JPH0347848A - Production of prepreg - Google Patents
Production of prepregInfo
- Publication number
- JPH0347848A JPH0347848A JP10901390A JP10901390A JPH0347848A JP H0347848 A JPH0347848 A JP H0347848A JP 10901390 A JP10901390 A JP 10901390A JP 10901390 A JP10901390 A JP 10901390A JP H0347848 A JPH0347848 A JP H0347848A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- bis
- prepreg
- oxazoline
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- -1 aromatic amine compound Chemical class 0.000 claims abstract description 36
- 239000004593 Epoxy Substances 0.000 claims abstract description 25
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000003277 amino group Chemical group 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000012779 reinforcing material Substances 0.000 claims abstract description 6
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 3
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 claims description 2
- KBPWECBBZZNAIE-UHFFFAOYSA-N aniline;hydron;bromide Chemical group Br.NC1=CC=CC=C1 KBPWECBBZZNAIE-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002723 alicyclic group Chemical group 0.000 abstract description 3
- 229930185605 Bisphenol Natural products 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000002966 varnish Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 150000000376 2-oxazolines Chemical class 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 238000009941 weaving Methods 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical group [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ASFHPAUFWGSVGY-UHFFFAOYSA-N (4-pentylphenyl) 4-propylcyclohexane-1-carboxylate Chemical compound C1=CC(CCCCC)=CC=C1OC(=O)C1CCC(CCC)CC1 ASFHPAUFWGSVGY-UHFFFAOYSA-N 0.000 description 1
- LPVHVQFTYXQKAP-YFKPBYRVSA-N (4r)-3-formyl-2,2-dimethyl-1,3-thiazolidine-4-carboxylic acid Chemical compound CC1(C)SC[C@@H](C(O)=O)N1C=O LPVHVQFTYXQKAP-YFKPBYRVSA-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
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical class CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- ZDNUPMSZKVCETJ-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=2OCCN=2)C=C1 ZDNUPMSZKVCETJ-UHFFFAOYSA-N 0.000 description 1
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 description 1
- FCDOETBDFXHVJZ-UHFFFAOYSA-N 2-aminobenzoic acid;4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1.NC1=CC=CC=C1C(O)=O FCDOETBDFXHVJZ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000004278 2-oxazolin-2-yl group Chemical group [H]C1([H])OC(*)=NC1([H])[H] 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- DEXHGMUVBNTXIN-UHFFFAOYSA-N 5-methyl-2-[4-(5-methyl-4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1C(C)CN=C1C1=CC=C(C=2OC(C)CN=2)C=C1 DEXHGMUVBNTXIN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- OPZQVVFELYHAPZ-UHFFFAOYSA-N Br.Br.Br.Br.CC Chemical compound Br.Br.Br.Br.CC OPZQVVFELYHAPZ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UJZMCJRSSA-N aniline;hydrochloride Chemical compound Cl.N[14C]1=[14CH][14CH]=[14CH][14CH]=[14CH]1 MMCPOSDMTGQNKG-UJZMCJRSSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical group 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- FUCOMWZKWIEKRK-UHFFFAOYSA-N iodocyclohexane Chemical compound IC1CCCCC1 FUCOMWZKWIEKRK-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000768 polyamine Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はスポーツ用品、航空機、産業機器、電気機器な
どの構造材料となる、新規なプリプレグの製造法に関す
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel method for producing prepreg, which is used as a structural material for sporting goods, aircraft, industrial equipment, electrical equipment, and the like.
従来の技術
従来より、繊維強化材に熱硬化性樹脂を含浸する方法に
より、種々のプリプレグが作られている。BACKGROUND OF THE INVENTION Conventionally, various prepregs have been made by impregnating a fiber reinforced material with a thermosetting resin.
用いられている樹脂としては、フェノール樹脂、エポキ
シ樹脂、不飽和ポリエステル樹脂、熱硬化ポリイミド樹
脂、イソシアン酸エステル−ビスマレイミド（ＢＴレジ
ン）などがよく知られている。Well-known resins used include phenol resin, epoxy resin, unsaturated polyester resin, thermosetting polyimide resin, and isocyanate bismaleimide (BT resin).
一方、ビス（２−オキサゾリン）化合物を原料とする種
々の熱硬化性樹脂が知られている。例えば、ジカルボン
酸に対し、約１モル以上のビス（２オキサゾリン）化合
物を有機面リン酸エステルの触媒の存在下に、加熱して
反応させることによって熱硬化性樹脂が得られることは
、米国特許第３゜４７６．７１２号明細書に記載されて
いる。また、ビス（２−オキサゾリン）化合物と芳香族
ジアミンとを加熱して反応させることによって熱硬化性
樹脂を得られることも、特開昭６２−１０４８３８号に
記載されている。更に、ビス（２−オキサゾリン）化合
物、ポリエポキシ化合物及びポリアミン化合物、分子内
酸無水物、芳香族ポリヒドロキシ化合物よりなる群から
選ばれた１種の化合物を酸性触媒下で加熱することによ
って、熱硬化性樹脂が得られることも特開昭６４−２６
６２８号に記載されている。On the other hand, various thermosetting resins made from bis(2-oxazoline) compounds are known. For example, it is disclosed in the US patent that a thermosetting resin can be obtained by heating and reacting about 1 mole or more of a bis(2oxazoline) compound with a dicarboxylic acid in the presence of an organic phosphate catalyst. No. 3°476.712. Furthermore, it is also described in JP-A-62-104838 that a thermosetting resin can be obtained by heating and reacting a bis(2-oxazoline) compound and an aromatic diamine. Furthermore, one type of compound selected from the group consisting of bis(2-oxazoline) compounds, polyepoxy compounds, polyamine compounds, intramolecular acid anhydrides, and aromatic polyhydroxy compounds is heated under an acidic catalyst to generate heat. It was also disclosed in JP-A-64-26 that a curable resin can be obtained.
It is described in No. 628.
また、ビス（２−オキサゾリン）化合物を原料とする熱
硬化性樹脂と繊維強化材との複合材は、優れた耐熱性を
持ち、高強度であることが認められている。そしてビス
（２−オキサゾリン）化合物と多価フェノール化合物と
の溶融物をアセトンに溶解し、そこへ繊維強化材を含浸
してプリプレグを作ることが報告されている。しかし、
ビス（２オキサゾリン）化合物−多（＋Ｉｌｉフェノー
ル化合物系よりも、伸びか大きく、繊維強化材とのなじ
みもよいビス（２−オキサゾリン）化合物−芳香族ジア
ミン系やビス（２−オキサゾリン）化合物−芳香族ジア
ミン−エポキシ化合物系のプリプレグは全く知られてい
ない。Moreover, a composite material of a thermosetting resin made from a bis(2-oxazoline) compound and a fiber reinforced material is recognized to have excellent heat resistance and high strength. It has also been reported that a prepreg is produced by dissolving a melt of a bis(2-oxazoline) compound and a polyhydric phenol compound in acetone and impregnating it with a fiber reinforcing material. but,
Bis(2-oxazoline) compound - Bis(2-oxazoline) compound - Aromatic diamine type and bis(2-oxazoline) compound - Aromatic Prepregs based on group diamine-epoxy compounds are completely unknown.
