CN114127152A - 固化性组合物、固化物、纤维增强复合材料及成型品 - Google Patents
固化性组合物、固化物、纤维增强复合材料及成型品 Download PDFInfo
- Publication number
- CN114127152A CN114127152A CN202080052781.2A CN202080052781A CN114127152A CN 114127152 A CN114127152 A CN 114127152A CN 202080052781 A CN202080052781 A CN 202080052781A CN 114127152 A CN114127152 A CN 114127152A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- curable composition
- fiber
- composition according
- cured product
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 27
- 239000003822 epoxy resin Substances 0.000 claims abstract description 103
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 103
- 239000000047 product Substances 0.000 claims abstract description 53
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 150000003077 polyols Chemical class 0.000 claims abstract description 43
- 229920005862 polyol Polymers 0.000 claims abstract description 38
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 36
- 229920000570 polyether Polymers 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 17
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 239000012783 reinforcing fiber Substances 0.000 claims description 24
- 150000008065 acid anhydrides Chemical class 0.000 claims description 21
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 6
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 description 45
- -1 polymethylene Polymers 0.000 description 35
- 238000001723 curing Methods 0.000 description 32
- 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 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 239000000835 fiber Substances 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- 229930185605 Bisphenol Natural products 0.000 description 11
- 229920000049 Carbon (fiber) Polymers 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 11
- 239000004917 carbon fiber Substances 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical class CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009730 filament winding Methods 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 4
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 239000002759 woven fabric Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- NHZLDRXCSVFATE-UHFFFAOYSA-N methyl perchlorate Chemical compound COCl(=O)(=O)=O NHZLDRXCSVFATE-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- QXKKYNIWAYERHT-UHFFFAOYSA-N 2,2-dimethylbutane-1,3-diol Chemical compound CC(O)C(C)(C)CO QXKKYNIWAYERHT-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 2
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-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
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method 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
- 238000004804 winding Methods 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 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
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- FDYWJVHETVDSRA-UHFFFAOYSA-N 1,1-diisocyanatobutane Chemical compound CCCC(N=C=O)N=C=O FDYWJVHETVDSRA-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-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
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- QYYCPWLLBSSFBW-UHFFFAOYSA-N 2-(naphthalen-1-yloxymethyl)oxirane Chemical group C=1C=CC2=CC=CC=C2C=1OCC1CO1 QYYCPWLLBSSFBW-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- OGRULRAOMCDCBO-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC1=CC=C2C=CC=CC2=C1OCC1CO1 OGRULRAOMCDCBO-UHFFFAOYSA-N 0.000 description 1
