two or more.
グアニジン誘導体の具体例としては、例えば、ジシアンジアミド、ジシアンジアミド−アニリン付加物、ジシアンジアミド−メチルアニリン付加物、ジシアンジアミド−ジアミノジフェニルメタン付加物、ジシアンジアミド−ジアミノジフェニルエーテル付加物等のジシアンジアミド誘導体、硝酸グアニジン、炭酸グアニジン、リン酸グアニジン、スルファミン酸グアニジン、重炭酸アミノグアニジン等のグアニジン塩、アセチルグアニジン、ジアセチルグアニジン、プロピオニルグアニジン、ジプロピオニルグアニジン、シアノアセチルグアニジン、コハク酸グアニジン、ジエチルシアノアセチルグアニジン、ジシアンジアミジン、Ｎ−オキシメチル−Ｎ’−シアノグアニジン、Ｎ、Ｎ’−ジカルボエトキシグアニジン等が挙げられるが、これらに特に限定されるものではない。 Specific examples of guanidine derivatives include dicyandiamide derivatives such as dicyandiamide, dicyandiamide-aniline adduct, dicyandiamide-methylaniline adduct, dicyandiamide-diaminodiphenylmethane adduct, dicyandiamide-diaminodiphenyl ether adduct, guanidine nitrate, guanidine carbonate, phosphorus Guanidine salts such as guanidine acid, guanidine sulfamate, aminoguanidine bicarbonate, acetylguanidine, diacetylguanidine, propionylguanidine, dipropionylguanidine, cyanoacetylguanidine, guanidine succinate, diethylcyanoacetylguanidine, dicyandiamidine, N-oxymethyl -N'-cyanoguanidine, N, N'-dicarboethoxyguanidine, etc. It is not particularly limited to these.
芳香族アミン化合物の具体例としては、例えば、メタフェニレンジアミン、パラフェニレンジアミン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルメタン、４、４’−ジアミノジフェニルエーテル等が挙げられるが、これらに特に限定されるものではない。 Specific examples of the aromatic amine compound include, for example, metaphenylene diamine, paraphenylene diamine, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl methane, 4, 4 ′. -Diamino diphenyl ether etc. are mentioned, However, It does not specifically limit to these.
ノボラック型フェノール樹脂の具体例としては、例えば、フェノールノボラック、ビスフェノールＡノボラック、クレゾールノボラック、ナフトールノボラック等が挙げられるが、これらに特に限定されるものではない。 Specific examples of the novolak type phenol resin include, but are not limited to, phenol novolak, bisphenol A novolak, cresol novolak, naphthol novolak, and the like.
（Ｂ）成分の配合量は、特に制限されるものではなく、所望の設計に応じて適宜設定されるが、（Ｂ）成分がグアニジン誘導体の場合、エポキシ樹脂の総量に対して２〜８質量％であることが好ましく、（Ｂ）成分が芳香族アミン化合物の場合はエポキシ樹脂の総量に対して１０〜５０質量％であることが好ましく、（Ｂ）成分がノボラック型フェノール樹脂の場合はエポキシ樹脂の総量に対して２０〜６０質量％であることが好ましい。配合量をこれらの範囲とすることは、硬化物の架橋密度の低下及びＴｇの低下を抑制し、耐湿性を確保する観点から好適である。 The blending amount of the component (B) is not particularly limited and is appropriately set according to a desired design. When the component (B) is a guanidine derivative, 2 to 8 mass based on the total amount of the epoxy resin. When the component (B) is an aromatic amine compound, it is preferably 10 to 50% by mass relative to the total amount of the epoxy resin, and when the component (B) is a novolac type phenol resin, an epoxy is preferable. It is preferable that it is 20-60 mass% with respect to the total amount of resin. Setting the blending amount within these ranges is preferable from the viewpoint of suppressing the decrease in the crosslinking density and the decrease in Tg of the cured product and ensuring the moisture resistance.
［（Ｃ）成分］
本実施の形態のエポキシ樹脂組成物には、さらに、
（Ｃ）ビスフェノールＡ型エポキシ樹脂及び／又はビスフェノールＦ型エポキシ樹脂、
が含まれていてもよい。
（Ｃ）成分の含有量は、エポキシ樹脂の総量に対して、好ましくは５〜６０質量％、より好ましくは１０〜４０質量％である。（Ｃ）成分の含有量を６０質量％以下とすることは、耐熱性を向上させる観点から好適である。一方、５質量％以上とすることは、プリプレグ作成時の樹脂の含浸を十分に行なう観点から好適である。
[Component (C)]
In the epoxy resin composition of the present embodiment,
(C) bisphenol A type epoxy resin and / or bisphenol F type epoxy resin,
May be included.
The content of the component (C) is preferably 5 to 60% by mass and more preferably 10 to 40% by mass with respect to the total amount of the epoxy resin. Setting the content of the component (C) to 60% by mass or less is preferable from the viewpoint of improving heat resistance. On the other hand, the content of 5% by mass or more is preferable from the viewpoint of sufficiently impregnating the resin at the time of preparing the prepreg.
ビスフェノールＡ型エポキシ樹脂としては、例えば、ＡＥＲ２６０（旭化成ケミカルズ（株）製、エポキシ当量１８９ｇ／ｅｑ）のようなエポキシ樹脂が挙げられる。
また、ビスフェノールＦ型エポキシ樹脂としては、例えば、ＥＰＩＣＬＯＮ８３０（大日本インキ化学工業（株）製、エポキシ当量１７９ｇ／ｅｑ）のようなエポキシ樹脂が挙げられる。
Examples of the bisphenol A type epoxy resin include an epoxy resin such as AER260 (manufactured by Asahi Kasei Chemicals Corporation, epoxy equivalent 189 g / eq).
Examples of the bisphenol F type epoxy resin include an epoxy resin such as EPICLON 830 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 179 g / eq).
［（Ｄ）成分］
本実施の形態のエポキシ樹脂組成物には、さらに、
（Ｄ）熱可塑性エラストマー及び／又は架橋ゴム、
が含まれていてもよい。
[(D) component]
In the epoxy resin composition of the present embodiment,
(D) a thermoplastic elastomer and / or a crosslinked rubber;
May be included.
熱可塑性エラストマーとしては、例えば、ポリエステル系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー等が挙げられ、後者の方が、繊維強化複合材料の圧縮強度、層間剪断強度等の物性に優れるため、好ましい。
架橋ゴムとしては、例えば、アクリロニトリル−ブタジエン共重合体、スチレン−ブタジエン共重合体等が挙げられ、前者の方が、エポキシ樹脂との相溶性の点から好ましい。
Examples of the thermoplastic elastomer include polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and the like. The latter is preferable because the physical properties such as compression strength and interlayer shear strength of the fiber-reinforced composite material are excellent.
Examples of the crosslinked rubber include acrylonitrile-butadiene copolymer and styrene-butadiene copolymer, and the former is preferable from the viewpoint of compatibility with the epoxy resin.
（Ｄ）熱可塑性エラストマー及び／又は架橋ゴムの含有量は、エポキシ樹脂組成物全体に対して、好ましくは１〜１０質量％、より好ましくは２〜７質量％である。（Ｄ）成分の含有量を１０質量％以下とすることは、樹脂粘度が増大してプリプレグへの樹脂の含浸性が悪くなることを防止する観点から好適である。一方、１質量％以上とすることは、プリプレグのタック性を良好に維持し、また、成型不良を抑制する観点から好適である。 (D) The content of the thermoplastic elastomer and / or the crosslinked rubber is preferably 1 to 10% by mass, more preferably 2 to 7% by mass, based on the entire epoxy resin composition. Setting the content of the component (D) to 10% by mass or less is preferable from the viewpoint of preventing the resin viscosity from increasing and impairing the resin into the prepreg. On the other hand, the content of 1% by mass or more is preferable from the viewpoint of maintaining good prepreg tackiness and suppressing molding defects.