発明が解決しようとする課題
本発明者らは、鋭意研究を重ね、ビス（２−オキサゾリ
ン）化合物−芳香族アミン化合物−エポキシ化合物系の
プリプレグを製造する方法を見いだし、この知見にもと
づき、本発明を完成するに至った。Problems to be Solved by the Invention The present inventors have conducted extensive research and discovered a method for producing a bis(2-oxazoline) compound-aromatic amine compound-epoxy compound based prepreg, and based on this knowledge, the present invention has been developed. I was able to complete it.
本発明は、ビスく２−オキサゾリン）化合物と芳香族ア
ミン化合物とエポキシ化合物の樹脂原料を繊維強化材に
含浸して、有用で新規なプリプレグを提供することを目
的とする。An object of the present invention is to provide a useful and novel prepreg by impregnating a fiber reinforced material with resin raw materials of a bis(2-oxazoline) compound, an aromatic amine compound, and an epoxy compound.
課題を解決するための手段
本発明によるプリプレグの製造方法は、（ａ） ビス
（２−オキサゾリン）化合物、（ｂ） 分子内に少な
くとも２個のエポキシ基を有するエポキシ化合物、
（ｃ） 分子内に少なくとも２個のアミ７基を有する
芳香族アミン化合物および
（ｄ） 硬化触媒を含有する有機溶媒溶液を繊維強化
材を含浸させた後、該溶媒を揮散させることを特徴とす
るプリプレグの製造法である。Means for Solving the Problems The method for producing prepreg according to the present invention comprises: (a) a bis(2-oxazoline) compound; (b) an epoxy compound having at least two epoxy groups in the molecule; A method for producing a prepreg, which comprises impregnating a fiber reinforcing material with an organic solvent solution containing an aromatic amine compound having at least two ami7 groups and (d) a curing catalyst, and then volatilizing the solvent. be.
本発明に用０られるビス（２−オキサゾリン）化合物と
しては、一般式
で表される（式中、Ｒ，、Ｒ２はそれぞれ水素又は炭素
数１〜３ケのアルキル基を示す。）化合物があげられる
。」二記一般式で表される化合物の具体的な例としては
、１，３−ビス（２−オキサゾリン２−イル）ベンゼン
、１，４−ビス（２−オキサゾリン−２−イル）ベンゼ
ン、１，３−ビス（５メチル−２−オキサゾリン−２−
イル）ベンゼン。Examples of the bis(2-oxazoline) compounds used in the present invention include compounds represented by the general formula (wherein R, and R2 each represent hydrogen or an alkyl group having 1 to 3 carbon atoms). It will be done. Specific examples of compounds represented by the general formula 2 include 1,3-bis(2-oxazolin-2-yl)benzene, 1,4-bis(2-oxazolin-2-yl)benzene, 1 ,3-bis(5methyl-2-oxazoline-2-
il) benzene.
１．４−ビス（５−メチル−２−オキサゾリン−２イル
）ベンゼンなどがあげられる。Examples include 1,4-bis(5-methyl-2-oxazolin-2yl)benzene.
これらのビス（２−オキサゾリン）化合物は単独または
２種以上の混合物で用いられる。These bis(2-oxazoline) compounds may be used alone or in a mixture of two or more.
また、ビス（２−オキサゾリン）化合物として主鎖中に
、たとえばエステル、カーボネート、エーテル結合など
を有し、両末端にオキサゾリン環を有する化合物も用い
ることができる。両末端にオキサゾリン環を有する化合
物は、たとえば両末端にカルボキシル基をもつ化合物１
モルとビス（２オキサゾリン）化合物２モル以上、好ま
しくは２モルを、約１００〜２００℃下で反応させるこ
とによって得ることができる。Further, as a bis(2-oxazoline) compound, a compound having, for example, an ester, carbonate, or ether bond in the main chain and having oxazoline rings at both ends can also be used. A compound having an oxazoline ring at both ends is, for example, compound 1 having a carboxyl group at both ends.
It can be obtained by reacting 2 mol or more, preferably 2 mol, of a bis(2oxazoline) compound at about 100 to 200°C.
両末端にカルボキシル基を有する化合物としては、たと
えば脂肪族ジカルボン酸、芳香族ジカルボン酸や、主鎖
にエステル、カーボネート、エーテル結合をもつオリゴ
マージカルボン酸などがあげられる。脂肪族ジカルボン
酸としては、具体的には、アジピン酸、セバシン酸、ド
デカンニ酸などがあげられ、芳香族ジカルボン酸として
テレフタル酸、ナフタレンジカルボン酸などがあげられ
る。オリゴマージカルボン酸はたとえばポリエステルジ
オール、ポリカーボネートジオール、ポリエーテルジオ
ールなどのオリゴマージオールを約１モルと２モル以上
、好ましくは２モルの酸無水物を約１００〜２００°Ｃ
で約１０分から２時間反応することにより得られる。酸
無水物としてはたとえば無水コハク酸、無水フタル酸、
テトラヒドロ無水フタル酸などがあげられる。オリゴマ
ージオールの分子量としては約３００〜３０００の範囲
のものか用いられる。必要に応じて前記一般式で表され
るビス（２−オキサゾリン）化合物と主鎖中に、たとえ
ばエステル、カーボネート、エーテル結合などを有し、
両末端にオキサゾリン環を有する化合物を混合して用い
てもよい。Examples of compounds having carboxyl groups at both ends include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and oligomeric dicarboxylic acids having ester, carbonate, or ether bonds in the main chain. Specific examples of aliphatic dicarboxylic acids include adipic acid, sebacic acid, and dodecanedioic acid, and examples of aromatic dicarboxylic acids include terephthalic acid and naphthalene dicarboxylic acid. Oligomeric dicarboxylic acids include, for example, about 1 mol of an oligomeric diol such as polyester diol, polycarbonate diol, polyether diol, and 2 or more mol, preferably 2 mol, of an acid anhydride at about 100 to 200°C.
It is obtained by reacting for about 10 minutes to 2 hours. Examples of acid anhydrides include succinic anhydride, phthalic anhydride,
Examples include tetrahydrophthalic anhydride. The molecular weight of the oligomer diol used is within the range of about 300 to 3,000. If necessary, the bis(2-oxazoline) compound represented by the above general formula has, for example, an ester, carbonate, or ether bond in the main chain,
A mixture of compounds having oxazoline rings at both ends may be used.
本発明に用いられる分子内に少なくとも２個のエポキシ
基を有するエポキシ化合物は、具体的には、たとえばビ
スフェノールＡジグリシジルエーテル、ビスフェノール
Ｆジグリシジルエーテル、テトラブロモビスフェノール
Ａジグリシジルエーテル等のビスフェノール型エポキシ
化合物、フタル酸ジグリシジルエステル、テレフタル酸
ジグリシジルエステル、テトラヒドロフタル酸ジグリシ
＝７−
ジルエステル、ヘキサヒドロフタル酸ジグリシジルエス
テル、ｐ−オキシ安息香酸ジグリシジルエステル、ダイ
ママ酸ジグリシジルエステル等のジグリシジルエステル
型エポキシ化合物、ノボラック型エポキシ化合物、脂環
式エポキシ化合物等をあげることができる。これらは、
単独で、又は混合物として用いられる。Specifically, the epoxy compound having at least two epoxy groups in the molecule used in the present invention includes bisphenol-type epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and tetrabromobisphenol A diglycidyl ether. compounds, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl p-oxybenzoate, diglycidyl dimamate, etc. Examples include ester type epoxy compounds, novolac type epoxy compounds, alicyclic epoxy compounds, and the like. these are,
Used alone or as a mixture.