- NKANYVMWDXJHLE-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1OCC1CO1 NKANYVMWDXJHLE-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- WTTXRLXWUGSITL-UHFFFAOYSA-N C(C)(=O)O.C(C)C(COCCO)O Chemical compound C(C)(=O)O.C(C)C(COCCO)O WTTXRLXWUGSITL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 239000002841 Lewis acid Substances 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- NCDNCNXCDXHOMX-UHFFFAOYSA-N Ritonavir Natural products C=1C=CC=CC=1CC(NC(=O)OCC=1SC=NC=1)C(O)CC(CC=1C=CC=CC=1)NC(=O)C(C(C)C)NC(=O)N(C)CC1=CSC(C(C)C)=N1 NCDNCNXCDXHOMX-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical class OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GMGLYSIINJPYLI-UHFFFAOYSA-N butan-2-one;propan-2-one Chemical compound CC(C)=O.CCC(C)=O GMGLYSIINJPYLI-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
- 229910052792 caesium Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-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
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- NCDNCNXCDXHOMX-XGKFQTDJSA-N ritonavir Chemical compound N([C@@H](C(C)C)C(=O)N[C@H](C[C@H](O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1SC=NC=1)CC=1C=CC=CC=1)C(=O)N(C)CC1=CSC(C(C)C)=N1 NCDNCNXCDXHOMX-XGKFQTDJSA-N 0.000 description 1
- 229960000311 ritonavir Drugs 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6407—Reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
本发明提供固化性组合物及其固化物、纤维增强复合材料、纤维增强树脂成型品以及纤维增强树脂成型品的制造方法,所述固化性组合物的特征在于:为将氨基甲酸酯改性环氧树脂(A)作为主剂的必须成分、将酸酐(B)作为固化剂的必须成分的固化性组合物,上述氨基甲酸酯改性环氧树脂(A)为将多异氰酸酯化合物(a1)、聚醚多元醇(a2)和含有羟基的环氧树脂(a3)作为必须的反应原料的反应生成物。该固化性组合物能够形成在固化物中具有优异的断裂韧性和抗拉强度的固化物。
Description
技术领域
本发明涉及固化物中的断裂韧性和抗拉强度优异的固化性组合物及其固化物、纤维增强复合材料、纤维增强树脂成型品以及纤维增强树脂成型品的制造方法。
背景技术
对于利用增强纤维进行了增强的纤维增强树脂成型品而言,轻量且机械强度优异这样的特征受到关注,以汽车、航空器、船舶等的壳体或各种构件为代表,在各种结构体用途中的利用正在扩大。纤维增强树脂成型品能够利用长丝缠绕法、压制成型法、手糊法、拉挤成型法、RTM法等成型方法将纤维增强复合材料成型,进行制造。
上述纤维增强复合材料为在增强纤维中含浸有树脂的纤维增强复合材料。对于纤维增强复合材料所使用的树脂而言,要求常温下的稳定性,以及固化物的耐久性、强度,因此一般而言大多使用热固性树脂。此外,如上述那样,使树脂含浸于增强纤维而使用,因此在含浸工序中越是低粘度越优选。
进一步,根据纤维增强树脂成型品的用途,对于树脂的要求特性也不同,例如,在用于发动机等结构部件、电线芯材的情况下,以纤维增强树脂成型品能够长期耐受苛刻的使用环境的方式,要求固化物中的耐热性、机械强度优异的树脂。此外,在用于高压罐的增强用途的情况下,要求伴随着高压气体的取出和放入的循环特性,这要求固化物中的断裂韧性、伸长这样的特性优异。
作为纤维增强复合材料用的树脂组合物,例如,广泛已知由包含双酚型环氧树脂的主剂与包含酸酐的固化剂形成的环氧树脂组合物(例如,参照专利文献1。)。这样的环氧树脂组合物具有对增强纤维的含浸性高、固化物中的耐热性等也优异的特征,但是,利用断裂韧性试验、抗拉强度试验进行了评价的机械强度并不充分。
现有技术文献
专利文献
专利文献1:日本特开2010-163573号公报
发明内容
发明所要解决的课题
因此,本发明所要解决的课题在于提供固化物中的断裂韧性和抗拉强度优异的固化性组合物及其固化物、纤维增强复合材料、纤维增强树脂成型品以及纤维增强树脂成型品的制造方法。
用于解决课题的方法
本发明人等为了解决上述课题而进行了深入研究,结果发现,作为环氧树脂成分,使用将多异氰酸酯化合物、聚醚多元醇和含有羟基的环氧树脂作为必须的反应原料的氨基甲酸酯改性环氧树脂,作为固化剂,使用酸酐,从而能够解决上述课题,由此完成了本发明。
即,本发明提供一种固化性组合物、其固化物、使用了上述固化性组合物的纤维增强复合材料、纤维增强树脂成型品以及纤维增强树脂成型品的制造方法,所述固化性组合物的特征在于,为将氨基甲酸酯改性环氧树脂(A)作为主剂的必须成分、将酸酐(B)作为固化剂的必须成分的固化性组合物,上述氨基甲酸酯改性环氧树脂(A)为将多异氰酸酯化合物(a1)、聚醚多元醇(a2)和含有羟基的环氧树脂(a3)作为必须的反应原料的反应生成物。
发明的效果
根据本发明,能够提供固化物中的断裂韧性和抗拉强度优异的固化性组合物及其固化物、纤维增强复合材料、纤维增强树脂成型品以及纤维增强树脂成型品的制造方法。
具体实施方式
本发明的固化性组合物的特征在于,为将氨基甲酸酯改性环氧树脂(A)作为主剂的必须成分、将酸酐(B)作为固化剂的必须成分的固化性组合物,上述氨基甲酸酯改性环氧树脂(A)为将多异氰酸酯化合物(a1)、聚醚多元醇(a2)和含有羟基的环氧树脂(a3)作为必须的反应原料的反应生成物。
作为上述氨基甲酸酯改性环氧树脂(A)的反应原料的上述多异氰酸酯化合物(a1)可举出例如,丁烷二异氰酸酯、1,6-己二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯等脂肪族二异氰酸酯化合物;降冰片烷二异氰酸酯、异佛尔酮二异氰酸酯、氢化苯二亚甲基二异氰酸酯、氢化二苯基甲烷二异氰酸酯等脂环式二异氰酸酯化合物;甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯等芳香族二异氰酸酯化合物;具有下述结构式(1)所示的重复结构的聚亚甲基聚苯基多异氰酸酯;它们的异氰脲酸酯改性体、缩二脲改性体、脲基甲酸酯改性体等。它们可以各自单独使用,也可以并用2种以上。