［（Ｅ）成分］
本実施の形態のエポキシ樹脂組成物には、さらに、（Ｅ）フィラー、が含まれていてもよい。（Ｅ）成分は、レオロジー制御すなわち増粘やチキソトロピー性付与効果があるため好ましい。
[(E) component]
The epoxy resin composition of the present embodiment may further contain (E) filler. The component (E) is preferable because it has rheology control, that is, thickening and thixotropy imparting effects.
フィラーとしては、例えば、タルク、ケイ酸アルミニウム、微粒状シリカ、炭酸カルシウム、マイカ、アルミナ水和物、亜鉛末、カーボンブラック、炭化ケイ素などが挙げられ、チキソトロピー性付与効果の点から微粒状シリカが好ましい。 Examples of the filler include talc, aluminum silicate, finely divided silica, calcium carbonate, mica, alumina hydrate, zinc powder, carbon black, silicon carbide, and the like. preferable.
（Ｅ）フィラーの含有量は、エポキシ樹脂組成物全体に対して、好ましくは１〜１０質量％、より好ましくは１〜５質量％である。（Ｅ）成分の含有量を１０質量％以下とすることは、樹脂粘度が高すぎてプリプレグへの樹脂の含浸が困難となって、プリプレグ間の接着強度が低下することを防止する観点から好適である。一方、１質量％以上とすることは、成型物表面に樹脂かすれが発生することを抑制する観点から好適である。 (E) Content of a filler becomes like this. Preferably it is 1-10 mass% with respect to the whole epoxy resin composition, More preferably, it is 1-5 mass%. Setting the content of the component (E) to 10% by mass or less is preferable from the viewpoint of preventing the resin viscosity from being too high and impregnating the resin into the prepreg and preventing the adhesive strength between the prepregs from decreasing. It is. On the other hand, the content of 1% by mass or more is preferable from the viewpoint of suppressing the occurrence of resin fading on the surface of the molded product.
本発明のエポキシ樹脂組成物は、プリプレグ用のマトリックス樹脂として６０℃の粘度が３００〜３０００Ｐa・ｓあることが好ましい。３００Ｐa・ｓより大きくすることで、過剰なタック性を防止でき、かつ、成型時の過剰な樹脂フローを抑制できて好ましい。また、３０００Ｐa・ｓより小さくすることで、プリプレグへの樹脂の含浸性を維持できて好ましい。より好ましい範囲としては５００〜１５００Ｐa・ｓである。 The epoxy resin composition of the present invention preferably has a viscosity at 60 ° C. of 300 to 3000 Pa · s as a matrix resin for prepreg. By making it larger than 300 Pa · s, excessive tackiness can be prevented and excessive resin flow during molding can be suppressed, which is preferable. Moreover, it is preferable to make it smaller than 3000 Pa · s because the impregnation property of the resin to the prepreg can be maintained. A more preferable range is 500 to 1500 Pa · s.
［エポキシ樹脂ワニス］
上記のエポキシ樹脂組成物は、好ましくは、溶媒中に均一に溶解又は分散させたエポキシ樹脂ワニスとして使用される。ここで用いる溶媒は、上記のエポキシ樹脂組成物を溶解又は分散可能なものであれば特に限定されるものではなく、例えば、アセトン、メチルエチルケトン、メチルセロソルブ、メチルイソブチルケトン、ジメチルホルムアミド、プロピレングリコールモノメチルエーテル、トルエン、キシレン等及びこれらの混合溶媒が挙げられる。
[Epoxy resin varnish]
The above epoxy resin composition is preferably used as an epoxy resin varnish uniformly dissolved or dispersed in a solvent. The solvent used here is not particularly limited as long as it can dissolve or disperse the above epoxy resin composition. For example, acetone, methyl ethyl ketone, methyl cellosolve, methyl isobutyl ketone, dimethylformamide, propylene glycol monomethyl ether , Toluene, xylene and the like, and mixed solvents thereof.
また、上記のエポキシ樹脂組成物又はエポキシ樹脂ワニスに、硬化促進剤をさらに配合して、エポキシ樹脂組成物の硬化速度の調整を行なうことも可能である。硬化促進剤としては、各種公知のものを特に制限なく用いることができるが、例えば、尿素化合物、イミダゾール類、第３級アミン類、ホスフィン類或いはアミノトリアゾール類等が挙げられ、また、上記（Ｂ）成分と公知の組み合わせを用いることができる。 It is also possible to adjust the curing rate of the epoxy resin composition by further blending a curing accelerator with the above epoxy resin composition or epoxy resin varnish. As the curing accelerator, various known ones can be used without particular limitation, and examples thereof include urea compounds, imidazoles, tertiary amines, phosphines, aminotriazoles, and the like (B ) Component and a known combination can be used.
［プリプレグ］
上記のエポキシ樹脂組成物を強化繊維シートに含浸させることにより、機械的強度が高められ且つ寸法安定性を増大された、プリプレグが作製される。
[Prepreg]
By impregnating the reinforcing fiber sheet with the epoxy resin composition described above, a prepreg having improved mechanical strength and increased dimensional stability is produced.
ここで用いる強化繊維シートとしては、各種公知のものを適宜選択して用いることができ、例えば、ロービングクロス、クロス、チョップドマット、サーフェシングマット等の各種ガラス布、アスベスト布、金属繊維布、及び、その他合成若しくは天然の無機繊維布；ポリビニルアルコール繊維、ポリエステル繊維、アクリル繊維、全芳香族ポリアミド繊維、ポリテトラフルオロエチレン繊維等の合成繊維から得られる織布又は不織布；綿布、麻布、フェルト等の天然繊維布；カーボン繊維布；クラフト紙、コットン紙、紙−ガラス混繊紙等の天然セルロース系布、等が挙げられ、中でも、低比重かつ比強度、比弾性率に優れた、カーボン繊維布が好ましい。
また、これらの強化繊維シートは、１種を単独で或いは２種以上を組み合わせて用いることができる。さらに、有機及び／又は無機の短繊維をエポキシ樹脂組成物に加えた後に半硬化させて成形することでプリプレグを作製してもよい。
As the reinforcing fiber sheet used here, various known materials can be appropriately selected and used, for example, various glass cloths such as roving cloth, cloth, chopped mat, surfacing mat, asbestos cloth, metal fiber cloth, and the like. , Other synthetic or natural inorganic fiber cloth; woven or non-woven fabric obtained from synthetic fibers such as polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, polytetrafluoroethylene fiber; cotton cloth, linen cloth, felt, etc. Natural fiber cloth; carbon fiber cloth; natural cellulosic cloth such as kraft paper, cotton paper, paper-glass mixed paper, and the like. Among them, carbon fiber cloth having low specific gravity, excellent specific strength, and excellent specific modulus. Is preferred.
Moreover, these reinforcing fiber sheets can be used individually by 1 type or in combination of 2 or more types. Further, a prepreg may be produced by adding organic and / or inorganic short fibers to the epoxy resin composition and then semi-curing and molding.
強化繊維シートの厚さは、プリプレグの厚さや、所望の機械的強度及び寸法安定性等に応じて適宜設定すればよく、通常、０．０５〜０．３０ｍｍ程度であるが、特に限定されるものではない。 The thickness of the reinforcing fiber sheet may be appropriately set according to the thickness of the prepreg, desired mechanical strength and dimensional stability, and is usually about 0.05 to 0.30 mm, but is particularly limited. It is not a thing.