上記したエポキシ化合物の中で、ビスフェノールＡジグ
リシジル、ビスフェノールジグリシジル、脂環式エポキ
シ化合物が好ましい。Among the above-mentioned epoxy compounds, bisphenol A diglycidyl, bisphenol diglycidyl, and alicyclic epoxy compounds are preferred.
本発明においては、上記エポキシ化合物と共に、分子内
に１個のエポキシ基を有するモノエポキシ化合物も用い
ることができる。このようなモノエポキシ化合物として
は、例えば、フェニルグリシジルエーテル、アリルグリ
シジルエーテル等をあげることができる。In the present invention, in addition to the above-mentioned epoxy compounds, monoepoxy compounds having one epoxy group in the molecule can also be used. Examples of such monoepoxy compounds include phenylglycidyl ether and allylglycidyl ether.
本発明において用いられる分子内に少なくとも２個のア
ミノ基を有する芳香族アミン化合物は単環式又は多環式
化合物のいずれであってもよく、具体的には、例えば、
０−ｌｍ−又はｐ−フェニルンジアミン、２，３−又は
２，４−又は２．５−１−ルイレンジアミン、４．４’
−ジアミノビフェニル、３．３−ジメトキシ−４，４°
−ジアミノビフェニル、４．４−ジアミノトリフェニル
メタン、３゜３′−ジメチル−４，４°−ジアミノビフ
ェニル、２．２’−，５，５’−テトラクロロ−４，４
′−ジアミノビフェニル、４．４′−メチレンビスアニ
リン、４．４−メチレンビス（２−クロロアニリン）、
２゜２゛−ビス［４−（４−アミノフェノキシ）フェニ
ル］プロパへ １，３−ビス（４−アミノフェノキシ）
ベンゼン、１，３−ビス（３〜アミノフエノキシ）ベン
ゼン、３．４’−ジアミノジフェニルエーテル、４．４
−ジアミノジフェニルスルホン、４，４ジアミノジフエ
ニルスルフイドや、４Ｉ４”−ビス（アミノフェニル）
アミン、４．４’−［１，３−フェニレンビス（１−メ
チルエチリデン）コビスアニリン、トリメチレンビス（
４−アミノベンゾエート）、次式
で表わされるポリテトラメチレンオキシドージｐ−アミ
ノヘンシェード等をあげることができる。The aromatic amine compound having at least two amino groups in the molecule used in the present invention may be either a monocyclic or polycyclic compound, and specifically, for example,
0-lm- or p-phenylene diamine, 2,3- or 2,4- or 2,5-1-lylene diamine, 4.4'
-diaminobiphenyl, 3,3-dimethoxy-4,4°
-diaminobiphenyl, 4,4-diaminotriphenylmethane, 3°3'-dimethyl-4,4°-diaminobiphenyl, 2,2'-,5,5'-tetrachloro-4,4
'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4-methylenebis(2-chloroaniline),
To 2゜2゛-bis[4-(4-aminophenoxy)phenyl]propa 1,3-bis(4-aminophenoxy)
Benzene, 1,3-bis(3-aminophenoxy)benzene, 3.4'-diaminodiphenyl ether, 4.4
-diaminodiphenyl sulfone, 4,4 diaminodiphenyl sulfide, 4I4''-bis(aminophenyl)
Amine, 4,4'-[1,3-phenylenebis(1-methylethylidene)cobisaniline, trimethylenebis(
4-aminobenzoate), polytetramethylene oxide di-p-aminohenshade represented by the following formula, and the like.
これら芳香族アミン化合物は単独にて、又は二種以上の
混合物として用いられる。These aromatic amine compounds may be used alone or as a mixture of two or more.
上記したなかでは、特に、４，４°−メチレンビスアニ
リン、４．４’−メチレンビス（２−クロロアニリン）
、１．３−ビス（４−アミノフェノキシ）ベンゼン、３
．４’−ジアミノジフェニルエーテル４．４′−ジアミ
ノジフェニルスルフィド、２．２ビス［１−（４−アミ
ノフェノキシ）フェニルＪプロパン等が好ましい。Among the above, in particular, 4,4°-methylenebisaniline, 4,4'-methylenebis(2-chloroaniline)
, 1.3-bis(4-aminophenoxy)benzene, 3
．． 4'-diaminodiphenyl ether 4.4'-diaminodiphenyl sulfide, 2.2bis[1-(4-aminophenoxy)phenyl J propane, etc. are preferred.
本発明においては、上記三成分以外にフェスの溶解性を
たかめたり、粘度を調整する目的で分子内にカルボキシ
ル基を少なくとも２つ有する多塩基酸や芳香族環にアミ
７基とカルボキシル基を併せ持つ化合物（以下、添加剤
化合物と呼ぶことがある。）を用いることもてきる。In the present invention, in addition to the above three components, polybasic acids having at least two carboxyl groups in the molecule and aromatic rings containing 7 amino groups and carboxyl groups are used for the purpose of increasing the solubility of Fes and adjusting the viscosity. Compounds (hereinafter sometimes referred to as additive compounds) may also be used.
上記添加剤化合物のうち多塩基酸としては、たとえばア
ジピン酸、アゼライン酸、セバシン酸、ドデカンニ酸、
タイマー酸などの脂肪族二基Ｌ（酸が、またテレフタル
酸、ナツタレンジカルホン酸などの芳香族二塩基酸があ
げられる。芳香族環にアミン基とカルホキシル基を併ゼ
持つ化合物の具体例としては、たとえばアントラニル酸
ｐ−アミノ安息香酸が用いられる。これらの添加剤化合
物は単独で２種以上の混合物として用いることができる
。Among the above additive compounds, polybasic acids include, for example, adipic acid, azelaic acid, sebacic acid, dodecanoic acid,
Examples include aliphatic dibasic acids such as timer acid and aromatic dibasic acids such as terephthalic acid and natutaledicarphonic acid.Specific examples of compounds having both an amine group and a carboxyl group in the aromatic ring For example, anthranilic acid p-aminobenzoic acid is used.These additive compounds can be used alone or as a mixture of two or more.
本発明において使用する３成分の配合割合は、ビス（２
−オキサゾリン）化合物と芳香族アミン化合物とエポキ
シ花台物の系においては、オキサゾリン環の数＋エポキ
シ基の数≧アミノ基の数を満足する範囲である。またそ
の際、エポキシ化合物は、芳香族アミン化合物の１アミ
ノ基当量に対し通常１エポキシ基当量以下の範囲で用い
られる。The blending ratio of the three components used in the present invention is bis(2
-oxazoline) compound, an aromatic amine compound, and an epoxy flower stand, the range satisfies the number of oxazoline rings+the number of epoxy groups≧the number of amino groups. Further, in this case, the epoxy compound is usually used in an amount of 1 epoxy group equivalent or less per 1 amino group equivalent of the aromatic amine compound.