[化1]
[式中,R1各自独立地为氢原子、碳原子数1~6的烃基的任一者。R2各自独立地为碳原子数1~4的烷基、或与结构式(1)所示的结构部位经由带有*标记的亚甲基而连接的结合点的任一者。m为0或1~3的整数,l为1以上的整数。]
即使在上述多异氰酸酯化合物(a1)中,从成为固化物中的断裂韧性和抗拉强度高、并且对增强纤维的含浸性也优异的固化性组合物的方面考虑,优选为各种二异氰酸酯化合物,更优选为分子结构中具有环结构的二异氰酸酯化合物,即,脂环式二异氰酸酯或芳香族二异氰酸酯。进一步,特别优选异氰酸酯基含量为35质量%以上的化合物。在并用多种上述多异氰酸酯化合物(a1)的情况下,优选其80质量%以上为二异氰酸酯化合物,更优选80质量%以上为脂环式二异氰酸酯或芳香族二异氰酸酯。
上述聚醚多元醇(a2)可举出2官能的聚醚二醇、3官能以上的聚醚多元醇。
作为聚醚二醇,优选为具有氧化烯基、且在聚合物末端、支链末端这样的任意的位置在分子内每一分子具有2个羟基的化合物。
作为这样的聚醚二醇,可举出例如,聚氧丙烯二醇、聚氧乙烯二醇、聚(氧丙烯基-氧乙烯基)二醇、聚四亚甲基醚二醇等2官能的聚环氧烷(polyalkylene oxide)等,不受特别限定。这些聚醚二醇例如,能够使用2官能引发剂,在开环聚合催化剂的存在下,将环氧烷进行开环聚合来制造。作为开环聚合催化剂,没有特别限定,可举出例如,氢氧化钾、氢氧化钠等碱金属化合物催化剂;氢氧化铯等铯金属化合物催化剂;六氰钴酸锌配位化合物等复合金属氰化物配位化合物催化剂;磷腈催化剂、含有亚氨基的磷腈盐催化剂、氢氧化钡催化剂等。这些催化剂可以使用一种或二种以上。
进一步可以直接使用市售品,具体而言,可举出三洋化成株式会社制SANNIX PP-1000、PP-2000、PP-3000、PP-4000,三井化学株式会社制Actcol P-22、P-21、P-23、P-28、ED-28,AGC株式会社制Excenol 720、1020、2020、3020、4020、510、4002、4010、4019、5001、5005、PREMINOL 4002、5005、PREMINOL S4004、4011、4012、4015、4008F、4013F、4318F,日油株式会社制UNIOL D-1000、D-1200、D-2000、D-4000、PB-700、PEG#1500、PEG#2000、Plonon#102、#104、#202B、#204,三菱化学株式会社制PTMG650、PTMG1000、PTMG1500、PTMG2000等。它们可以单独使用,也可以将多种聚醚二醇混合来使用。这些之中,从断裂韧性优异的观点考虑,优选具有氧丙烯基、四亚甲基醚基。
另外,上述聚醚二醇的数均分子量(Mn)优选为500~4,000的范围,进一步优选为1,000~3,000的范围。另外,数均分子量是指基于聚醚二醇的羟值(按照JIS K1557 6.4测定得到的值,OHV,单位为mgKOH/g),计算得到的值。
作为上述3官能以上的聚醚多元醇,具有氧化烯基,在聚合物末端、支链末端这样的任意的位置,在分子内每一分子具有至少3个以上的羟基。
可举出例如,聚氧丙烯多元醇、聚氧乙烯多元醇、聚(氧丙烯基-氧乙烯基)多元醇等3官能以上的聚环氧烷,不受特别限定,具体而言,能够作为三洋化成株式会社制SANNIXGP-400、GP-600、GP-1000、GP-1500、GP-3000、GP-4000V、GA-5000S、FA-908、FA-961、FA-921、FA-703、FA-757,三井化学株式会社制Actcol G-28、MN-5000、MN-4000、P-31、MN-1500,AGC株式会社制Excenol 1030、4030、5030、230、828、837、PREMINOL 3005、3010、3015、3020、7001、7006、7012、PREMINOL S3006、3011、PREMINOL 7021(4官能)等市售品来获得。
作为3官能以上的聚醚多元醇,每一分子的羟基数优选为3~6的范围,进一步优选为3~4的范围。
3官能以上的聚醚多元醇的数均分子量(Mn)优选为500~4,000的范围,特别优选为1,000~3,000的范围。另外,数均分子量与聚醚二醇同样,为由羟值算出的值。
这些之中,为了成为固化物中的断裂韧性和抗拉强度高、并且对增强纤维的含浸性也优异的固化性组合物,优选为聚醚二醇。在使用多种聚醚多元醇(a2)的情况下,聚醚多元醇(a2)中的聚醚二醇的含有率优选为80质量%以上。
上述含有羟基的环氧树脂(a3)只要在分子结构中具有羟基和缩水甘油基,就没有特别限定。此外,上述含有羟基的环氧树脂(a3)可以单独使用一种,也可以并用2种以上。其中,为了成为固化物中的断裂韧性和抗拉强度高、并且对增强纤维的含浸性也优异的固化性组合物,优选为将二醇化合物进行缩水甘油醚化而得的、2官能型含有羟基的环氧树脂。
上述2官能型含有羟基的环氧树脂的理论结构例如,能够以下述结构式(2)来表示。
[化2]
(式中X为来源于二醇化合物的结构部位,n为0或1以上的整数,n的平均值为超过0的值。)
上述二醇化合物可举出例如,乙二醇、丙二醇、1,3-丙二醇、2-甲基丙二醇、1,2,2-三甲基-1,3-丙二醇、2,2-二甲基-3-异丙基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、3-甲基-1,3-丁二醇、1,5-戊二醇、3-甲基1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-双(羟基甲基)环己烷、2,2,4-三甲基-1,3-戊二醇等脂肪族二醇化合物;联苯酚、四甲基联苯酚、双酚A、双酚AP、双酚B、双酚BP、双酚C、双酚E、双酚F、双酚S等芳香族二醇化合物等。
其中,从成为除了固化物中的断裂韧性和抗拉强度以外、耐热性等也优异的固化性组合物的方面考虑,优选采用使用上述芳香族二醇化合物而得的芳香族2官能型含有羟基的环氧树脂。在作为上述含有羟基的环氧树脂(a3)并用多种的情况下,上述芳香族2官能型含有羟基的环氧树脂相对于上述含有羟基的环氧树脂(a3)的总质量的比例优选为35质量%以上,更优选为40~90质量%的范围。
上述含有羟基的环氧树脂(a3)的环氧当量优选为100~400g/当量的范围,更优选为100~250g/当量的范围。此外,其羟基当量更优选为600~3500g/当量的范围。
在本申请发明中,上述含有羟基的环氧树脂(a3)的羟基当量为利用以下方法测定得到的值。
1.在烧瓶内添加含有羟基的环氧树脂(a3)约100g和无水二甲基甲醛25mL,使它们溶解。
2.添加二丁基锡月桂酸酯约30mg和苯基异氰酸酯无水甲苯溶液(1mol/L)20mL,将烧瓶浸于50℃的热水浴中,搅拌60分钟。
3.添加二丁基胺无水甲苯溶液(2mol/L)20mL,在室温下搅拌30分钟。
4.添加甲基溶纤剂30mL、溴甲酚绿指示剂0.5mL,使用高氯酸甲酯溶纤剂溶液(1mol/L)进行滴定。同时也进行空白测定。
5.利用下述计算式计算含有羟基的环氧树脂(a3)的羟基当量。
(羟基当量(g/当量))=1000×(含有羟基的环氧树脂(a3)的样品量[g])/[(高氯酸甲酯溶纤剂溶液浓度[1mol/L])×{(含有羟基的环氧树脂(a3)溶液的滴定量[mL])-(空白的滴定量[mL])}]