プリプレグにおいて強化繊維シートの占める割合は、所望のプリプレグの性能に応じて適宜設定され、特に限定されるものではなく、プリプレグの総量に対し、３０〜９０質量％であることが好ましく、４０〜８０質量％であることがより好ましく、５０〜７０質量％であることがさらに好ましい。強化繊維シートを３０質量％以上とすることは、寸法安定性及び強度により一層優れる硬化物を得る観点から好適である。一方、強化繊維シートを９０質量％以下とすることは、密着性により一層優れる硬化物を得る観点から好適である。尚、プリプレグの総量に対し、３０〜９０質量％となる場合に、本実施の形態において、含浸性良好と呼ぶ。 The proportion of the reinforcing fiber sheet in the prepreg is appropriately set according to the desired performance of the prepreg, and is not particularly limited, and is preferably 30 to 90% by mass with respect to the total amount of the prepreg, and 40 to 80 More preferably, it is 50 mass%, and it is further more preferable that it is 50-70 mass%. Setting the reinforcing fiber sheet to 30% by mass or more is preferable from the viewpoint of obtaining a cured product that is more excellent in dimensional stability and strength. On the other hand, setting the reinforcing fiber sheet to 90% by mass or less is preferable from the viewpoint of obtaining a cured product that is more excellent in adhesion. In addition, in this Embodiment, when it becomes 30-90 mass% with respect to the total amount of a prepreg, it is called favorable impregnation property.
プリプレグの製造方法としては、例えば、エポキシ樹脂組成物及び必要に応じ他の成分を、強化繊維シートに含浸させた後に乾燥する方法が挙げられる。強化繊維シートへのエポキシ樹脂組成物の含浸は、例えば、エポキシ樹脂組成物或いはエポキシ樹脂ワニスを基材に塗布したり、エポキシ樹脂ワニス中に強化繊維シートを浸漬（ディッピング）したりすることより実施できる。この含浸処理は、必要に応じ複数回繰り返して行なうことも可能であり、また、その際に組成や濃度の異なる複数のエポキシ樹脂組成物或いはエポキシ樹脂ワニスを用いて含浸を繰り返して行ない、所望の樹脂組成及び樹脂量に調整することも可能である。さらに、含浸強化繊維シートの乾燥の際、加熱の程度を調節してエポキシ樹脂組成物を半硬化させた状態、いわゆるＢステージ状態にすることが好ましい。含浸強化繊維シートの乾燥条件は、所望のプリプレグの素材や厚さ等に応じて適宜設定され、通常、乾燥温度１００〜２００℃、乾燥時間１〜３０分程度の条件下である。 Examples of the method for producing the prepreg include a method of impregnating a reinforcing fiber sheet with an epoxy resin composition and other components as required, followed by drying. The impregnation of the epoxy resin composition into the reinforcing fiber sheet is performed by, for example, applying the epoxy resin composition or the epoxy resin varnish to the base material, or immersing (dipping) the reinforcing fiber sheet in the epoxy resin varnish. it can. This impregnation treatment can be repeated a plurality of times as necessary, and at that time, the impregnation is repeatedly performed using a plurality of epoxy resin compositions or epoxy resin varnishes having different compositions and concentrations. It is also possible to adjust the resin composition and the resin amount. Furthermore, when the impregnated reinforcing fiber sheet is dried, it is preferable to adjust the degree of heating to a semi-cured state of the epoxy resin composition, that is, a so-called B-stage state. The drying conditions of the impregnated reinforcing fiber sheet are appropriately set according to the desired material and thickness of the prepreg, and are usually a drying temperature of 100 to 200 ° C. and a drying time of about 1 to 30 minutes.
プリプレグの製造の際、エポキシ樹脂組成物と強化繊維シートとの界面における接着性を改善する目的で、必要に応じエポキシ樹脂組成物或いはエポキシ樹脂ワニスに、カップリング剤を添加することができる。ここで用いるカップリング剤としては、各種公知のものを適宜選択して用いることができ、例えば、シランカップリング剤、チタネートカップリング剤、アルミニウム系カップリング剤、ジルコアルミネートカップリング剤が挙げられるが、これらに特に限定されるものではない。 During the production of the prepreg, a coupling agent can be added to the epoxy resin composition or the epoxy resin varnish as necessary for the purpose of improving the adhesion at the interface between the epoxy resin composition and the reinforcing fiber sheet. As a coupling agent used here, various well-known things can be selected suitably and can be used, for example, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirco aluminate coupling agent is mentioned. However, it is not particularly limited to these.
［炭素繊維強化複合材料］
炭素繊維強化複合材料は、上記のプリプレグを積層し、加熱加圧成形することにより製造することができる。加熱加圧成形は、常法にしたがって行なえばよく、例えば、温度８０〜３００℃、圧力０．０１〜１００ＭＰａ、時間１分〜１０時間の条件下、より好ましくは、温度１２０〜２５０℃、圧力０．１〜１０ＭＰａ、時間１分〜５時間の条件下で行なうことができる。
[Carbon fiber reinforced composite material]
The carbon fiber reinforced composite material can be manufactured by laminating the above-described prepreg and heating and pressing. The heating and pressing may be performed according to a conventional method, for example, a temperature of 80 to 300 ° C., a pressure of 0.01 to 100 MPa, and a time of 1 minute to 10 hours, more preferably a temperature of 120 to 250 ° C. and a pressure. It can be carried out under conditions of 0.1 to 10 MPa and a time of 1 minute to 5 hours.
以下、合成例、実施例及び比較例を挙げて本実施の形態を詳細に説明する。なお、以下において、「部」及び「％」は、「質量部」及び「質量％」を各々意味する。 Hereinafter, the present embodiment will be described in detail with reference to synthesis examples, examples, and comparative examples. In the following, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.
［測定方法］ 本明細書中の物性等の測定方法は以下の通りである。
（１）エポキシ当量
１ｇ当量のエポキシ基を含む樹脂の質量であり、ＪＩＳ Ｋ−７２３６に準拠して求めた。
（２）ＩＲ強度比
赤外分光光度測定（測定装置：日本分光（株）社製 ＦＴ／ＩＲ−６１００）により、イソシアヌレート環由来の波数１，７１０ｃｍ−１の吸光度Ａと、オキサゾリドン環由来の波数１，７５０ｃｍ−１の吸光度Ｂとの比（Ａ／Ｂ）を算出した。
（３）加水分解性塩素（ｐｐｍ）
試料中に含まれる加水分解性塩素量を測定した。試料３ｇを２５ｍｌのトルエンに溶解し、これに０．１規定のＫＯＨ−メタノール溶液２０ｍｌを加えて１５分間煮沸した後に、硝酸銀で滴定して得られる値から、同じく試料をトルエンに溶解し、そのまま硝酸銀で滴定して得られる無機塩素量の値を差し引いて求めた値である。
（４）軟化点
ＪＩＳ Ｋ−７２３４に準拠し、環球法にて求めた。
（５）エポキシ樹脂溶融粘度（１００℃）
合成例１〜５及び実施例・比較例の配合エポキシ樹脂について、粘度測定装置ＲＳ６００（英弘精機（株）製）を用い、ディスクプレート上に各エポキシ樹脂サンプル約０．５ｇを載せ、ローターとプレートとの間隔を０．１ｍｍとして回転させ、測定雰囲気温度が１００℃で安定となる粘度を測定した。
（６）エポキシ樹脂組成物粘度（６０℃）
実施例１，３，４，６，８，９及び比較例４，６，７，８のエポキシ樹脂組成物について、硬化剤と硬化促進剤以外の原料を予め１００℃で溶融させ、６０℃に冷却した後、硬化剤と硬化促進剤を添加して３０分混合した各サンプル約０．５ｇを、粘度測定装置ＲＳ６００のディスクプレート上に載せ、ローターとプレートとの間隔を０．５ｍｍとし、１０ラジアン／秒のシェアで回転させ、測定雰囲気温度が６０℃で安定となる粘度を測定した。
（７）プリプレグ取り扱い性
実施例１〜９及び比較例１〜９のエポキシ樹脂組成物について、作成したエポキシ樹脂ワニスの炭素繊維への含浸性及び作成したプリプレグのタック性を下記の基準にて評価した。
◎：含浸性良好、かつ、タック性も適度で取扱い性良好
○：含浸性良好、タック性はやや強いか、又はやや不足であるが実用可能
△：含浸性に欠け、タック性もやや不足で実用困難
×：含浸性が不良、またはタック性が強すぎて実用不可
（８）ガラス転移温度 実施例１〜９及び比較例１〜９のエポキシ樹脂組成物の硬化物について、動的粘弾性測定装置ＤＤＶ−２５ＦＰ（オリエンテック（株）製）を用い、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍの試験片を、２℃／分で昇温させ、ｔａｎδが最大となる温度として求めた。
（９）破壊靭性（ＫＩＣ） 実施例１〜９及び比較例１〜９のエポキシ樹脂組成物の硬化物について、弾塑性破壊靭性試験方法（ＪＳＭＥ Ｓ ００１−１９８１）に準拠し測定した。試験方法は、試験片中央に約２．５ｍｍのクラックを入れた長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍの試験片を、圧子移動速度０．５ｍｍ／分、支点間距離１７．６ｍｍでの３点曲げ試験にて測定した。
[Measuring method] Measuring methods for physical properties and the like in the present specification are as follows.