ビス（２−オキサゾリン）化合物、芳香族アミン化合物
およびエポキシ化合物に更に添加剤化合物を加える系に
おいては、使用する原料割合はオキサゾリン環の数＋エ
ポキシ基の数≧アミノ基の数＋カルボキシル基の数を満
足する範囲内で用いられる。In systems in which additive compounds are added to bis(2-oxazoline) compounds, aromatic amine compounds, and epoxy compounds, the ratio of raw materials used is the number of oxazoline rings + the number of epoxy groups ≧ the number of amino groups + the number of carboxyl groups. It is used within the range that satisfies the following.
本発明においてプリプレグを製造するちととなるフェス
（有機溶媒溶液）は、ビス（２−オキサゾリン）化合物
２分子内に少なくとも２個のエポキシ基を有するエポキ
シ化合物１分子内に少なくとも２個のアミノ基を有する
芳香族アミン化合物硬化触媒および有機溶媒を混合する
ことにより調整される。具体的には、ビス（２−オキサ
ゾリン）化合物、芳香族アミン化合物、エポキシ化合物
を加熱溶解し、必要により芳香族アミン化合物とエポキ
シ化合物とを反応させた後、触媒および溶媒を加えて調
整するか、またはあらかじめ芳香族アミン化合物とエポ
キシ化合物を加熱溶解し、必要により反応させた後に、
ビス（２−オキサゾリン）化合物、触媒および溶媒を加
えるなどの方法により調整される。この際、用いられる
有機溶媒は、樹脂原料を均一に溶解させることができ、
また樹脂原料を付着させた繊維強化材から溶媒を比較的
低温で除去できることが望ましい。かかる条件を満足す
る溶媒として好ましいのは、たとえば低級アルコール、
エチレングリコールモノアルキルエーテルまたはそのア
シレートなどかあげられる。In the present invention, the substrate (organic solvent solution) used to produce the prepreg is a bis(2-oxazoline) compound having at least two epoxy groups in two molecules, and at least two amino groups in one molecule of the epoxy compound. It is prepared by mixing an aromatic amine compound curing catalyst and an organic solvent. Specifically, a bis(2-oxazoline) compound, an aromatic amine compound, and an epoxy compound are heated and dissolved, and if necessary, the aromatic amine compound and the epoxy compound are reacted, and then a catalyst and a solvent are added. , or after heating and dissolving the aromatic amine compound and the epoxy compound in advance and reacting if necessary,
It is prepared by adding a bis(2-oxazoline) compound, a catalyst, and a solvent. At this time, the organic solvent used can uniformly dissolve the resin raw material,
Further, it is desirable that the solvent can be removed at a relatively low temperature from the fiber reinforced material to which the resin raw material is attached. Preferred solvents that satisfy these conditions include lower alcohols,
Examples include ethylene glycol monoalkyl ether or its acylate.
低級アルコールとしては、たとえばメタノールエタノー
ル、イソプロピルアルコール、ｎ−７’タノールなどが
、エチレングリコールモノアルキルエーテルとしてはた
とえばエチレングリコールモノメチルエーテル、エチレ
ングリコールモノエチルエーテルなどが、またアシレー
トとしては、たとえばエチレングリコールモノエチルエ
ーテルの酢酸エステルなどがあげられる。エチレングリ
コールモノアルキルエーテルに低級アルコールを加えて
もよい。その混合割合は低級アルコール／エチレングリ
コールモノアルキルエーテルまたはそのアシレートが重
量比で約１０／９０〜９０／１０の範囲のものが使用さ
れる。溶媒は、フェス中の樹脂固形分の割合が約２０〜
８０重量％、より好ましくは約３０〜７０重量％となる
量が使用される。溶解の温度は個々の樹脂原料の種類や
量により異なるが、多くの場合的５０℃ないし１８０℃
、好ましくは約１００’ないし１５０°Ｃの範囲であり
、時間は約５ないし６０分程度である。溶解および反応
に要する時間は、原料の種類、量、加熱温度にもよるが
、約５分〜５時間、好ましくは約２０分から１．５時間
である。Examples of lower alcohols include methanol ethanol, isopropyl alcohol, and n-7'tanol; examples of ethylene glycol monoalkyl ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; and examples of acylates include ethylene glycol monoalkyl ether. Examples include acetate ester of ethyl ether. A lower alcohol may be added to the ethylene glycol monoalkyl ether. The mixing ratio of lower alcohol/ethylene glycol monoalkyl ether or its acylate is in the range of about 10/90 to 90/10 by weight. The solvent has a resin solid content ratio of about 20 to
An amount of 80% by weight is used, more preferably about 30-70% by weight. The melting temperature varies depending on the type and amount of individual resin raw materials, but in most cases it is between 50℃ and 180℃.
, preferably in the range of about 100' to 150°C, and for about 5 to 60 minutes. The time required for dissolution and reaction depends on the type and amount of raw materials and the heating temperature, but is about 5 minutes to 5 hours, preferably about 20 minutes to 1.5 hours.
本発明に使用される硬化触媒は、樹脂溶液の調整や乾燥
工程でゲル化させることな（、また、得られたプリプレ
グが安定であり、しかも成形にあたっては、速やかに硬
化させる触媒が望ましい。The curing catalyst used in the present invention is preferably a catalyst that does not cause gelation during the preparation of the resin solution or during the drying process (also, the obtained prepreg is stable, and is capable of curing quickly during molding).
かかる触媒としては、たとえばハロゲン元素の結合した
脂肪族炭化水素の炭素を持つ化合物および芳香族モノア
ミンの）・ロゲン化水素酸塩があげられる。Such catalysts include, for example, compounds having an aliphatic hydrocarbon carbon to which a halogen element is bonded and hydrohalides of aromatic monoamines.
ハロゲン元素の結合した脂肪族炭化水素の炭素を持つ化
合物の好ましい例は、モノハロアルカン及びポリハロア
ルカンであって、例えば、具体的には、ヨウ化メチル、
塩化ブチル、臭化ブチル、ヨウ化ブチル、臭化ｎ−ヘキ
シル、塩化オクチル、臭化ｎ−オクチル、臭化ラウリル
、臭化ステア １Ｊノペ臭化アリル、四臭化エタン等で
あり、他の好ましい具体例として、例えば、臭化ヘンシ
ル、ｐ。Preferred examples of compounds having an aliphatic hydrocarbon carbon to which a halogen element is bonded are monohaloalkanes and polyhaloalkanes, such as methyl iodide,
Butyl chloride, butyl bromide, butyl iodide, n-hexyl bromide, octyl chloride, n-octyl bromide, lauryl bromide, stear bromide, 1J nope allyl bromide, ethane tetrabromide, etc. Preferred examples include, for example, Hensyl bromide, p.