上述氨基甲酸酯改性环氧树脂(A)将上述多异氰酸酯化合物(a1)、聚醚多元醇(a2)和含有羟基的环氧树脂(a3)作为必须的反应原料,但是也可以并用除了这些以外的其它反应原料。作为其它反应原料,可举出例如,脂肪族多元醇、芳香族多元醇、聚酯多元醇、聚烯烃型多元醇、聚碳酸酯多元醇等。在使用其它反应原料的情况下,从充分地发挥固化物中的断裂韧性和抗拉强度优异的本发明的效果的方面考虑,相对于氨基甲酸酯改性环氧树脂(A)的反应原料的总质量,上述多异氰酸酯化合物(a1)、聚醚多元醇(a2)和含有羟基的环氧树脂(a3)的合计质量优选为70质量%以上,更优选为90质量%以上。
上述氨基甲酸酯改性环氧树脂(A)如果将上述多异氰酸酯化合物(a1)、聚醚多元醇(a2)和含有羟基的环氧树脂(a3)作为必须的反应原料,则其制造方法不受限定,可以利用任何方法来制造。作为制造方法的一例,例如,可举出以下那样的方法。
方法1:将全部反应原料一并加入并进行反应的方法
方法2:使上述多异氰酸酯化合物(a1)、上述聚醚多元醇(a2)和根据需要所使用的其它多元醇化合物进行反应以获得含有异氰酸酯基的中间体,接着使上述含有羟基的环氧树脂(a3)进行反应的方法
方法3:使上述多异氰酸酯化合物(a1)与上述含有羟基的环氧树脂(a3)进行反应以获得含有异氰酸酯基的中间体,接着使上述聚醚多元醇(a2)和根据需要所使用的其它多元醇化合物进行反应的方法
方法4:使上述多异氰酸酯化合物(a1)、上述聚醚多元醇(a2)的一部分~全部、上述含有羟基的环氧树脂(a3)的一部分~全部、以及根据需要所使用的其它多元醇化合物的一部分~全部进行反应以获得含有异氰酸酯基的中间体,接着,使其余的上述聚醚多元醇(a2)、上述含有羟基的环氧树脂(a3)、上述其它多元醇化合物进行反应的方法
在上述方法1~方法4的任一情况下,关于反应原料中的异氰酸酯基与羟基的摩尔比[(NCO)/(OH)],从成为保存稳定性等优异的固化性组合物的方面考虑,优选为1/0.95~1/5.0的范围。
进一步,关于反应原料中的异氰酸酯基与聚醚多元醇(a2)的羟基的摩尔比即[(NCO)/(OH)],从固化物的断裂韧性优异方面考虑,优选为1/0.4~1/0.7的范围,更优选为1/0.55~1/0.70的范围。
此外,从固化物中的断裂韧性和抗拉强度优异的效果更显著地表现方面考虑,上述聚醚多元醇(a2)相对于反应原料的总质量的比例优选为5~50质量%的范围,更优选为15~35质量%的范围。
关于上述氨基甲酸酯改性环氧树脂(A)的环氧当量,从成为除了固化物中的断裂韧性和抗拉强度以外,固化性、对增强纤维的含浸性等也优异的固化性组合物方面考虑,优选为150~300g/当量的范围。
本发明的固化性组合物中的主剂中,除了上述氨基甲酸酯改性环氧树脂(A)以外,也可以含有其它成分。作为其它成分,可举出例如,上述氨基甲酸酯改性环氧树脂(A)以外的其它环氧树脂。
上述其它环氧树脂可举出例如,二缩水甘油基氧基苯、二缩水甘油基氧基萘、脂肪族环氧树脂、联苯酚型环氧树脂、双酚型环氧树脂、酚醛清漆型环氧树脂、三苯酚甲烷型环氧树脂、四苯酚乙烷型环氧树脂、苯酚或萘酚芳烷基型环氧树脂、亚苯基或亚萘基醚型环氧树脂、二环戊二烯-苯酚加成反应物型环氧树脂、含有酚性羟基的化合物-含有烷氧基的芳香族化合物共缩合型环氧树脂、缩水甘油胺型环氧树脂、这些以外的含有萘骨架的环氧树脂等。
上述脂肪族环氧树脂可举出例如,各种脂肪族多元醇化合物的缩水甘油醚化物。脂肪族环氧树脂可以单独使用一种,也可以并用2种以上。上述脂肪族多元醇化合物可举出例如,乙二醇、丙二醇、1,3-丙二醇、2-甲基丙二醇、1,2,2-三甲基-1,3-丙二醇、2,2-二甲基-3-异丙基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、3-甲基-1,3-丁二醇、1,5-戊二醇、3-甲基1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-双(羟基甲基)环己烷、2,2,4-三甲基-1,3-戊二醇等脂肪族二醇化合物;三羟甲基乙烷、三羟甲基丙烷、甘油、己三醇、季戊四醇、双三羟甲基丙烷、二季戊四醇等3官能以上的脂肪族多元醇化合物等。
上述联苯酚型环氧树脂可举出例如,将联苯酚、四甲基联苯酚等联苯酚化合物利用表卤代醇进行了聚缩水甘油醚化的联苯酚型环氧树脂。其中,优选环氧当量为150~200g/eq的范围的联苯酚型环氧树脂。
上述双酚型环氧树脂可举出例如,将双酚A、双酚F、双酚S等双酚化合物利用表卤代醇进行了聚缩水甘油醚化的双酚型环氧树脂。其中,优选环氧当量为158~200g/eq的范围的双酚型环氧树脂。
上述酚醛清漆型环氧树脂可举出例如,将由苯酚、甲酚、萘酚、双酚、联苯酚等各种酚化合物的一种~多种形成的酚醛清漆树脂利用表卤代醇进行了聚缩水甘油醚化的酚醛清漆型环氧树脂。
上述三苯酚甲烷型环氧树脂可举出例如,具有下述结构式(3)所示的结构部位作为重复结构单元的三苯酚甲烷型环氧树脂。
[化3]
[式中R3、R4各自独立地为氢原子或与结构式(3)所示的结构部位经由带有*标记的次甲基而连接的结合点的任一者。n为1以上的整数。]
上述苯酚或萘酚芳烷基型环氧树脂可举出例如,缩水甘油基氧基苯或缩水甘油基氧基萘结构具有利用下述结构式(4-1)~(4-3)的任一者所示的结构部位连接的分子结构的苯酚或萘酚芳烷基型环氧树脂。
[化4]
(式中X为碳原子数2~6的亚烷基、醚键、羰基、羰氧基、硫醚基、砜基的任一者。]
上述含有萘骨架的环氧树脂可举出例如,下述结构式(5-1)~(5-3)的任一者所示的环氧化合物等。
[化5]
上述其它环氧树脂之中,从固化物中的断裂韧性和抗拉强度高、并且对增强纤维的含浸性优异方面考虑,优选为脂肪族环氧树脂、双酚型环氧树脂、三苯酚甲烷型环氧树脂、缩水甘油胺型环氧树脂、含有萘骨架的环氧树脂的任一者,更优选为脂肪族环氧树脂或双酚型环氧树脂,特别优选为脂肪族环氧树脂。
主剂中的各环氧树脂的含量没有特别限定,能够根据所期望的性能、用途等进行适当调整。更优选上述氨基甲酸酯改性环氧树脂(A)相对于环氧树脂成分的总质量的比例优选为30~100质量%的范围。在使用脂肪族环氧树脂作为上述其它环氧树脂的情况下,两者的质量比[氨基甲酸酯改性环氧树脂(A)/脂肪族环氧树脂]优选为30/70~100/0的范围。
本发明的固化性组合物中的固化剂将酸酐(B)作为必须成分。酸酐(B)可以单独使用一种,也可以并用二种以上。作为酸酐(B)的具体例,可举出四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、甲基内亚乙基四氢邻苯二甲酸酐、三烷基四氢邻苯二甲酸酐、甲基纳迪克酸酐、邻苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、马来酸酐等。这些之中,从对增强纤维的含浸性的观点考虑,更优选使用甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、甲基内亚乙基四氢邻苯二甲酸酐。
本发明中,可以与上述酸酐(B)一起,使用其它固化剂或固化促进剂(B’)。其它固化剂或固化促进剂(B’)一般而言,作为环氧树脂与酸酐的固化促进剂而使用的物质即使在本发明中也能够使用,具体而言,可举出咪唑衍生物、叔胺、胺配合体盐、酰胺化合物、含有酚性羟基的化合物或酚醛树脂、磷系化合物、脲衍生物、有机酸金属盐、路易斯酸等。
本发明的固化性组合物中,主剂与固化剂的配合比例没有特别限定,能够根据所期望的固化物性能、用途进行适当调整。作为配合的一例,例如,优选相对于上述主剂中环氧树脂成分所具有的环氧基1摩尔,上述固化剂中的酸酐(B)所具有的酸酐基的合计为0.5~1.05摩尔的范围。
此外,在使用上述其它固化剂或固化促进剂(B’)的情况下,其配合比例没有特别限定,能够根据所期望的固化物性能、用途进行适当调整。特别优选在固化性组合物中以0.1~30质量%的比例进行配合。其它固化剂或固化促进剂(B’)可以与上述酸酐(B)一起配合于固化剂中,也可以在配合主剂和固化剂时进行添加来使用。