(1) Epoxy equivalent The mass of a resin containing 1 g equivalent of an epoxy group, which was determined according to JIS K-7236.
(2) IR intensity ratio By infrared spectrophotometry (measuring device: FT / IR-6100 manufactured by JASCO Corporation), an absorbance A having a wave number of 1,710 cm −1 derived from an isocyanurate ring and an oxazolidone ring The ratio (A / B) with the absorbance B at a wave number of 1,750 cm −1 was calculated.
(3) Hydrolyzable chlorine (ppm)
The amount of hydrolyzable chlorine contained in the sample was measured. 3 g of the sample was dissolved in 25 ml of toluene, 20 ml of 0.1 N KOH-methanol solution was added thereto, boiled for 15 minutes, and then the value obtained by titration with silver nitrate was similarly dissolved in toluene. It is a value obtained by subtracting the value of the amount of inorganic chlorine obtained by titration with silver nitrate.
(4) Softening point It calculated | required by the ring and ball method based on JISK-7234.
(5) Epoxy resin melt viscosity (100 ° C)
About compounded epoxy resins of Synthesis Examples 1 to 5 and Examples / Comparative Examples Using a viscosity measuring device RS600 (manufactured by Eihiro Seiki Co., Ltd.), about 0.5 g of each epoxy resin sample was placed on a disk plate, and the rotor and plate The viscosity at which the measurement ambient temperature is stable at 100 ° C. was measured.
(6) Viscosity of epoxy resin composition (60 ° C)
For the epoxy resin compositions of Examples 1, 3, 4, 6, 8, and 9 and Comparative Examples 4, 6, 7, and 8, raw materials other than the curing agent and the curing accelerator were previously melted at 100 ° C., and then heated to 60 ° C. After cooling, about 0.5 g of each sample added with a curing agent and a curing accelerator and mixed for 30 minutes is placed on the disk plate of the viscosity measuring device RS600, and the distance between the rotor and the plate is set to 0.5 mm. The sample was rotated at a shear of radians / second, and the viscosity at which the measurement ambient temperature was stable at 60 ° C. was measured.
(7) Prepreg handling property For the epoxy resin compositions of Examples 1 to 9 and Comparative Examples 1 to 9, the impregnation property of the prepared epoxy resin varnish into carbon fibers and the tack property of the prepared prepreg were evaluated according to the following criteria. did.
◎: Good impregnation, good tackiness and good handleability ○: Good impregnation, slightly strong tackiness or slightly insufficient, but practical use △: Poor impregnation, slightly poor tackiness Practical difficulty x: impregnation property is poor or tack property is too strong to be practically used (8) Glass transition temperature Dynamic viscosity measurement of cured products of the epoxy resin compositions of Examples 1 to 9 and Comparative Examples 1 to 9 Using a device DDV-25FP (manufactured by Orientec Co., Ltd.), a test piece having a length of 20 mm × width of 4 mm × thickness of 2 mm was heated at 2 ° C./min to obtain a temperature at which tan δ was maximized.
(9) Fracture toughness (K IC ) The cured products of the epoxy resin compositions of Examples 1 to 9 and Comparative Examples 1 to 9 were measured according to an elastoplastic fracture toughness test method (JSMES 001-1981). The test method consists of a test piece of length 20 mm × width 4 mm × thickness 2 mm with a crack of about 2.5 mm in the center of the test piece, 3 at an indenter moving speed of 0.5 mm / min and a fulcrum distance of 17.6 mm. It was measured by a point bending test.
［合成例１］
反応器内に、原料グリシジル化合物としてビスフェノールＡ型エポキシ樹脂（商品名：ＡＥＲ２６０、旭化成ケミカルズ（株）製、エポキシ当量１８９ｇ／ｅｑ）１００部、及び、オキサゾリドン環形成触媒としてテトラブチルアンモニウムブロマイド（商品名：臭化テトラ−ｎ−ブチルアンモニウム、和光純薬工業（株）製）０．０４部を投入し、撹拌加熱し、内温を１７５℃にした。さらに、原料イソシアネート化合物としてナフタレンジイソシアネート（商品名：デスモジュール１５（商標）、住友バイエルウレタン（株）製）１３．９部を９０分かけて反応器内に投入した。投入終了後、反応温度を１７５℃に保ち、８時間撹拌し、オキサゾリドン環含有エポキシ樹脂Ｉを得た。
[Synthesis Example 1]
In the reactor, 100 parts of bisphenol A type epoxy resin (trade name: AER260, manufactured by Asahi Kasei Chemicals Corporation, epoxy equivalent 189 g / eq) as a raw material glycidyl compound, and tetrabutylammonium bromide (trade name) as an oxazolidone ring formation catalyst 0.04 part of tetra-n-butylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred and heated to adjust the internal temperature to 175 ° C. Furthermore, 13.9 parts of naphthalene diisocyanate (trade name: Desmodur 15 (trademark), manufactured by Sumitomo Bayer Urethane Co., Ltd.) as a raw material isocyanate compound was charged into the reactor over 90 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 8 hours to obtain an oxazolidone ring-containing epoxy resin I.
［合成例２］
反応器内に、原料グリシジル化合物としてフェノールノボラック型エポキシ樹脂（商品名：ＥＰＮ１１３８、旭化成ケミカルズ（株）製、エポキシ当量１８２ｇ／ｅｑ）１００部、及び、オキサゾリドン環形成触媒としてテトラブチルアンモニウムブロマイド０．０４部を投入し、撹拌加熱し、内温を１７５℃にした。さらに、原料イソシアネート化合物としてナフタレンジイソシアネート（商品名：デスモジュール１５）、５．９部を６０分かけて反応器内に投入した。投入終了後、反応温度を１７５℃に保ち、８時間撹拌し、オキサゾリドン環含有エポキシ樹脂ＩＩを得た。
[Synthesis Example 2]
In the reactor, 100 parts of a phenol novolac type epoxy resin (trade name: EPN1138, manufactured by Asahi Kasei Chemicals Corporation, epoxy equivalent 182 g / eq) as a raw material glycidyl compound, and 0.04 of tetrabutylammonium bromide as an oxazolidone ring formation catalyst The part was charged and stirred and heated, so that the internal temperature was 175 ° C. Further, 5.9 parts of naphthalene diisocyanate (trade name: Desmodur 15) as a raw material isocyanate compound was charged into the reactor over 60 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 8 hours to obtain an oxazolidone ring-containing epoxy resin II.