ｐ′−ジクロロメチルベンセン等のモノハロメチルベン
ゼンやポリハロメチルベンゼン、２−ブロモプロピオン
酸エチル、２−ブロモイソ酪酸エチル等のハロゲン化脂
肪酸エステルをあげることができる。更に、塩化シクロ
ヘキシル、臭化シクロヘキシル、ヨウ化シクロヘキシル
等のハロゲン化ンクロヘキシルも用いることができる。Examples include monohalomethylbenzene such as p'-dichloromethylbenzene, polyhalomethylbenzene, and halogenated fatty acid esters such as ethyl 2-bromopropionate and ethyl 2-bromoisobutyrate. Furthermore, cyclohexyl halides such as cyclohexyl chloride, cyclohexyl bromide, and cyclohexyl iodide can also be used.
芳香族モノアミンのハロゲン化水素酸塩としては、たと
えば、アニリン、メチルアニリン、エチルアニリン等の
アルキルアニリン、トルイジン類、キシリジン類、ナフ
チルアミン類等の芳香族モノアミンの塩酸塩、臭化水素
酸塩、ヨウ化水素酸塩があげられる。Examples of hydrohalides of aromatic monoamines include alkylanilines such as aniline, methylaniline, and ethylaniline, hydrochlorides, hydrobromides, and iodine of aromatic monoamines such as toluidines, xylidines, and naphthylamines. Examples include hydrochloride.
上記した触媒は、単独で、又は２種以上が併用される。The above catalysts may be used alone or in combination of two or more.
上記したなかで、特にアニリンの塩酸塩、臭化水素酸塩
、２−ブロモイソ酪酸エチル、２−ブロモプロピオン酸
エチル、臭化シクロヘキシル、塩化ｎ−オクチルが好ま
しい。Among the above, particularly preferred are aniline hydrochloride, hydrobromide, ethyl 2-bromoisobutyrate, ethyl 2-bromopropionate, cyclohexyl bromide, and n-octyl chloride.
本発明の方法において、これらの触媒は、樹脂原料、す
なわち、前記したビス（２−オキサゾリン）化合物、エ
ポキシ化合物及び芳香族アミン化合物（添加剤化合物を
用いるときは、その量を含めて）の合計重量に基ついて
、約０．０５〜５重量％の範囲で用いられ、好ましくは
約００１〜２重量％の範囲で用いられる。In the method of the present invention, these catalysts are added to the resin raw materials, i.e., the sum of the above-mentioned bis(2-oxazoline) compounds, epoxy compounds and aromatic amine compounds (including the amount of additive compounds, if used). A range of about 0.05 to 5% by weight is used, preferably a range of about 0.001 to 2% by weight.
本発明において、プリプレグの流動性を調整する為にワ
ニスにエアロジル等の増粘剤を加えてもよい。また溶媒
の水分が硬化性に影響することがあるので水分の少ない
溶媒を用いるとか、ワニス調整時、モレキュラーシーブ
なとの脱水剤を加えることも有用である。In the present invention, a thickener such as Aerosil may be added to the varnish in order to adjust the fluidity of the prepreg. Furthermore, since the water content of the solvent may affect the curability, it is also useful to use a solvent with low water content or to add a dehydrating agent such as molecular sieve when preparing the varnish.
このようにして調整したワニスを繊維強化材に含浸させ
る。The fiber reinforcement material is impregnated with the varnish thus prepared.
本発明に用いられる繊維強化材の代表的なものとしては
、たとえばガラス繊維、炭素繊維および芳香族ポリアミ
ド系繊維などがあげられるが、ガラス繊維としては、そ
の原料面から、Ｅ−グラス、５
６
Ｃ−グラス、Ａ−グラスおよびＳ−グラスなどいずれの
種類のものも適用できる。炭素繊維としては、ポリアク
リロニトリル系繊維、セルロース系繊維、ピッチ、芳香
族炭化水素またはカーボンブラックなどを原料として製
造されるものがあげられる。また芳香族ポリアミド系繊
維としては、ポリ−ｐ−フェニレンテトラフタルアミド
、ポリ−ルアミノベンズアミドなどがあげられる。Typical fiber reinforcement materials used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, etc.; Any type of glass such as C-glass, A-glass and S-glass can be applied. Examples of carbon fibers include those manufactured using polyacrylonitrile fibers, cellulose fibers, pitch, aromatic hydrocarbons, carbon black, and the like as raw materials. Examples of aromatic polyamide fibers include poly-p-phenylenetetraphthalamide and poly-ruaminobenzamide.
これらの繊維強化材は、その形状によりロービング、チ
ョツプドストランドマット、コンティニアスマット、ク
ロス、ロービングクロス、サーフェシングマットおよび
チョツプドストランドがあるが、上記した如き種類や形
状は、目的とする成形物の用途および性能により適宜選
択されるものであって、必要によっては二以上の種類ま
たは形状からの混合使用であってもよい。These fiber reinforced materials can be classified into rovings, chopped strand mats, continuous mats, cloths, roving cloths, surfacing mats, and chopped strands depending on their shape. They are appropriately selected depending on the intended use and performance of the product, and two or more types or shapes may be used in combination if necessary.
ワニスを繊維強化材に含浸させる操作は、ワニスの入っ
た容器に繊維強化材を浸けるかあるいは繊維強化材にワ
ニスを散布するなどによりおこなわれる。この操作は室
温またはそれ以上の温度で行なわれる。含浸した繊維強
化材からの溶媒除去は加熱することによって行なわれる
。その条件は５０〜２００℃で５分〜１時間である。The operation of impregnating the fiber reinforced material with varnish is carried out by dipping the fiber reinforced material into a container containing the varnish or by sprinkling the varnish onto the fiber reinforced material. This operation is carried out at room temperature or above. Solvent removal from the impregnated fiber reinforcement is accomplished by heating. The conditions are 50 to 200°C for 5 minutes to 1 hour.
このようにして作られたプリプレグは、目的に応じた形
に切断し、重ねて、プレスにセットされた離型剤を吹き
つけておいた型に入れ、温度と圧力をかけて硬化させ、
目的の繊維強化された成形物を得ることができる。この
際、使用される温度は約１２０〜２００℃であり、圧力
は約０．５〜３０ ｋｇ／ ｃｍ”、好ましくは約０
、５〜ｌ Ｏｋｇ／ ａｍ’。The prepreg made in this way is cut into shapes according to the purpose, stacked, placed in a mold set in a press and sprayed with a mold release agent, and cured by applying temperature and pressure.
The desired fiber-reinforced molded product can be obtained. At this time, the temperature used is about 120-200°C, and the pressure is about 0.5-30 kg/cm", preferably about 0.
, 5~l Okg/am'.
硬化時間は約１０分〜２時間２通常約３０分〜１時間で
ある。Curing time is about 10 minutes to 2 hours, usually about 30 minutes to 1 hour.