本发明的固化性组合物可以在主剂或固化剂的任一者或其两者中,含有其它树脂成分、各种添加剂。作为上述其它树脂成分,可举出例如,酸改性聚丁二烯、聚醚砜树脂、聚碳酸酯树脂、聚苯醚树脂等。
上述酸改性聚丁二烯可举出将聚丁二烯进行不饱和羧酸改性而得的物质。此外,作为市售的酸改性聚丁二烯,能够使用例如,Evonik Degussa公司制马来酸酐改性液状聚丁二烯(polyvest MA75,Polyvest EP MA120等)、kuraray公司制马来酸酐改性聚异戊二烯(LIR-403,LIR-410)等。
上述聚碳酸酯树脂可举出例如,2价或2官能型的苯酚与卤化羰基的缩聚物、或者使2价或2官能型的苯酚与碳酸二酯通过酯交换法聚合而得的物质。此外,上述聚碳酸酯树脂除了其聚合物链的分子结构为直链结构的聚碳酸酯树脂以外,其也可以具有支链结构。
上述聚苯醚树脂可以为在其树脂结构中利用接枝反应、共聚等某种方法导入了羧基、环氧基、氨基、巯基、甲硅烷基、羟基、二羧酸酐基等反应性官能团而得的改性聚苯醚树脂。
上述各种添加剂可举出例如,阻燃剂或阻燃助剂、填充材、其它添加剂、有机溶剂等。作为上述阻燃剂或阻燃助剂,可举出例如,磷系阻燃剂、氮系阻燃剂、有机硅系阻燃剂、金属氢氧化物、金属氧化物、金属碳酸盐化合物、金属粉、硼化合物、低熔点玻璃、二茂铁、乙酰丙酮金属配位化合物、有机金属羰基化合物、有机钴盐化合物、有机磺酸金属盐、金属原子与芳香族化合物或杂环化合物进行了离子结合或配位结合的化合物等。它们可以分别单独使用,也可以并用2种以上。
上述填充材可举出例如,氧化钛、玻璃珠、玻璃薄片、玻璃纤维、碳酸钙、碳酸钡、硫酸钙、硫酸钡、钛酸钾、硼酸铝、硼酸镁、熔融二氧化硅、结晶二氧化硅、氧化铝、氮化硅、氢氧化铝、洋麻纤维、碳纤维、氧化铝纤维、石英纤维等纤维状增强剂、非纤维状增强剂等。它们可以分别单独使用,也可以并用2种以上。此外,它们可以被有机物、无机物等被覆。
此外,在使用玻璃纤维作为填充材的情况下,能够从长纤维型的粗纱、短纤维型的短切束(chopped strands)、研磨纤维等中选择来使用。玻璃纤维优选使用对于所使用的树脂用进行了表面处理的物质。通过配合填充材,从而能够进一步提高燃烧时生成的不燃层(或碳化层)的强度。燃烧时一度生成的不燃层(或碳化层)变得不易破损,能够发挥稳定的绝热能力,获得更大的阻燃效果。进一步,也能够对于材料赋予高的刚性。
上述其它添加剂可举出例如,增塑剂、抗氧化剂、紫外线吸收剂、光稳定剂等稳定剂、抗静电剂、导电性赋予剂、应力缓和剂、脱模剂、结晶化促进剂、水解抑制剂、润滑剂、冲击赋予剂、滑动性改良剂、增容剂、成核剂、强化剂、增强剂、流动调节剂、染料、敏化材、着色用颜料、橡胶质聚合物、增稠剂、防沉降剂、防流挂剂、消泡剂、偶联剂、防锈剂、抗菌/防霉剂、防污剂、导电性高分子等。
上述有机溶剂例如,对于使用本发明的固化性组合物利用长丝缠绕法制造纤维增强树脂成型品的情况等是有用的。有机溶剂的种类、添加量没有特别限定,根据本发明的固化性组合物所含有的各种化合物的溶解性、成型工序中的操作性等进行适当选择。作为其一例,可举出例如,甲基乙基酮丙酮、二甲基甲酰胺、甲基异丁基酮、甲氧基丙醇、环己酮、甲基溶纤剂、乙基二乙二醇乙酸酯、丙二醇单甲基醚乙酸酯等。
本发明的固化性组合物能够用于涂料、电气/电子材料、粘接剂、成型品等各种用途。本发明的固化性组合物除了使其本身固化而使用的用途以外,也能够适合用于纤维增强复合材料、纤维增强树脂成型品等。
作为由本发明的固化性组合物获得固化物的方法,只要按照一般的环氧树脂组合物的固化方法即可,例如加热温度条件只要根据组合的固化剂的种类、用途等进行适当选择即可。可举出例如,将固化性组合物在室温~250℃左右的温度范围进行加热的方法。成型方法等也能够使用固化性组合物的一般的方法,特别是本发明的固化性组合物不需要特殊的条件。
所谓本发明的纤维增强复合材料,为使固化性组合物含浸于增强纤维之后的固化前的状态的材料。这里,增强纤维只要为有捻线、解捻线或无捻线等任一者即可,解捻线、无捻线在纤维增强复合材料中具有优异的成型性,因此优选。进一步,增强纤维的形态能够使用纤维方向沿一个方向进行了并丝的形态、织物。织物能够从平纹织物,缎纹织物等,根据所使用的部位、用途进行自由地选择。具体而言,从机械强度、耐久性优异的方面考虑,可举出碳纤维、玻璃纤维、芳族聚酰胺纤维、硼纤维、氧化铝纤维、碳化硅纤维等,也能够并用它们的2种以上。这些之中特别是从成型品的强度变得良好方面考虑,优选为碳纤维,这样的碳纤维能够使用聚丙烯腈系、沥青系、人造丝系等各种碳纤维。
作为由本发明的固化性组合物获得纤维增强复合材料的方法,没有特别限定,可举出例如下述的方法:将构成固化性组合物的各成分均匀地混合以调制清漆,接着,在由上述获得的清漆中浸渍将增强纤维沿一个方向并丝的一个方向增强纤维的方法(利用拉挤成型法、长丝缠绕法的固化前的状态);将增强纤维的织物重叠并设置于凹模,然后,利用凸模密闭之后,注入树脂以使其压力含浸的方法(利用RTM法的固化前的状态);等。
作为上述碳纤维,不受特别限定,从机械强度、刚性的观点考虑,优选抗拉强度为3,000MPa~7,000MPa的范围,拉伸伸长率为1.5~2.3%的范围,拉伸弹性模量为200MPa以上。进一步,更优选抗拉强度为4,500MPa~6,500MPa的范围,拉伸伸长率为1.7~2.3%的范围,拉伸弹性模量为230MPa以上。这里,作为市售的碳纤维制品,可举出“Torayca(注册商标)”T800S-24000、“Torayca(注册商标)”T700SC-12000、“Torayca(注册商标)”T700SC-24000、“Torayca(注册商标)”T300-3000等。
此外,碳纤维束优选一条纤维束中的长丝数为3,000~5,0000根的范围。如果长丝数小于3000根,则纤维易于弯曲,因此有时成为强度降低的原因。相反地,50,000以上时,易于引起树脂的含浸不良,因此更优选为5,000~40,000的长丝数。
进一步,本发明的纤维增强复合材料中,增强纤维相对于纤维增强复合材料的总体积的体积含有率优选为40%~85%,从强度方面考虑,进一步优选为50%~70%的范围。在体积含有率小于40%的情况下,存在上述固化性组合物的含量过多而获得的固化物的阻燃性不足、或不能满足比弹性模量和比强度优异的纤维增强复合材料所要求的各特性的情况。此外,如果体积含有率超过85%,则存在增强纤维与树脂组合物的粘接性会降低的情况。
所谓本发明的纤维增强树脂成型品,为具有增强纤维和固化性组合物的固化物的成型品,为使纤维增强复合材料热固化而得的物质。作为本发明的纤维增强树脂成型品,具体而言,纤维增强成型品中的增强纤维的体积含有率优选为40%~85%的范围,从强度的观点考虑,特别优选为50%~70%的范围。作为这样的纤维增强树脂成型品,可举出例如,前副车架、后副车架、前柱、中柱、侧梁(side member)、横梁、侧边梁(side sill)、车顶架、螺旋桨轴等汽车部件、电线电缆的芯构件、海底油田用的管材、印刷机用辊/管材、遥控设备叉(robot fork)材、航空器的一次结构材、二次结构材等。
作为由本发明的固化性组合物获得纤维增强成型品的方法,没有特别限定,优选使用拉拔成型法(拉挤成型法)、长丝缠绕法、RTM法等。所谓拉拔成型法(拉挤成型法),为将纤维增强复合材料导入至模具内,进行加热固化之后,利用拉拔装置进行拉拔,从而将纤维增强树脂成型品成型的方法;所谓长丝缠绕法,为一边使纤维增强复合材料(包含一个方向纤维)沿铝内胆(aluminium liner)、塑料内胆(plastic liner)等旋转一边卷绕之后,使其加热固化以将纤维增强树脂成型品成型的方法;所谓RTM法,为使用凹模和凸模这2种模具的方法,为在上述模具内使纤维增强复合材料加热固化以将纤维增强树脂成型品成型的方法。另外,在将大型制品、复杂形状的纤维增强树脂成型品成型的情况下,优选使用RTM法。