［合成例３］
反応器内に、原料グリシジル化合物としてビスフェノールＡ型エポキシ樹脂（商品名：ＡＥＲ２６０）１００部、及び、オキサゾリドン環形成触媒としてテトラブチルアンモニウムブロマイド０．０４部を投入し、撹拌加熱し、内温を１７５℃にした。さらに、原料イソシアネート化合物としてトリレンジイソシアネート（商品名：コロネートＴ−８０（商標）、日本ポリウレタン工業（株）製）１６．１部を１２０分かけて反応器内に投入した。投入終了後、反応温度を１７５℃に保ち、８時間撹拌し、オキサゾリドン環含有エポキシ樹脂ＩＩＩを得た。
[Synthesis Example 3]
In the reactor, 100 parts of bisphenol A type epoxy resin (trade name: AER260) as a raw material glycidyl compound and 0.04 part of tetrabutylammonium bromide as an oxazolidone ring-forming catalyst were added, stirred and heated, and the internal temperature was 175. C. Furthermore, 16.1 parts of tolylene diisocyanate (trade name: Coronate T-80 (trademark), manufactured by Nippon Polyurethane Industry Co., Ltd.) as a raw material isocyanate compound was charged into the reactor over 120 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 8 hours to obtain an oxazolidone ring-containing epoxy resin III.
［合成例４］
反応器内に、原料グリシジル化合物としてビスフェノールＡ型エポキシ樹脂（商品名：ＡＥＲ２６０）１００部、及び、オキサゾリドン環形成触媒としてテトラブチルアンモニウムブロマイド０．０４部を投入し、撹拌加熱し、内温を１７５℃にした。さらに、原料イソシアネート化合物としてトリレンジイソシアネート（商品名：コロネートＴ−８０）２０．９部を１８０分かけて反応器内に投入した。投入終了後、反応温度を１７５℃に保ち、８時間撹拌し、オキサゾリドン環含有エポキシ樹脂ＩＶを得た。
[Synthesis Example 4]
In the reactor, 100 parts of bisphenol A type epoxy resin (trade name: AER260) as a raw material glycidyl compound and 0.04 part of tetrabutylammonium bromide as an oxazolidone ring-forming catalyst were added, stirred and heated, and the internal temperature was 175. C. Furthermore, 20.9 parts of tolylene diisocyanate (trade name: Coronate T-80) as a raw material isocyanate compound was charged into the reactor over 180 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 8 hours to obtain an oxazolidone ring-containing epoxy resin IV.
［合成例５］
反応器内に、原料グリシジル化合物としてクレゾールノボラック型エポキシ樹脂（商品名：ＥＣＮ１２７３、旭化成ケミカルズ（株）製、エポキシ当量２１５ｇ／ｅｑ）１００部、及び、オキサゾリドン環形成触媒としてテトラブチルアンモニウムブロマイド０．０４部を投入し、撹拌加熱し、内温を１７５℃にした。さらに、原料イソシアネート化合物としてナフタレンジイソシアネート（商品名：デスモジュール１５）、４．９部を６０分かけて反応器内に投入した。投入終了後、反応温度を１７５℃に保ち、８時間撹拌し、オキサゾリドン環含有エポキシ樹脂Ｖを得た。
表１に、オキサゾリドン環含有エポキシ樹脂Ｉ、ＩＩ、ＩＩＩ、ＩＶ及びＶの各種性状を示す。
[Synthesis Example 5]
In the reactor, 100 parts of a cresol novolac type epoxy resin (trade name: ECN1273, manufactured by Asahi Kasei Chemicals Corporation, epoxy equivalent 215 g / eq) as a raw material glycidyl compound, and tetrabutylammonium bromide 0.04 as an oxazolidone ring formation catalyst The part was charged and stirred and heated, so that the internal temperature was 175 ° C. Further, 4.9 parts of naphthalene diisocyanate (trade name: Desmodur 15) as a raw material isocyanate compound was charged into the reactor over 60 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 8 hours to obtain an oxazolidone ring-containing epoxy resin V.
Table 1 shows various properties of the oxazolidone ring-containing epoxy resins I, II, III, IV and V.
[実施例１]
密閉容器内に、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、ジシアンジアミド（和光純薬工業（株）製）を４．３部、２−メチルイミダゾール（略称：２ＭＩ、和光純薬工業（株）製）を０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、実施例１のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、強化繊維シートとしての炭素繊維（商品名：トレカクロスＣＯ−６３６３、東レ（株）製、目付１９８ｇ／ｍ２）に含浸塗布し、１７０℃で乾燥させて、実施例１のプリプレグを作製した。実施例１のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、ジシアンジアミド／メチルセロソルブ１０％液を４３．０部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 1]
In a closed container, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 4.3 parts of dicyandiamide (manufactured by Wako Pure Chemical Industries, Ltd.), 2-methylimidazole (abbreviation: 2MI, Wako Pure Chemical Industries) 0.05 parts of Kogyo Co., Ltd.) and 65 parts of methyl ethyl ketone and 65 parts of propylene glycol monomethyl ether as solvents were shaken for 1 hour, left to stand for 1 hour, and the epoxy of Example 1 A resin varnish was prepared. Next, the obtained epoxy resin varnish was impregnated and applied to carbon fibers (trade name: TORAYCA CROSS CO-6363, manufactured by Toray Industries, Inc., 198 g / m 2) as a reinforcing fiber sheet, and dried at 170 ° C. A prepreg of Example 1 was produced. When the impregnation amount of the prepreg of Example 1 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 43.0 parts of dicyandiamide / methylcellosolve 10% solution, and 2 parts of MI were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[実施例２] 密閉容器内に、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、ジアミノジフェニルスルホン（和光純薬工業（株）製）を２１．２部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン７０部及びプロピレングリコールモノメチルエーテル７０部を投入し、１時間振とうさせた後、１時間静置して、実施例２のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、実施例２のプリプレグを作製した。実施例２のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、ジアミノジフェニルスルホン２１．２部、２ＭＩ／メチルセロソルブ２％液を２．５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 2] In an airtight container, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 21.2 parts of diaminodiphenylsulfone (manufactured by Wako Pure Chemical Industries, Ltd.), 0.05 of 2MI Then, 70 parts of methyl ethyl ketone and 70 parts of propylene glycol monomethyl ether were added as solvents, shaken for 1 hour, and allowed to stand for 1 hour to prepare an epoxy resin varnish of Example 2. Next, the obtained epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Example 2. When the impregnation amount of the prepreg of Example 2 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 21.2 parts of diaminodiphenylsulfone, and 2.5 parts of 2MI / methylcellosolve 2% solution were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured into a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[実施例３]
密閉容器内に、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを８７部、ビスフェノールＡ型エポキシ樹脂（ＡＥＲ２６０）１３部、ジシアンジアミド４．６部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、実施例３のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、実施例３のプリプレグを作製した。実施例３のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを８７部、ＡＥＲ２６０を１３部、ジシアンジアミド／メチルセロソルブ１０％液を４６部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 3]
In a closed container, 87 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 13 parts of bisphenol A type epoxy resin (AER260), 4.6 parts of dicyandiamide, 0.05 parts of 2MI, and methyl ethyl ketone as a solvent The epoxy resin varnish of Example 3 was prepared by adding 65 parts and 65 parts of propylene glycol monomethyl ether, shaking for 1 hour, and allowing to stand for 1 hour. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Example 3. When the impregnation amount of the prepreg of Example 3 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
In addition, 87 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 13 parts of AER260, 46 parts of 10% dicyandiamide / methylcellosolve solution, and 0.05 parts of 2MI were uniformly dissolved, and then in a 120 ° C. vacuum dryer. Then, the solvent was removed, and the molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and cured by heating in an oven at a temperature of 180 ° C. for 2 hours.