発明の効果
本発明の方法によれば、ビス（２−オキサゾリン）化合
物、芳香族アミン化合物、エポキシ化合物、硬化触媒、
及び有機溶媒を用いてプリプレグ用ワニスを作り、それ
に繊維強化材を浸けて、引き上げ乾燥することによって
、貯蔵安定性が良く、取り扱いが容易であり、硬化成形
にあたっては、樹脂の流出もなくすみやかに硬化するブ
リブレグを得ることができる。そしてその成形物は耐熱
性に富み、高強度であり、繊維強化材との密着性が大き
いので、高い層間ぜん断強さを持っており、産業上極め
て有用である。Effects of the Invention According to the method of the present invention, a bis(2-oxazoline) compound, an aromatic amine compound, an epoxy compound, a curing catalyst,
By making prepreg varnish using organic solvent and soaking the fiber reinforcement material in it and pulling it up and drying it, it has good storage stability, is easy to handle, and can be cured and molded quickly without resin leakage. It is possible to obtain brevlegs that harden. The molded product is highly heat resistant, has high strength, and has great adhesion to the fiber reinforcing material, so it has high interlaminar shear strength and is extremely useful industrially.
実施例 以下に実施例を挙げて本発明を説明する。Example The present invention will be explained below with reference to Examples.
実施例１
１．３−ビス（２−オキサゾリン−２−イル）ベンゼン
１０８１０８Ｏモル）、４，４′−メチレンビスアニリ
ン７９２ｇ（４モル）、エピクロン８６０（大日本イン
キ化学工業（株）要目０００ｇ（２モル相当）をはかり
とり、１５０℃の油浴中で溶解させた後、１２０〜１３
０℃で３０分反応させる。Example 1 1.3-bis(2-oxazolin-2-yl)benzene 108,108 O mol), 4,4'-methylenebisaniline 792 g (4 mol), Epicron 860 (Dainippon Ink & Chemicals Co., Ltd.) 000 g (equivalent to 2 moles) was weighed, dissolved in an oil bath at 150°C, and 120 to 13
React at 0°C for 30 minutes.
次いでメタ／−ルとメチルセａソルブ１：Ｉの混合物５
Ｉ２を加え溶解させる。この樹脂液を室温まで冷却し２
−ブロモイン酪酸エチル５７ｇを加えワニスを調整した
。得られたワニスは透明で低粘度の溶液である。３００
０本の炭素繊維フィラメントを束ねた糸を１３本／イン
チの打込み密度で平織した織布を室温下でワニスに浸け
、含浸後引き上げ１００’Ｃで１０分間乾燥してプリプ
レグを得た。このプリプレグ室温に放置しておいても安
定であり、適当な靭性をもち、取り扱い易い。このプリ
プレグを１２枚積層し１６０℃、 ５ ｋｇ／ａｍ’
の加熱加圧下で１時間硬化させ、厚さ２．５ｍｍの複合
材を得た。Then a mixture of methanol and methylceasolve 1:I 5
Add I2 and dissolve. Cool this resin liquid to room temperature and
- A varnish was prepared by adding 57 g of ethyl bromoinbutyrate. The resulting varnish is a clear, low viscosity solution. 300
A woven fabric made by plain weaving yarns made of bundles of 0 carbon fiber filaments at a weaving density of 13 threads/inch was dipped in varnish at room temperature, and after impregnation, it was pulled up and dried at 100'C for 10 minutes to obtain a prepreg. This prepreg is stable even when left at room temperature, has appropriate toughness, and is easy to handle. Twelve sheets of this prepreg were laminated at 160℃ and 5 kg/am'
The mixture was cured for 1 hour under heat and pressure to obtain a composite material with a thickness of 2.5 mm.
複合材の物性は以下の通りであった。The physical properties of the composite material were as follows.
曲げ強さ（ｋｇｆ／＋ｎｍ２） １０３ 、４曲
げ強さ（ｋｇｆ／ｍｍ”） ６０５０層間せん断
強度（ｋｇｆ／ｍｍ”） ７．２実施例２
１．３−ビス（２−オキサゾリン−２−イル）ベンゼン
８６４ｇ（４モル）とセバシン酸２０２ｇ（１モル）を
はかりとり、１５０°Ｃ油浴上で内温１４０′Ｃで３０
分加熱し、溶解反応させ透明な液を得た。また、４．４
’−メチレンビスアミノアニリン７９２ｇ（４モル）と
エピコート８２８（油化シェル（株）製）３７０ｇ（１
モル相当）を１３５℃の油浴上で内温１２０°Ｃ前後で
４０分加熱し、溶解反応させ透明な液を得た。それぞれ
の液を混合し、１１０℃に冷却しイソプロピルアルコー
ルとセロソルブアセテートの４：６の混合物４１２を加
え均一に溶解した後、２−ブロモプロピオン酸エチル３
３ｇを加え透明なワニスを得た。平織ガラスクロス（日
東紡績（株）製 ＷＥ−２２Ｄ１０４ＢＺ２）を室温下
でつけて、引き上げ１２０℃で１５分間乾燥し、プリプ
レグを得た。このプリプレグを１４枚積層し、１６０°
Ｃ，５ｋｇ／ｃｍ’の加熱加圧下で１時間硬化させ厚さ
３．０ｍｍの複合材を得た。Bending strength (kgf/+nm2) 103, 4 Bending strength (kgf/mm") 6050 Interlaminar shear strength (kgf/mm") 7.2 Example 2 1.3-Bis(2-oxazolin-2-yl) Weighed out 864 g (4 mol) of benzene and 202 g (1 mol) of sebacic acid, and heated them on a 150°C oil bath at an internal temperature of 140'C for 30 minutes.
The mixture was heated for 1 minute to cause a dissolution reaction and a clear liquid was obtained. Also, 4.4
'-Methylenebisaminoaniline 792g (4 mol) and Epicote 828 (manufactured by Yuka Shell Co., Ltd.) 370g (1
molar equivalent) was heated on an oil bath at 135°C for 40 minutes at an internal temperature of around 120°C to cause a dissolution reaction and obtain a transparent liquid. The respective liquids were mixed, cooled to 110°C, and a 4:6 mixture of isopropyl alcohol and cellosolve acetate 412 was added and dissolved uniformly. Ethyl 2-bromopropionate 3
3 g was added to obtain a transparent varnish. A plain weave glass cloth (WE-22D104BZ2 manufactured by Nitto Boseki Co., Ltd.) was applied at room temperature, pulled up and dried at 120°C for 15 minutes to obtain a prepreg. Laminated 14 sheets of this prepreg, 160°
It was cured for 1 hour under heat and pressure of C, 5 kg/cm' to obtain a composite material with a thickness of 3.0 mm.
複合材の物性は下記の通りであった。The physical properties of the composite material were as follows.