作为纤维增强树脂成型品的成型条件,优选使纤维增强复合材料在50℃~250℃的温度范围进行热固化来成型,更优选在70℃~220℃的温度范围进行成型。这是因为,如果该成型温度过低,则有时得不到充分的快速固化性,相反地如果过高,则有时易于产生由热应变引起的翘曲。作为其它成型条件,可举出使纤维增强复合材料在50℃~100℃预固化,制成无粘性状的固化物之后,进一步,在120℃~200℃的温度条件进行处理等以2个阶段使其固化的方法等。
作为由本发明的固化性组合物获得纤维增强成型品的其它方法,可举出:在模具上敷设纤维骨料,将上述清漆、纤维骨料多重层叠的手工涂敷法、喷涂成型法;使用阳模、阴模的任一者,一边使清漆含浸于由增强纤维形成的基材一边进行累积并成型,盖上能够使压力作用于成型物的柔性的模具,对经气密密封的成型物进行真空(减压)成型的真空袋法;预先将含有增强纤维的清漆制成片状而得的物质利用模具进行压缩成型的SMC压制法等。
实施例
接下来,通过实施例、比较例,具体地说明本发明,但是以下,“份”和“%”只要没有特别规定,就是指质量基准。
制造例1氨基甲酸酯改性环氧树脂(A-1)的制造
在设置有氮气导入管、冷却管、温度计和搅拌机的4口烧瓶中,加入异佛尔酮二异氰酸酯80质量份,加热直至80℃。接着,作为聚醚多元醇,添加三洋化成株式会社制SANNIXPP-2000(数均分子量2000)447质量份。然后,添加氨基甲酸酯化催化剂(日东化成株式会社制“Neostann U-28”)0.1质量份,进一步反应2小时,获得了异氰酸酯基含量为2.1质量%的中间体(1)。
接着,作为双酚A型环氧树脂,添加DIC株式会社制EPICLON850-S(环氧当量188g/当量,羟基当量2900g/当量)940质量份,在80℃的温度条件下,使其反应直至确认异氰酸酯基的消失,获得了氨基甲酸酯改性环氧树脂(A-1)。氨基甲酸酯改性环氧树脂(A-1)的环氧当量为293g/eq。
制造例2~10氨基甲酸酯改性环氧树脂(A-2)~(A-10)的制造
在制造例1中,使所使用的原料为表1所记载的原料,除此以外,同样地操作,获得了氨基甲酸酯改性环氧树脂(A-2)~(A-10)。另外,制造例10中,将作为双酚A型环氧树脂的DIC株式会社制EPICLON850-S与Nagase ChemteX株式会社制1,4-丁二醇型环氧树脂EX-214并用来反应。
[表1]
制造例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
环氧树脂 | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | A-9 | A-10 |
IPDI | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | ||
TDI | 62.6 | 62.6 | ||||||||
PP2000 | 447 | 447 | 447 | |||||||
PP1000 | 223 | 180 | 270 | |||||||
PTMG2000 | 447 | |||||||||
PEG2000 | 447 | |||||||||
PEG400 | 89.5 | |||||||||
P3000 | 454 | |||||||||
850-S | 940 | 954 | 941 | 1212 | 690 | 940 | 940 | 941 | 941 | 954 |
EX-214 | 585 | |||||||||
EE(g/eq) | 293 | 288 | 249 | 228 | 283 | 293 | 293 | 222 | 295 | 219 |
表1中的化合物
IPDI:异佛尔酮二异氰酸酯Evonik Japan株式会社制“VESTANAT IPDI”
TDI:甲苯二异氰酸酯三井化学株式会社制“COSMONATE T-80”
PP2000:聚氧丙烯二醇三洋化成株式会社制“SANNIX PP-2000”羟值56.1mgKOH/g数均分子量2,000
PP1000:聚氧丙烯二醇三洋化成株式会社制“SANNIX PP-1000”羟值109mgKOH/g数均分子量1,030
PTMG2000:聚氧1,4-丁二醇三菱化学株式会社制“PTMG2000”羟值56.7mgKOH/g数均分子量1,980
PEG2000:聚氧乙烯二醇日油株式会社制“PEG#2000”羟值56.3mgKOH/g平均分子量1,990
PEG400:聚氧乙烯二醇日油株式会社制“PEG#400”羟值282mgKOH/g平均分子量400
GP3000:聚氧丙烯二醇三洋化成株式会社制“GP-3000”羟值55.7mgKOH/g数均分子量3,020
850-S:双酚A型环氧树脂DIC株式会社制环氧当量188g/当量,羟基当量2900g/当量
EX-214:1,4-丁二醇型环氧树脂Nagase ChemteX株式会社制环氧当量137g/当量羟基当量1460g/当量
实施例1~11、比较例1
按照下述表2~3所示的配合,配合各成分,均匀地搅拌混合,获得了固化性组合物。对于该固化性组合物,以下述要领进行各种评价试验。将结果示于表2中。
实施例和比较例所使用的各成分的详细情况如下所述。
·环氧树脂(C-1):Nagase ChemteX株式会社制“Denacol EX-214”,1,4-丁二醇型环氧树脂,环氧当量137g/当量,
·双酚型环氧树脂:DIC株式会社制“EPICLON 850-S”环氧当量188g/当量
·酸酐(B-1):甲基四氢邻苯二甲酸酐(DIC株式会社制“EPICLON B-570-H”)
·酸酐(B-2):甲基六氢邻苯二甲酸酐(日立化成株式会社制“HN-5500”)
·固化促进剂:N,N-二甲基苄基胺
断裂韧性的测定
向200mm×100mm×6mm的铸模中注入固化性组合物,在120℃加热固化2小时,接着在140℃加热固化2小时,获得了固化物。关于所得的固化物,按照ASTM D 5045,测定KIC的值。
伸长率的测定
向200mm×100mm×4mm的铸模中注入固化性组合物,在120℃加热固化2小时,接着在140℃加热固化2小时,获得了固化物。关于所得的固化物,按照JIS K7162,实施拉伸试验,测定伸长值。
抗拉强度的测定
使用长丝缠绕装置,一边使固化性组合物含浸于碳纤维(东丽株式会社制,“T700SC-12,000”),一边卷绕,在120℃加热固化2小时,接着在140℃加热固化2小时,获得了纤维体积含有率(Vf)60%、厚度2mm的纤维增强树脂成型物。将该板切断,按照JISK7165,实施了拉伸试验。
[表2]
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | |
(A-1) | 41 | |||||
(A-2) | 41 | |||||
(A-3) | 39 | |||||
(A-4) | 38 | |||||
(A-5) | 40 | |||||
(A-6) | 41 | |||||
(A-7) | ||||||
(A-8) | ||||||
(A-9) | ||||||
(A-10) | ||||||
环氧树脂(C-1) | 16 | 16 | 16 | 15 | 16 | 16 |
双酚型环氧树脂 | ||||||
酸酐(B-1) | 43 | 43 | 45 | 46 | 43 | 43 |
酸酐(B-2) | ||||||
固化促进剂 | 1 | 1 | 1 | 1 | 1 | 1 |
断裂韧性(K<sub>IC</sub>)[MPa/m<sup>1/2</sup>] | 1.25 | 1.2 | 0.82 | 0.7 | 0.95 | 1.19 |
伸长[%] | 13.2 | 12.7 | 12 | 8.5 | 8 | 14 |
抗拉强度[MPa] | 2,190 | 2,100 | 2,080 | 2,070 | 2,110 | 2,150 |
[表3]