[実施例４] 密閉容器内に、合成例２で得たオキサゾリドン環含有エポキシ樹脂ＩＩを１００部、ジシアンジアミドを５．９部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、実施例４のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、実施例４のプリプレグを作製した。実施例４のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例２で得たオキサゾリドン環含有エポキシ樹脂ＩＩを１００部、ジシアンジアミド／メチルセロソルブ１０％液を５９部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 4] In an airtight container, 100 parts of the oxazolidone ring-containing epoxy resin II obtained in Synthesis Example 2, 5.9 parts of dicyandiamide, 0.05 parts of 2MI, 65 parts of methyl ethyl ketone as a solvent and propylene glycol The epoxy resin varnish of Example 4 was prepared by adding 65 parts of monomethyl ether, shaking for 1 hour, and allowing to stand for 1 hour. Next, the resulting epoxy resin varnish was impregnated and applied to Trecacloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Example 4. When the impregnation amount of the prepreg of Example 4 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin II obtained in Synthesis Example 2, 59 parts of dicyandiamide / methylcellosolve 10% solution, and 2 parts of MI were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[実施例５] 密閉容器内に、合成例２で得たオキサゾリドン環含有エポキシ樹脂ＩＩを１００部、ジアミノジフェニルスルホンを２９．２部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン７５部及びプロピレングリコールモノメチルエーテル７５部を投入し、１時間振とうさせた後、１時間静置して、実施例５のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、実施例５のプリプレグを作製した。実施例５のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例２で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、ジアミノジフェニルスルホン２９．２部、２ＭＩ／メチルセロソルブ２％液を２．５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 5] In an airtight container, 100 parts of the oxazolidone ring-containing epoxy resin II obtained in Synthesis Example 2, 29.2 parts of diaminodiphenylsulfone, 0.05 parts of 2MI, and 75 parts of methyl ethyl ketone as a solvent and The epoxy resin varnish of Example 5 was prepared by adding 75 parts of propylene glycol monomethyl ether, shaking for 1 hour, and allowing to stand for 1 hour. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Example 5. When the impregnation amount of the prepreg of Example 5 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 2, 29.2 parts of diaminodiphenylsulfone, and 2.5 parts of 2MI / methylcellosolve 2% solution were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured into a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[実施例６] 密閉容器内に、合成例２で得たオキサゾリドン環含有エポキシ樹脂ＩＩを８７部、ＡＥＲ２６０を１３部、ジシアンジアミドを６．０部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、実施例６のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、実施例６のプリプレグを作製した。実施例６のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例２で得たオキサゾリドン環含有エポキシ樹脂ＩＩを８７部、ＡＥＲ２６０を１３部、ジシアンジアミド／メチルセロソルブ１０％液を６０部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 6] In an airtight container, 87 parts of the oxazolidone ring-containing epoxy resin II obtained in Synthesis Example 2, 13 parts of AER260, 6.0 parts of dicyandiamide, 0.05 parts of 2MI, and methyl ethyl ketone as a solvent The epoxy resin varnish of Example 6 was prepared by adding 65 parts and 65 parts of propylene glycol monomethyl ether, shaking for 1 hour, and allowing to stand for 1 hour. Next, the resulting epoxy resin varnish was impregnated and applied to Trecacloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Example 6. When the impregnation amount of the prepreg of Example 6 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Also, 87 parts of the oxazolidone ring-containing epoxy resin II obtained in Synthesis Example 2, 13 parts of AER260, 60 parts of 10% dicyandiamide / methylcellosolve solution, and 0.05 parts of 2MI were uniformly dissolved, and then in a 120 ° C. vacuum dryer. Then, the solvent was removed, and the molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and cured by heating in an oven at a temperature of 180 ° C. for 2 hours.
[実施例７]
密閉容器内に、合成例５で得たオキサゾリドン環含有エポキシ樹脂Ｖを１００部、ジアミノジフェニルスルホンを２４．８部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン７５部及びプロピレングリコールモノメチルエーテル７５部を投入し、１時間振とうさせた後、１時間静置して、実施例７のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、実施例７のプリプレグを作製した。実施例５のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例５で得たオキサゾリドン環含有エポキシ樹脂Ｖを１００部、ジアミノジフェニルスルホン２４．８部、２ＭＩ／メチルセロソルブ２％液を２．５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 7]
In a sealed container, 100 parts of the oxazolidone ring-containing epoxy resin V obtained in Synthesis Example 5, 24.8 parts of diaminodiphenylsulfone, 0.05 parts of 2MI, and 75 parts of methyl ethyl ketone and propylene glycol monomethyl ether 75 as solvents. The epoxy resin varnish of Example 7 was prepared by placing the part and shaking for 1 hour and then allowing to stand for 1 hour. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Example 7. When the impregnation amount of the prepreg of Example 5 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin V obtained in Synthesis Example 5 and 24.8 parts of diaminodiphenylsulfone and 2.5 parts of 2MI / methyl cellosolve 2% solution were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured into a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[実施例８]
密閉容器内に、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、カルボキシル基含有固形アクリロニトリルブタジエンゴム（商品名：ＮＩＰＯＬ１０７２，日本ゼオン（株）製）を５部、ジシアンジアミドを４．３部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、実施例８のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、実施例８のプリプレグを作製した。実施例８のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、ＮＩＰＯＬ１０７２を５部、ジシアンジアミド／メチルセロソルブ１０％液を４３部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 8]
In a sealed container, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 5 parts of carboxyl group-containing solid acrylonitrile butadiene rubber (trade name: NIPOL1072, manufactured by Nippon Zeon Co., Ltd.), and dicyandiamide of 4.3 parts Part, 2MI 0.05 parts, and methyl ethyl ketone 65 parts and propylene glycol monomethyl ether 65 parts as a solvent, shaken for 1 hour, allowed to stand for 1 hour, and the epoxy resin varnish of Example 8 was obtained. It was adjusted. Next, the resulting epoxy resin varnish was impregnated and applied to Trecacloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Example 8. When the impregnation amount of the prepreg of Example 8 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 5 parts of NIPOL1072, 43 parts of 10% dicyandiamide / methylcellosolve solution, and 0.05 parts of 2MI were uniformly dissolved, and then in a 120 ° C. vacuum dryer. Then, the solvent was removed, and the molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and cured by heating in an oven at a temperature of 180 ° C. for 2 hours.
[実施例９]
密閉容器内に、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、微粒子シリカ（商品名：アエロジルＲＹ２００、日本アエロジル（株）製）を３部、ジシアンジアミドを４．３部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、３０分静置して、実施例９のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、実施例９のプリプレグを作製した。実施例９のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例１で得たオキサゾリドン環含有エポキシ樹脂Ｉを１００部、アエロジルＲＹ２００を３部、ジシアンジアミド／メチルセロソルブ１０％液を４３部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Example 9]
In an airtight container, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 3 parts of fine particle silica (trade name: Aerosil RY200, manufactured by Nippon Aerosil Co., Ltd.), 4.3 parts of dicyandiamide, 2MI 0.05 part and 65 parts of methyl ethyl ketone and 65 parts of propylene glycol monomethyl ether as a solvent were added, shaken for 1 hour, and allowed to stand for 30 minutes to prepare the epoxy resin varnish of Example 9. Next, the obtained epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Example 9. When the impregnation amount of the prepreg of Example 9 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin I obtained in Synthesis Example 1, 3 parts of Aerosil RY200, 43 parts of 10% dicyandiamide / methylcellosolve solution and 0.05 part of 2MI were uniformly dissolved, and then vacuum dried at 120 ° C. The solvent was removed in the machine, the molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and cured by heating in an oven at a temperature of 180 ° C. for 2 hours.
[比較例１]
密閉容器内に、合成例３で得たオキサゾリドン環含有エポキシ樹脂ＩＩＩを１００部、ジシアンジアミドを３．７部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、比較例１のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例１のプリプレグを作製した。比較例１のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。また、合成例３で得たオキサゾリドン環含有エポキシ樹脂ＩＩＩを１００部、ジシアンジアミド／メチルセロソルブ１０％液を３７部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 1]
In a sealed container, 100 parts of the oxazolidone ring-containing epoxy resin III obtained in Synthesis Example 3, 3.7 parts of dicyandiamide, 0.05 parts of 2MI, and 65 parts of methyl ethyl ketone and 65 parts of propylene glycol monomethyl ether as solvents. The epoxy resin varnish of Comparative Example 1 was prepared by charging, shaking for 1 hour, and allowing to stand for 1 hour. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363, and dried at 170 ° C. to prepare a prepreg of Comparative Example 1. When the impregnation amount of the prepreg of Comparative Example 1 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%. Further, 100 parts of the oxazolidone ring-containing epoxy resin III obtained in Synthesis Example 3, 37 parts of dicyandiamide / methylcellosolve 10% solution and 0.05 part of 2MI were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[比較例２]
密閉容器内に、合成例３で得たオキサゾリドン環含有エポキシ樹脂ＩＩＩを１００部、ジアミノジフェニルスルホンを１８．０部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン７０部及びプロピレングリコールモノメチルエーテル７０部を投入し、１時間振とうさせた後、１時間静置して、比較例２のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例２のプリプレグを作製した。比較例２のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例３で得たオキサゾリドン環含有エポキシ樹脂ＩＩＩを１００部、ジアミノジフェニルスルホン１８．０部、２ＭＩ／メチルセロソルブ２％液を２．５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 2]
In a sealed container, 100 parts of the oxazolidone ring-containing epoxy resin III obtained in Synthesis Example 3, 18.0 parts of diaminodiphenylsulfone, 0.05 parts of 2MI, and 70 parts of methyl ethyl ketone and propylene glycol monomethyl ether 70 as solvents. The epoxy resin varnish of Comparative Example 2 was prepared by placing the part and shaking for 1 hour and then allowing to stand for 1 hour. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Comparative Example 2. When the impregnation amount of the prepreg of Comparative Example 2 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin III obtained in Synthesis Example 3 and 18.0 parts of diaminodiphenylsulfone and 2.5 parts of 2MI / methylcellosolve 2% solution were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured into a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[比較例３]
密閉容器内に、合成例４で得たオキサゾリドン環含有エポキシ樹脂ＩＶを１００部、ジアミノジフェニルスルホンを１４．９部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン７０部及びプロピレングリコールモノメチルエーテル７０部を投入し、１時間振とうさせた後、１時間静置して、比較例３のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例３のプリプレグを作製した。比較例３のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例４で得たオキサゾリドン環含有エポキシ樹脂ＩＶを１００部、ジアミノジフェニルスルホン１４．９部、２ＭＩ／メチルセロソルブ２％液を２．５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 3]
In a sealed container, 100 parts of the oxazolidone ring-containing epoxy resin IV obtained in Synthesis Example 4, 14.9 parts of diaminodiphenylsulfone, 0.05 parts of 2MI, and 70 parts of methyl ethyl ketone and propylene glycol monomethyl ether 70 as solvents. The epoxy resin varnish of Comparative Example 3 was prepared by placing the part and shaking for 1 hour, and then allowing to stand for 1 hour. Next, the obtained epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Comparative Example 3. When the impregnation amount of the prepreg of Comparative Example 3 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 100 parts of the oxazolidone ring-containing epoxy resin IV obtained in Synthesis Example 4, 14.9 parts of diaminodiphenylsulfone, and 2.5 parts of 2MI / methylcellosolve 2% solution were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured into a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[比較例４]
密閉容器内に、ＥＰＮ１１３８（旭化成ケミカルズ（株）製、エポキシ当量１７９ｇ／ｅｑ）を１００部、ジシアンジアミドを５．９部、２ＭＩを０．０１部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、比較例４のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例４のプリプレグを作製した。比較例４のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、ＥＰＮ１１３８を１００部、ジシアンジアミド／メチルセロソルブ１０％液を５９部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 4]
In a sealed container, 100 parts of EPN1138 (Asahi Kasei Chemicals Corporation, epoxy equivalent 179 g / eq), 5.9 parts of dicyandiamide, 0.01 parts of 2MI, 65 parts of methyl ethyl ketone and propylene glycol monomethyl ether as a solvent 65 parts was added, shaken for 1 hour, and allowed to stand for 1 hour to prepare the epoxy resin varnish of Comparative Example 4. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Comparative Example 4. When the impregnation amount of the prepreg of Comparative Example 4 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
In addition, 100 parts of EPN1138, 59 parts of dicyandiamide / methylcellosolve 10% solution, and 0.05 parts of 2MI were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer to obtain a molten resin composition having a length of 20 mm × It was poured into a Teflon (registered trademark) casting plate having a width of 4 mm and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[比較例５]
密閉容器内に、ＥＰＮ１１３８を１００部、ジアミノジフェニルスルホンを３４．０部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン８０部及びプロピレングリコールモノメチルエーテル８０部を投入し、１時間振とうさせた後、１時間静置して、比較例５のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例５のプリプレグを作製した。比較例５のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、ＥＰＮ１１３８を１００部、ジアミノジフェニルスルホンを３４．０部、２ＭＩ／メチルセロソルブ２％液２．５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 5]
In a sealed container, 100 parts of EPN1138, 34.0 parts of diaminodiphenylsulfone, 0.05 part of 2MI, and 80 parts of methyl ethyl ketone and 80 parts of propylene glycol monomethyl ether as solvents were added and shaken for 1 hour. Thereafter, the epoxy resin varnish of Comparative Example 5 was prepared by allowing to stand for 1 hour. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Comparative Example 5. When the impregnation amount of the prepreg of Comparative Example 5 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
After 100 parts of EPN1138, 34.0 parts of diaminodiphenylsulfone and 2.5 parts of 2MI / methyl cellosolve 2% solution were uniformly dissolved, the solvent was removed in a 120 ° C. vacuum dryer, and the molten resin composition was It was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured for 2 hours in an oven at a temperature of 180 ° C.
[比較例６]
密閉容器内に、合成例３で得たオキサゾリドン環含有エポキシ樹脂ＩＩＩを７４部、ＡＥＲ２６０を２６部、ジシアンジアミドを４．５部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、比較例６のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例６のプリプレグを作製した。比較例６のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。また、合成例３で得たオキサゾリドン環含有エポキシ樹脂ＩＩＩを７４部、ＡＥＲ２６０を２６部、ジシアンジアミド／メチルセロソルブ１０％液を４５部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 6]
In a sealed container, 74 parts of the oxazolidone ring-containing epoxy resin III obtained in Synthesis Example 3, 26 parts of AER260, 4.5 parts of dicyandiamide, 0.05 parts of 2MI, 65 parts of methyl ethyl ketone as a solvent and propylene glycol 65 parts of monomethyl ether was added, shaken for 1 hour, and allowed to stand for 1 hour to prepare an epoxy resin varnish of Comparative Example 6. Next, the obtained epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Comparative Example 6. When the impregnation amount of the prepreg of Comparative Example 6 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%. Further, 74 parts of the oxazolidone ring-containing epoxy resin III obtained in Synthesis Example 3, 26 parts of AER260, 45 parts of 10% dicyandiamide / methylcellosolve solution, and 0.05 part of 2MI were uniformly dissolved, and then in a 120 ° C. vacuum dryer. Then, the solvent was removed, and the molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and cured by heating in an oven at a temperature of 180 ° C. for 2 hours.
[比較例７]
密閉容器内に、合成例４で得たオキサゾリドン環含有エポキシ樹脂ＩＶを６３部、ＡＥＲ２６０を３７部、ジシアンジアミドを４．４部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、比較例７のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例７のプリプレグを作製した。比較例７のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、合成例４で得たオキサゾリドン環含有エポキシ樹脂ＩＶを６３部、ＡＥＲ２６０を３７部、ジシアンジアミド／メチルセロソルブ１０％液を４４部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 7]
In a sealed container, 63 parts of the oxazolidone ring-containing epoxy resin IV obtained in Synthesis Example 4, 37 parts of AER260, 4.4 parts of dicyandiamide, 0.05 parts of 2MI, 65 parts of methyl ethyl ketone and propylene glycol as a solvent 65 parts of monomethyl ether was added, shaken for 1 hour, and allowed to stand for 1 hour to prepare an epoxy resin varnish of Comparative Example 7. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Comparative Example 7. When the impregnation amount of the prepreg of Comparative Example 7 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
In addition, 63 parts of the oxazolidone ring-containing epoxy resin IV obtained in Synthesis Example 4, 37 parts of AER260, 44 parts of dicyandiamide / methylcellosolve 10% solution, and 2 parts of 2MI were uniformly dissolved, and then 120 ° C in a vacuum dryer. Then, the solvent was removed, and the molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and cured by heating in an oven at a temperature of 180 ° C. for 2 hours.