引張り強さ（ｋｇｆ／ｍｍリ ４２，３引張弾性率
（ｋｇＪ／ｍｍ２） ｌ ９４０曲げ強さ （ｋｇｆ
／ｍｍ’） ５１ 、８曲げ弾性率（ｋｇｆ／ｍ
ｍ”） ２１４０圧縮強さ （ｋｇｆ／ｍｍ”）
５２ 、９実施例３
１．３−ビス（２−オキサゾリン−２−イル）ベンゼン
８６４ｇ（４モル）、パラアミ７安息香酸６９ｇ（０，
５モル）、２，２”−ビス［４−（４−アミノフェノキ
シ）フェニル］プロパン８２０ｇ（２モル）、分子末端
に芳香族アミン基を有するポリエーテル骨格オリゴマー
（イハラケミカル（株）製エラスマ−１０００）１２３
０ ｇ（１モル相当とエピコート８１５（油化シェル（
株）製）５５５ｇ（１，５モル）をはかりとり１４０℃
の油浴中で１時間溶解反応させた。次にエタノール−エ
チルセロソルブの１＝１の混合物５Ｑを加え、次いで臭
化シクロヘキシル７１ｇを加え透明なワニスを得た。室
温まで冷却し炭素繊維ロービング（倉敷紡績（株）製Ｃ
２００ＣＤ）を浸けて引き上げ１１００Ｃで１０分乾燥
しプリプレグを得た。このプリプレグは室温に放置して
おいても安定であり、適当な靭性をもち取り扱い易い。Tensile strength (kgf/mm2) 42.3 Tensile modulus (kgJ/mm2) 940 Bending strength (kgf
/mm') 51, 8 Flexural modulus (kgf/m
m”) 2140 Compressive strength (kgf/mm”)
52,9 Example 3 1.3-bis(2-oxazolin-2-yl)benzene 864 g (4 mol), para-amino-7 benzoic acid 69 g (0,
5 moles), 820 g (2 moles) of 2,2"-bis[4-(4-aminophenoxy)phenyl]propane, polyether skeleton oligomer having an aromatic amine group at the molecular end (elasmer manufactured by Ihara Chemical Co., Ltd.) 1000) 123
0 g (equivalent to 1 mol) and Epicote 815 (Yuka Shell (
Co., Ltd.) 555g (1.5 mol) was weighed and heated to 140°C.
The mixture was dissolved and reacted in an oil bath for 1 hour. Next, 5Q, a 1=1 mixture of ethanol and ethyl cellosolve, was added, followed by 71 g of cyclohexyl bromide to obtain a transparent varnish. Cool to room temperature and carbon fiber roving (C manufactured by Kurashiki Boseki Co., Ltd.)
200CD) was immersed, pulled up and dried at 1100C for 10 minutes to obtain a prepreg. This prepreg is stable even when left at room temperature, has appropriate toughness, and is easy to handle.
実施例４
ワニスの調製
４．４′−ジアミノジフェニルメタン２６４ｇ（１，３
３モル）とエポキシ樹脂エピコート８２８（油化シェル
エポキシ社製）１２３ｇ（０，３３モル）をヒーカーに
秤りとり、これにエチレングリコールモノメチルエーテ
ル４００ｇを加えて溶解させた。Example 4 Preparation of varnish 4.264 g of 4'-diaminodiphenylmethane (1,3
3 mol) and 123 g (0.33 mol) of epoxy resin Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) were weighed in a heater, and 400 g of ethylene glycol monomethyl ether was added thereto and dissolved.
次に２．２”−（１，３−フェニレン）ビス−２−オキ
サゾリン２８８ｇ（１，３３モル）を別のビーカーに秤
りとり、エチレングリコールモノメチルエーテル６００
ｇを加え、油浴につけ６０′Ｃに加温して溶解させた。Next, 288 g (1,33 mol) of 2.2"-(1,3-phenylene)bis-2-oxazoline was weighed into another beaker, and 600 g of ethylene glycol monomethyl ether
g was added, and the mixture was placed in an oil bath and heated to 60'C to dissolve it.
これら２つの溶液を合して、そこへ塩化カルシウム約２
０ｇを加え、よく撹拌して溶液中の水分を脱水した。そ
の後、アニリンの臭化水素酸塩１４ｇとアエロジル＃３
００ ２７ｇを加えてよく撹拌して、半透明で低粘度の
ワニスを得た。Combine these two solutions and add about 2 ounces of calcium chloride to it.
0 g was added and stirred thoroughly to remove water in the solution. Then, 14 g of aniline hydrobromide and Aerosil #3
00 was added and stirred thoroughly to obtain a translucent, low viscosity varnish.
プリプレグの調製
３．０００本のフィラメントを束ねた炭素繊維を１３本
／インチの打込み密度で平織りした織布に室温て上記の
ワニスを含浸し、１００°Ｃのオーブン９１０分間放置
して乾燥し、プリプレグを得た。Preparation of Prepreg A woven fabric made by plain weaving carbon fibers made of bundles of 3,000 filaments at a weaving density of 13 filaments/inch was impregnated with the above varnish at room temperature, and left in an oven at 100°C for 910 minutes to dry. Got prepreg.
プリプレグの積層と物性の測定
上記のプリプレグを１２枚積層し、１３０°Ｃの金型に
おき、５ ｋｇ／ ｃｍ’の圧をかけ１時間型締めして
硬化させ、２．５ｍｍ厚さの積層板を得た。この積層板
の強度を測定して、下記の結果を得た。Lamination of prepreg and measurement of physical properties Twelve sheets of the prepreg described above were laminated, placed in a mold at 130°C, and clamped under a pressure of 5 kg/cm' for 1 hour to harden, resulting in a laminate of 2.5 mm thickness. Got the board. The strength of this laminate was measured and the following results were obtained.
ショートビーム層間せん断強度 ３ 、７ ｋｇ／ｍｍ
２３点曲げ強度 ４ 、４ ｋｇ／ｍ
ｍ２３点曲げ弾性率 ５６５０ ｋｇ／ｍ
ｍ’実施例５
ワニスの調製
実施例４と同様にした。Short beam interlaminar shear strength 3,7 kg/mm
23-point bending strength 4,4 kg/m
m23 point bending modulus 5650 kg/m
m' Example 5 Preparation of varnish The same procedure as in Example 4 was carried out.
プリプレグの調製
ワニスを１２，０００本のフィラメントを束ねた炭素繊
維に含浸し、１４０°Ｃて４０秒間乾燥し、ヤーン状の
プリプレグを得た。Preparation of Prepreg Carbon fibers made of 12,000 filaments were impregnated with varnish and dried at 140°C for 40 seconds to obtain a yarn-like prepreg.
プリプレグの積層と物性の測定 このプリプレグを、幅１２．７ｍｍ、高さ２ ｍｍ。Lamination of prepreg and measurement of physical properties This prepreg has a width of 12.7 mm and a height of 2 mm.
長さ２５０＋ｎｍの金型（温度；１３０°Ｃ）に３４本
セットし、３０ｋｇ／Ｃｍ’の圧をかけて１時間型を閉
じた。こうして得られた厚さ２ｍｍの、一方向の複合材
の物性を測定して下記の値を得た。34 pieces were set in a mold with a length of 250+ nm (temperature: 130°C), and the mold was closed for 1 hour by applying a pressure of 30 kg/cm'. The physical properties of the unidirectional composite material having a thickness of 2 mm thus obtained were measured and the following values were obtained.
ショートビーム層間せん断強度 １０．８ｋｇ／ ｍｍ
”３点曲げ強度 １７５ｋｇ／ｍｍ２
３点曲げ弾性率 ＩＩ、 ６００ｋｇ／
ｍｍ”実施例６
ワニスの調製
実施例４と同様にした。Short beam interlaminar shear strength 10.8kg/mm
”3-point bending strength 175kg/mm2
3-point bending modulus II, 600kg/
mm'' Example 6 Preparation of varnish The same procedure as in Example 4 was carried out.
プリプレグの調製
ワニスを１ｍ当りの重量が０．１１５ｇの一方向ガラス
ロービングに含浸し、１４０°Ｃで４０秒間乾燥してヤ
ーン状のプリプレグを得た。Preparation of Prepreg A unidirectional glass roving having a weight of 0.115 g per meter was impregnated with varnish and dried at 140° C. for 40 seconds to obtain a yarn-like prepreg.
プリプレグの積層と物性の測定 このプリプレグを、幅１２．７ｍｍ、高さ２ｍｍ。Lamination of prepreg and measurement of physical properties This prepreg has a width of 12.7 mm and a height of 2 mm.
長さ２５０ｍｍの金型（温度１３０°Ｃ）にセットし、
３０ｋｇ／ｃｍ’の圧で１時間型を閉じて硬化させ、厚
さ１ 、９ ｍｍの一方向複合材を得た。そしてこの材
料の物性を測定して、下記の値を得た。Set in a mold with a length of 250 mm (temperature 130°C),
The mold was closed and cured under a pressure of 30 kg/cm' for 1 hour to obtain a unidirectional composite material with a thickness of 1.9 mm. The physical properties of this material were measured and the following values were obtained.
Claims (4)
ポキシ化合物、 （ｃ）分子内に少なくとも２個のアミノ基を有する芳香
族アミン化合物および （ｄ）硬化触媒を含有する有機溶媒溶液を繊維強化材に
含浸させた後、該溶媒を揮散させることを特徴とするプ
リプレグの製造法。(1) (a) bis(2-oxazoline) compound, (b) epoxy compound having at least two epoxy groups in the molecule, (c) aromatic amine compound having at least two amino groups in the molecule, and (d) A method for producing a prepreg, which comprises impregnating a fiber reinforcing material with an organic solvent solution containing a curing catalyst, and then volatilizing the solvent.
（２−オキサゾリン−２−イル）ベンゼンであり、芳香
族アミン化合物が４，４′−メチレンビスアニリンであ
る請求項（１）記載のプリプレグの製造法。(2) Claim (1) wherein the bis(2-oxazoline) compound is 1,3-bis(2-oxazolin-2-yl)benzene and the aromatic amine compound is 4,4'-methylenebisaniline. Prepreg manufacturing method.
ロモイソ酪酸アルキルエステルである請求項（１）記載
のプリプレグの製造法。(3) The method for producing a prepreg according to claim (1), wherein the curing catalyst is aniline hydrobromide or 2-bromoisobutyric acid alkyl ester.
テルまたはそのアシレートである請求項（１）記載のプ
リプレグの製造法。(4) The method for producing a prepreg according to claim (1), wherein the organic solvent is ethylene glycol monoalkyl ether or its acylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10859489 | 1989-04-26 | ||
| JP1-108594 | 1989-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0347848A true JPH0347848A (en) | 1991-02-28 |
Family
ID=14488765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10901390A Pending JPH0347848A (en) | 1989-04-26 | 1990-04-25 | Production of prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0347848A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002121302A (en) * | 2000-10-11 | 2002-04-23 | Nagoya Oil Chem Co Ltd | Resin-impregnated porous matter and molded article |
| EP1935924A1 (en) | 2002-09-12 | 2008-06-25 | Shin-Etsu Chemical Company, Ltd. | Novel organopolysiloxane polymer, pasty composition, and cosmetic preparation containing the same |
| EP1946799A2 (en) | 2007-01-19 | 2008-07-23 | Shin-Etsu Chemical Co., Ltd. | Silicone copolymer and cosmetics comprising the same |
| EP2014701A2 (en) | 2007-06-18 | 2009-01-14 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane, a method of preparing the same and a cosmetic comprising the same |
| EP2103301A1 (en) | 2008-03-21 | 2009-09-23 | Shin-Etsu Chemical Co., Ltd. | Polyglycerin-modified silicone and a cosmetic comprising the same |
| JP2016060898A (en) * | 2014-09-22 | 2016-04-25 | 京セラケミカル株式会社 | Two-pack casting epoxy resin composition, and coil component |
| WO2017130257A1 (en) | 2016-01-29 | 2017-08-03 | 信越化学工業株式会社 | Water absorbent resin having siloxane skeleton, and cosmetic including same |
| WO2018020585A1 (en) * | 2016-07-26 | 2018-02-01 | 日立化成株式会社 | Molded resin body and resin gear |
| JP2021533219A (en) * | 2018-07-27 | 2021-12-02 | 浙江三時紀新材科技有限公司Zhejiang Third Age Material Technology Co., Ltd | Method for preparing spherical or angular powder filler, spherical or angular powder filler obtained from the same, and its use. |
-
1990
- 1990-04-25 JP JP10901390A patent/JPH0347848A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002121302A (en) * | 2000-10-11 | 2002-04-23 | Nagoya Oil Chem Co Ltd | Resin-impregnated porous matter and molded article |
| EP1935924A1 (en) | 2002-09-12 | 2008-06-25 | Shin-Etsu Chemical Company, Ltd. | Novel organopolysiloxane polymer, pasty composition, and cosmetic preparation containing the same |
| EP1992656A1 (en) | 2002-09-12 | 2008-11-19 | Shin-Etsu Chemical Company, Ltd. | Novel Organopolysiloxanpolymer, Pasty Composition, and Cosmetic Preparation Containing the Composition |
| EP1946799A2 (en) | 2007-01-19 | 2008-07-23 | Shin-Etsu Chemical Co., Ltd. | Silicone copolymer and cosmetics comprising the same |
| EP2014701A2 (en) | 2007-06-18 | 2009-01-14 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane, a method of preparing the same and a cosmetic comprising the same |
| EP2103301A1 (en) | 2008-03-21 | 2009-09-23 | Shin-Etsu Chemical Co., Ltd. | Polyglycerin-modified silicone and a cosmetic comprising the same |
| JP2016060898A (en) * | 2014-09-22 | 2016-04-25 | 京セラケミカル株式会社 | Two-pack casting epoxy resin composition, and coil component |
| WO2017130257A1 (en) | 2016-01-29 | 2017-08-03 | 信越化学工業株式会社 | Water absorbent resin having siloxane skeleton, and cosmetic including same |
| US10786440B2 (en) | 2016-01-29 | 2020-09-29 | Shin-Etsu Chemical Co., Ltd. | Water absorbing resin having siloxane skeleton and cosmetic containing the same |
| WO2018020585A1 (en) * | 2016-07-26 | 2018-02-01 | 日立化成株式会社 | Molded resin body and resin gear |
| JPWO2018020585A1 (en) * | 2016-07-26 | 2019-01-17 | 日立化成株式会社 | Resin molded body and resin gear |
| JP2021533219A (en) * | 2018-07-27 | 2021-12-02 | 浙江三時紀新材科技有限公司Zhejiang Third Age Material Technology Co., Ltd | Method for preparing spherical or angular powder filler, spherical or angular powder filler obtained from the same, and its use. |
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