实施例7 | 实施例8 | 实施例9 | 实施例10 | 实施例11 | 比较例1 | |
(A-1) | ||||||
(A-2) | 41 | |||||
(A-3) | ||||||
(A-4) | ||||||
(A-5) | ||||||
(A-6) | ||||||
(A-7) | 41 | |||||
(A-8) | 38 | |||||
(A-9) | 41 | |||||
(A-10) | 57 | |||||
环氧树脂(C-1) | 16 | 15 | 16 | 16 | ||
双酚型环氧树脂 | 53 | |||||
酸酐(B-1) | 43 | 47 | 43 | 43 | 47 | |
酸酐(B-2) | 43 | |||||
固化促进剂 | 1 | 1 | 1 | 1 | 1 | 1 |
断裂韧性(K<sub>IC</sub>)[MPa/m<sup>1/2</sup>] | 1.03 | 0.72 | 0.94 | 1.22 | 1.12 | 0.55 |
伸长[%] | 7.5 | 7.9 | 6.3 | 12.9 | 10.2 | 4.8 |
抗拉强度[MPa] | 2,180 | 2,080 | 2,110 | 2,090 | 2,180 | 1970 |
Claims (13)
1.一种固化性组合物,其特征在于,为将氨基甲酸酯改性环氧树脂(A)作为主剂的必须成分、将酸酐(B)作为固化剂的必须成分的固化性组合物,所述氨基甲酸酯改性环氧树脂(A)为将多异氰酸酯化合物(a1)、聚醚多元醇(a2)和含有羟基的环氧树脂(a3)作为必须的反应原料的反应生成物。
2.根据权利要求1所述的固化性组合物,所述聚醚多元醇(a2)为数均分子量(Mn)500~4,000的聚醚二醇。
3.根据权利要求1所述的固化性组合物,所述聚醚多元醇(a2)中的聚醚二醇的含有率为80质量%以上。
4.根据权利要求1所述的固化性组合物,所述多异氰酸酯化合物(a1)的异氰酸酯基含量为35质量%以上。
5.根据权利要求1所述的固化性组合物,所述氨基甲酸酯改性环氧树脂(A)相对于所述主剂所含有的环氧树脂成分的总质量的比例为30~100质量%的范围。
6.根据权利要求1所述的固化性组合物,所述主剂中,除了所述氨基甲酸酯改性环氧树脂(A)以外,含有脂肪族环氧树脂。
7.根据权利要求6所述的固化性组合物,所述氨基甲酸酯改性环氧树脂(A)与所述脂肪族环氧树脂的质量比、即氨基甲酸酯改性环氧树脂(A)/脂肪族环氧树脂为30/70~100/0的范围。
8.根据权利要求1~7中任一项所述的固化性组合物,所述酸酐(B)为甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐或甲基内亚乙基四氢邻苯二甲酸酐。
9.根据权利要求1~8中任一项所述的固化性组合物,其进一步含有固化促进剂(C)。
10.权利要求1~9中任一项所述的固化性组合物的固化物。
11.一种纤维增强复合材料,其将权利要求1~9中任一项所述的固化性组合物以及增强纤维作为必须成分。
12.一种纤维增强树脂成型品,其将权利要求10所述的固化物和增强纤维作为必须成分。
13.一种纤维增强树脂成型品的制造方法,其使权利要求12所述的纤维增强复合材料热固化。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019144483 | 2019-08-06 | ||
JP2019-144483 | 2019-08-06 | ||
PCT/JP2020/029181 WO2021024893A1 (ja) | 2019-08-06 | 2020-07-30 | 硬化性組成物、硬化物、繊維強化複合材料及び成形品 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114127152A true CN114127152A (zh) | 2022-03-01 |
CN114127152B CN114127152B (zh) | 2024-05-31 |
Family
ID=
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116535822A (zh) * | 2023-06-29 | 2023-08-04 | 泰和新材集团股份有限公司 | 一种用于芳纶复合材料iv型瓶的树脂胶液及制备方法 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58191723A (ja) * | 1982-05-04 | 1983-11-09 | Dainippon Ink & Chem Inc | エポキシシ−トモ−ルデイングコンパウンドの製造方法 |
JP2011105916A (ja) * | 2009-11-20 | 2011-06-02 | Kyocera Chemical Corp | プリプレグ、多層プリント配線板およびフレキシブルプリント配線板 |
CN103113604A (zh) * | 2013-01-28 | 2013-05-22 | 北京化工大学常州先进材料研究院 | 一种聚氨酯预聚体改善中低温固化预浸料层间剪切强度的制备方法 |
JP2014077074A (ja) * | 2012-10-11 | 2014-05-01 | Nagoya Electrical Educational Foundation | ポリウレタン変性エポキシ樹脂とその製造方法および硬化物 |
JP2015081329A (ja) * | 2013-10-24 | 2015-04-27 | Dic株式会社 | ウレタン変性エポキシ樹脂、硬化性組成物、その硬化物、繊維強化複合材料、及び繊維強化樹脂成型品 |
JP2015086374A (ja) * | 2013-09-26 | 2015-05-07 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物 |
JP2016011409A (ja) * | 2014-06-03 | 2016-01-21 | 学校法人 名古屋電気学園 | ポリウレタン変性エポキシ樹脂、その製造方法、エポキシ樹脂組成物および硬化物 |
CN106232692A (zh) * | 2014-04-15 | 2016-12-14 | 三菱瓦斯化学株式会社 | 纤维强化复合材料 |
JP2017002130A (ja) * | 2015-06-05 | 2017-01-05 | Dic株式会社 | ポリウレタン変性エポキシ樹脂及び接着剤 |
JP2017078125A (ja) * | 2015-10-21 | 2017-04-27 | 新日鉄住金化学株式会社 | ウレタン変性エポキシ樹脂組成物、およびその硬化物 |
CN106715581A (zh) * | 2014-09-25 | 2017-05-24 | Dic株式会社 | 环氧树脂组合物、固化物、纤维增强复合材料、纤维增强树脂成形品、及纤维增强树脂成形品的制造方法 |
CN106867008A (zh) * | 2017-03-24 | 2017-06-20 | 北京化工大学 | 一种增韧中温固化预浸料的制备方法 |
CN107001567A (zh) * | 2014-10-13 | 2017-08-01 | Sika技术股份公司 | 作为环氧制剂中的抗冲改进剂的聚酯预聚物 |
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58191723A (ja) * | 1982-05-04 | 1983-11-09 | Dainippon Ink & Chem Inc | エポキシシ−トモ−ルデイングコンパウンドの製造方法 |