[比較例８]
密閉容器内に、ＡＥＲ２６０を５部、ビスフェノールＡ型エポキシ樹脂（商品名：ＡＥＲ６００２、旭化成ケミカルズ（株）製、エポキシ当量６３７ｇ／ｅｑ、軟化点８０℃）を６５部、ＥＰＮ１１３８を３０部、ジシアンジアミドを３．７部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン６５部及びプロピレングリコールモノメチルエーテル６５部を投入し、１時間振とうさせた後、１時間静置して、比較例８のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例８のプリプレグを作製した。比較例８のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、ＡＥＲ２６０を５部、ＡＥＲ６００２を６５部、ＥＰＮ１１３８を３０部、ジシアンジアミド／メチルセロソルブ１０％液を３７部、２ＭＩを０．０５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 8]
In a sealed container, 5 parts of AER260, 65 parts of bisphenol A type epoxy resin (trade name: AER6002, manufactured by Asahi Kasei Chemicals Corporation, epoxy equivalent 637 g / eq, softening point 80 ° C.), 30 parts of EPN1138, dicyandiamide 3.7 parts, 0.05 parts of 2MI, and 65 parts of methyl ethyl ketone and 65 parts of propylene glycol monomethyl ether as a solvent were added, shaken for 1 hour, allowed to stand for 1 hour, and the epoxy of Comparative Example 8 A resin varnish was prepared. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363, and dried at 170 ° C. to prepare a prepreg of Comparative Example 8. When the impregnation amount of the prepreg of Comparative Example 8 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
Further, 5 parts of AER260, 65 parts of AER6002, 30 parts of EPN1138, 37 parts of 10% dicyandiamide / methylcellosolve solution and 0.05 part of 2MI were uniformly dissolved, and then the solvent was removed in a 120 ° C. vacuum dryer. The molten resin composition was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured in an oven at a temperature of 180 ° C. for 2 hours.
[比較例９]
密閉容器内に、テトラグリシジルジアミノジフェニルメタン（商品名：ＭＹ７２１、ハンツマン・ジャパン（株）製、エポキシ当量１１２ｇ／ｅｑ）を１００部、ジアミノジフェニルスルホンを５５．２部、２ＭＩを０．０５部、並びに、溶媒としてメチルエチルケトン８０部及びプロピレングリコールモノメチルエーテル８０部を投入し、１時間振とうさせた後、１時間静置して、比較例９のエポキシ樹脂ワニスを調整した。次に、得られたエポキシ樹脂ワニスを、トレカクロスＣＯ−６３６３に含浸塗布し、１７０℃で乾燥させて、比較例９のプリプレグを作製した。比較例９のプリプレグの含浸量を測定したところ、エポキシ樹脂組成分が４０％であり、強化繊維シート分が６０％であった。
また、ＭＹ７２１を１００部、ジアミノジフェニルスルホンを５５．２部、２ＭＩ／メチルセロソルブ２％液２．５部を均一溶解後、１２０℃真空乾燥機内で溶媒を除去し、溶融樹脂組成物を、長さ２０ｍｍ×幅４ｍｍ×厚さ２ｍｍのテフロン（登録商標）製注型板に注いで、温度１８０℃のオーブン内で２時間加熱硬化した。
[Comparative Example 9]
In a sealed container, tetraglycidyldiaminodiphenylmethane (trade name: MY721, manufactured by Huntsman Japan KK, epoxy equivalent 112 g / eq) 100 parts, diaminodiphenylsulfone 55.2 parts, 2MI 0.05 parts, and Then, 80 parts of methyl ethyl ketone and 80 parts of propylene glycol monomethyl ether were added as solvents, shaken for 1 hour, and allowed to stand for 1 hour to prepare an epoxy resin varnish of Comparative Example 9. Next, the resulting epoxy resin varnish was impregnated and applied to TORAYCA cloth CO-6363 and dried at 170 ° C. to prepare a prepreg of Comparative Example 9. When the impregnation amount of the prepreg of Comparative Example 9 was measured, the epoxy resin composition was 40% and the reinforcing fiber sheet content was 60%.
In addition, 100 parts of MY721, 55.2 parts of diaminodiphenylsulfone, and 2.5 parts of 2MI / methyl cellosolve 2% solution were uniformly dissolved, and then the solvent was removed in a vacuum dryer at 120 ° C. to obtain a molten resin composition. It was poured onto a Teflon (registered trademark) casting plate having a length of 20 mm, a width of 4 mm, and a thickness of 2 mm, and heat-cured for 2 hours in an oven at a temperature of 180 ° C.
上記表１〜３の結果から、以下の事項を読み取ることができる。
（１）本実施の形態のエポキシ樹脂組成物は、優れた樹脂粘度特性と、その硬化物の耐熱性・破壊靭性に優れることから、成型プロセスと硬化物特性を同時に満たすことが出来て、プリプレグ取扱い性及び耐熱性のバランスに優れている。
（２）本実施の形態のオキサゾリドン環含有エポキシ樹脂Ｉは、比較品のオキサゾリドン環含有エポキシ樹脂ＩＩＩに比べて、単独で硬化させた場合の耐熱性が優れる（実施例１と比較例１）だけでなく、プリプレグへの樹脂の含浸性を考慮して適正な樹脂組成物粘度に調整した配合物においても耐熱性と破壊靭性に優れていると言える。（実施例３と比較例６）
（３）本実施の形態のオキサゾリドン環含有エポキシ樹脂ＩＩは、比較品のテトラグリシジルジアミノジフェニルメタンに比べて、プリプレグ取扱い性と破壊靭性に優れる。（実施例５と比較例９）これは、テトラグリシジルジアミノジフェニルメタンに比べ、適正な樹脂溶融粘度を有していることが理由の一つに挙げられる。そのため、配合物においても、本発明品は高軟化点樹脂（例としてビスＡ型固形樹脂。耐熱性低い。）を併用する必要がないため、優れた耐熱性と破壊靭性を付与できる。（実施例６と比較例８）
The following items can be read from the results of Tables 1 to 3 above.
(1) Since the epoxy resin composition of the present embodiment is excellent in resin viscosity characteristics and heat resistance / fracture toughness of the cured product, it can satisfy the molding process and cured product characteristics at the same time. Excellent balance between handleability and heat resistance.
(2) The oxazolidone ring-containing epoxy resin I of this embodiment is superior in heat resistance when cured alone (Example 1 and Comparative Example 1) as compared to the comparative oxazolidone ring-containing epoxy resin III. In addition, it can be said that the heat resistance and fracture toughness are excellent even in a blend adjusted to an appropriate resin composition viscosity in consideration of the resin impregnation into the prepreg. (Example 3 and Comparative Example 6)
(3) The oxazolidone ring-containing epoxy resin II of the present embodiment is excellent in prepreg handling and fracture toughness as compared with the comparative product tetraglycidyldiaminodiphenylmethane. (Example 5 and Comparative Example 9) One reason for this is that it has an appropriate resin melt viscosity as compared with tetraglycidyldiaminodiphenylmethane. Therefore, even in the blend, the product of the present invention does not require the use of a high softening point resin (for example, bis A type solid resin; low heat resistance), and therefore can impart excellent heat resistance and fracture toughness. (Example 6 and Comparative Example 8)
Claims (8)
（Ｂ）硬化剤と、を含み、
前記（Ａ）が下記一般式（１）で表される構造を有するエポキシ樹脂である、エポキシ樹脂組成物；
(B) a curing agent,
An epoxy resin composition in which (A) is an epoxy resin having a structure represented by the following general formula (1);
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