JP2011105916A (ja) * | 2009-11-20 | 2011-06-02 | Kyocera Chemical Corp | プリプレグ、多層プリント配線板およびフレキシブルプリント配線板 |
JP2014077074A (ja) * | 2012-10-11 | 2014-05-01 | Nagoya Electrical Educational Foundation | ポリウレタン変性エポキシ樹脂とその製造方法および硬化物 |
CN103113604A (zh) * | 2013-01-28 | 2013-05-22 | 北京化工大学常州先进材料研究院 | 一种聚氨酯预聚体改善中低温固化预浸料层间剪切强度的制备方法 |
JP2015086374A (ja) * | 2013-09-26 | 2015-05-07 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物 |
JP2015081329A (ja) * | 2013-10-24 | 2015-04-27 | Dic株式会社 | ウレタン変性エポキシ樹脂、硬化性組成物、その硬化物、繊維強化複合材料、及び繊維強化樹脂成型品 |
CN106232692A (zh) * | 2014-04-15 | 2016-12-14 | 三菱瓦斯化学株式会社 | 纤维强化复合材料 |
JP2016011409A (ja) * | 2014-06-03 | 2016-01-21 | 学校法人 名古屋電気学園 | ポリウレタン変性エポキシ樹脂、その製造方法、エポキシ樹脂組成物および硬化物 |
CN106414542A (zh) * | 2014-06-03 | 2017-02-15 | 新日铁住金化学株式会社 | 聚氨酯改性环氧树脂、其制造方法、环氧树脂组合物及固化物 |
CN106715581A (zh) * | 2014-09-25 | 2017-05-24 | Dic株式会社 | 环氧树脂组合物、固化物、纤维增强复合材料、纤维增强树脂成形品、及纤维增强树脂成形品的制造方法 |
CN107001567A (zh) * | 2014-10-13 | 2017-08-01 | Sika技术股份公司 | 作为环氧制剂中的抗冲改进剂的聚酯预聚物 |
JP2017002130A (ja) * | 2015-06-05 | 2017-01-05 | Dic株式会社 | ポリウレタン変性エポキシ樹脂及び接着剤 |
JP2017078125A (ja) * | 2015-10-21 | 2017-04-27 | 新日鉄住金化学株式会社 | ウレタン変性エポキシ樹脂組成物、およびその硬化物 |
CN106867008A (zh) * | 2017-03-24 | 2017-06-20 | 北京化工大学 | 一种增韧中温固化预浸料的制备方法 |
Non-Patent Citations (2)
Title |
---|
HUEI-HSIUNG WANG 等: "Toughening of epoxy resin by functional-terminated polyurethanes and/or semicrystalline polymer powders", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 82, no. 12, 2 October 2001 (2001-10-02), pages 2903 - 2912 * |
李祥新 等: "聚氨酯改性室温固化环氧结构胶粘剂的研究", 粘接, vol. 27, no. 6, 15 December 2006 (2006-12-15), pages 1 - 3 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116535822A (zh) * | 2023-06-29 | 2023-08-04 | 泰和新材集团股份有限公司 | 一种用于芳纶复合材料iv型瓶的树脂胶液及制备方法 |
CN116535822B (zh) * | 2023-06-29 | 2023-10-17 | 泰和新材集团股份有限公司 | 一种用于芳纶复合材料iv型瓶的树脂胶液及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2021024893A1 (ja) | 2021-02-11 |
JPWO2021024893A1 (ja) | 2021-09-13 |
JP6958751B2 (ja) | 2021-11-02 |
US20220251285A1 (en) | 2022-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1954759B1 (en) | Curable compositions | |
JP5954516B1 (ja) | エポキシ樹脂組成物、硬化物、繊維強化複合材料、繊維強化樹脂成形品、及び繊維強化樹脂成形品の製造方法 | |
EP2331624B1 (en) | Benzoxazine-based compositions containing isocyanate-based tougheners | |
US20230167228A1 (en) | Curable composition and fiber reinforced composite material | |
EP3708600B1 (en) | Curable composition and fiber-reinforced composite material | |
JP6825757B1 (ja) | エポキシ樹脂組成物、硬化物、繊維強化複合材料、プリプレグ及びトウプリプレグ | |
JP6304525B2 (ja) | ウレタン変性エポキシ樹脂、硬化性組成物、その硬化物、繊維強化複合材料、及び繊維強化樹脂成型品 | |
JP6923090B2 (ja) | 硬化性組成物、硬化物、繊維強化複合材料、成形品及びその製造方法 | |
CN114127152B (zh) | 固化性组合物、固化物、纤维增强复合材料及成型品 | |
JP6958751B2 (ja) | 硬化性組成物、硬化物、繊維強化複合材料及び成形品 | |
KR102297539B1 (ko) | 에폭시 접착제 조성물을 위한 트리블록 구조의 폴리우레탄 강인화제 | |
US20220403099A1 (en) | Curable composition, cured product, fiber-reinforced composite material, and molded article, and method for manufacturing same | |
EP4101878A1 (en) | Molding material and fiber reinforced composite material | |
JP6780317B2 (ja) | 硬化性組成物及び繊維強化複合材料 | |
JP6780318B2 (ja) | 硬化性組成物及び繊維強化複合材料 | |
JP6606924B2 (ja) | エポキシ樹脂組成物、硬化物、繊維強化複合材料、繊維強化樹脂成形品、及び繊維強化樹脂成形品の製造方法 | |
JP7160219B1 (ja) | 熱硬化性エポキシ樹脂組成物とその成形品、繊維強化複合材料、繊維強化複合材料用成形材料、および繊維強化複合材料の製造方法 | |
JP2018141143A (ja) | 繊維強化プラスチック用樹脂組成物、その硬化物、及び該硬化物を含有する繊維強化プラスチック |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant |