JPH0253468B2 - - Google Patents
Info
- Publication number
- JPH0253468B2 JPH0253468B2 JP9972381A JP9972381A JPH0253468B2 JP H0253468 B2 JPH0253468 B2 JP H0253468B2 JP 9972381 A JP9972381 A JP 9972381A JP 9972381 A JP9972381 A JP 9972381A JP H0253468 B2 JPH0253468 B2 JP H0253468B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- copolymer
- resin
- weight
- block copolymer
- 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.)
- Expired
Links
- -1 vinyl aromatic compound Chemical class 0.000 claims description 68
- 229920001400 block copolymer Polymers 0.000 claims description 61
- 229920002554 vinyl polymer Polymers 0.000 claims description 59
- 239000000178 monomer Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 49
- 239000011342 resin composition Substances 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 32
- 229920001577 copolymer Polymers 0.000 claims description 31
- 229920005992 thermoplastic resin Polymers 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 229920000578 graft copolymer Polymers 0.000 claims description 26
- 125000003277 amino group Chemical group 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920006122 polyamide resin Polymers 0.000 claims description 5
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000000113 methacrylic resin Substances 0.000 claims description 2
- CRQSAKXMWFFXJG-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methyl]oxirane Chemical compound C1=CC(C=C)=CC=C1CC1OC1 CRQSAKXMWFFXJG-UHFFFAOYSA-N 0.000 claims 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229920001002 functional polymer Polymers 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ARYIITVULFDIQB-UHFFFAOYSA-N (2-methyloxiran-2-yl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1(C)CO1 ARYIITVULFDIQB-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- SYJPAKDNFZLSMV-HYXAFXHYSA-N (Z)-2-methylpropanal oxime Chemical compound CC(C)\C=N/O SYJPAKDNFZLSMV-HYXAFXHYSA-N 0.000 description 1
- PNNFEYPWPCDLOC-UPHRSURJSA-N (z)-2,3-dichlorobut-2-enedioic acid Chemical compound OC(=O)C(\Cl)=C(\Cl)C(O)=O PNNFEYPWPCDLOC-UPHRSURJSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-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
- UTQHMFFTYBUYGA-UHFFFAOYSA-N 2-(3-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=CC(C=C)=C1 UTQHMFFTYBUYGA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ZPBLGHJTLUGKTG-UHFFFAOYSA-N 2-(3-phenylprop-2-enyl)oxirane Chemical compound C1OC1CC=CC1=CC=CC=C1 ZPBLGHJTLUGKTG-UHFFFAOYSA-N 0.000 description 1
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- MUUOUUYKIVSIAR-UHFFFAOYSA-N 2-but-3-enyloxirane Chemical compound C=CCCC1CO1 MUUOUUYKIVSIAR-UHFFFAOYSA-N 0.000 description 1
- JRKURGYOYLHRHT-UHFFFAOYSA-N 2-ethenyl-2,3-dimethyloxirane Chemical compound CC1OC1(C)C=C JRKURGYOYLHRHT-UHFFFAOYSA-N 0.000 description 1
- FVCDMHWSPLRYAB-UHFFFAOYSA-N 2-ethenyl-2-methyloxirane Chemical compound C=CC1(C)CO1 FVCDMHWSPLRYAB-UHFFFAOYSA-N 0.000 description 1
- SZERAFCDZCHRQS-UHFFFAOYSA-N 2-ethenyl-3-methyloxirane Chemical compound CC1OC1C=C SZERAFCDZCHRQS-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- AAYSXEMBWUMDIZ-UHFFFAOYSA-N 2-methyl-n,n-dipropylprop-2-enamide Chemical compound CCCN(CCC)C(=O)C(C)=C AAYSXEMBWUMDIZ-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920013632 Ryton Polymers 0.000 description 1
- 239000004736 Ryton® Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- FRAZBEUBMBOYDF-UHFFFAOYSA-N butoxymethanamine Chemical compound CCCCOCN FRAZBEUBMBOYDF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 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
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- LZMQMUZCPILQGI-UHFFFAOYSA-N n,n-dibutyl-2-methylprop-2-enamide Chemical compound CCCCN(C(=O)C(C)=C)CCCC LZMQMUZCPILQGI-UHFFFAOYSA-N 0.000 description 1
- DLJMSHXCPBXOKX-UHFFFAOYSA-N n,n-dibutylprop-2-enamide Chemical compound CCCCN(C(=O)C=C)CCCC DLJMSHXCPBXOKX-UHFFFAOYSA-N 0.000 description 1
- JMCVCHBBHPFWBF-UHFFFAOYSA-N n,n-diethyl-2-methylprop-2-enamide Chemical compound CCN(CC)C(=O)C(C)=C JMCVCHBBHPFWBF-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 1
- WKEHOEOBHHJZPS-UHFFFAOYSA-N n-[2-(4-ethenylphenyl)ethyl]propan-2-amine Chemical compound CC(C)NCCC1=CC=C(C=C)C=C1 WKEHOEOBHHJZPS-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- QQZXAODFGRZKJT-UHFFFAOYSA-N n-tert-butyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC(C)(C)C QQZXAODFGRZKJT-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XYKIUTSFQGXHOW-UHFFFAOYSA-N propan-2-one;toluene Chemical compound CC(C)=O.CC1=CC=CC=C1 XYKIUTSFQGXHOW-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Description
本発明は、反応性官能基を有する重合体を２種
以上ブレンドすることにより製造されるグラフト
共重合体から成る耐衝撃性、機械的特性、成形加
工性に優れた熱可塑性樹脂組成物に関する。
さらに詳しくは、エポキシ基含有ビニル単量
体、アミノ基含有ビニル単量体のうちから選ばれ
る少なくとも１種の単量体と当該単量体と共重合
し得る他のビニル系単量体１種以上とを共重合し
て成る多元共重合体と、ビニル芳香族化合物―共
役ジエン化合物共重合体をエチレン系不飽和ジカ
ルボン酸またはその誘導体で変性したブロツク共
重合体と、エチレン系不飽和ジカルボン酸無水物
を重合体構成成分として含まない熱可塑性樹脂と
を含有して成る耐衝撃性、機械的強度に優れた熱
可塑性樹脂組成物に関する。
従来、熱可塑性樹脂の耐衝撃性改良剤として
は、例えば、ポリブタジエン、スチレン―ブタジ
エン共重合体のごときゴム状物質がよく知られて
いる。
これらのゴム状物質の使用態様としては、熱可
塑性樹脂に直接ブレンドしてゴム状物質を樹脂中
に分散させる方法や、ゴム状物質の存在下にビニ
ル単量体をラジカル重合し、生成する熱可塑性樹
脂中にラジカルグラフト変性したゴム状物質をミ
クロ分散させる方法が公知となつている。
しかし、前者のゴム状物質を熱可塑性樹脂に直
接ブレンドする方法は、必ずしも耐衝撃性の向上
が期待できるものではなく、ブレンド物の種類、
ブレンド物組成、ブレンド方法、ブレンド物の成
形条件等によつてその効果は大きく変化する。例
えば、スチレン―ブタジエンブロツク共重合体／
ポリスチレンから成るブレンド物は、耐衝撃性の
向上を期待できるものの、ブレンド物のブレンド
方法、成形条件によつて耐衝撃性が大きく変化し
やすい。また、スチレン―ブタジエンブロツク共
重合体／スチレン―アクリロニトリル共重合体
（AS樹脂）から成るブレンド物は、両者の相溶性
が極めて悪く、耐衝撃性等の機械的強度を向上す
ることが難しいのが現状である。
一方、ゴム状物質の存在下にビニル単量体をグ
ラフト重合して得られるグラフト物（ゴム補強樹
脂；例えばハイインパクトポリスチレン等）につ
いても、近年、樹脂の耐衝撃性の改良がかなり試
みられているが、ゴム状物質のビニル単量体への
溶解性に制限があるとか、重合コントロールに極
めて煩雑な手法が要求されるなどの問題があり、
また工業規模で使用されるビニル単量体の種類が
限定されるため、得られるゴム補強樹脂も制限さ
れているのが現状である。
本発明者らは、このような背景のもとで、上記
の問題点を改良すべく鋭意研究を重ね、すでに特
願昭55−147552号では、エチレン系不飽和ジカル
ボン酸無水物と該モノマーと共重合可能なビニル
系モノマーを共重合して得られる多元共重合体の
耐衝撃性、機械的強度、耐熱性の改良を提案し
た。その後さらに官能性重合体のブレンドに関し
て研究を進めた結果、反応性官能基を有する重合
体を２種以上ブレンドして得られるグラフト組成
物が、エチレン系不飽和ジカルボン酸無水物を重
合体構成成分として含まない熱可塑性樹脂の所望
の性質を損なうことなしに優れた耐衝撃性を発揮
し、成形材料用途等に好適な組成物であることを
見出し、本発明に到達した。
すなわち、本発明は、(A)成分；エポキシ基含有
ビニル単量体、アミノ基含有ビニル単量体のうち
から選ばれる少なくとも１種の単量体と、当該単
量体と共重合し得る他のビニル系単量体の１種以
上とを共重合して得られる多元共重合体と、(B)成
分；少なくとも１個のビニル芳香族化合物を主体
とする重合体ブロツクと、少なくとも１個の共役
ジエン化合物を主体とする重合体ブロツクとから
成るブロツク共重合体100重量部あたりに、エチ
レン系不飽和ジカルボン酸基またはその誘導体基
を含む分子単位を0.05〜20重量部結合せしめて成
る変性ブロツク共重合体と(C)成分；エチレン系不
飽和ジカルボン酸無水物を重合体構成成分として
含まないスチレン系樹脂、ポリオレフイン系樹
脂、アクリロニトリル系樹脂、メタクリル樹脂、
ポリカーボネート、ポリスルフオン、塩化ビニル
系樹脂、ポリエステル樹脂、ポリアミド樹脂、ポ
リフエニレンサルフアイド、ポリイミド、ポリフ
エニレンオキシド、ふつ素樹脂、塩化ビニリデン
樹脂から選ばれた熱可塑性樹脂１種または２種以
上から成り、かかる(B)成分の変性ブロツク共重合
体のビニル芳香族化合物の含有量が５〜60重量％
の場合、配合組成比が(A)＋(B)／(C)＝５〜50／95〜
50（重量％）であり、かかる(B)成分の変性ブロツ
ク共重合体のビニル芳香族化合物の含有量が60重
量％を超え95重量％以下の場合、配合組成比が(A)
＋(B)／(C)＝５〜99／95〜１（重量％）であること
を特徴とするグラフト共重合体樹脂組成物に関す
る。
以下、本発明に関して詳細に説明する。
本発明の目的を達成するには、本発明の構成成
分である(A)成分、(B)成分、(C)成分が不可欠であ
り、これらの成分のうちどの一つが欠けても本発
明の目的は達成できない。すなわち、本発明は、
従来のブレンド組成物と異なり、官能基が有して
いる反応性を利用し、官能性重合体を２種以上ブ
レンドすることによりグラフト組成物を得るとい
う技術的に意義深い思想に基づくものであり、本
発明の(A)成分、(B)成分および(C)成分を必須構成成
分とすることによつてのみ達成されるグラフト共
重合体樹脂組成物である。
本発明で用いられる(A)成分の多元共重合体は、
エポキシ基含有ビニル単量体、アミノ基含有ビニ
ル単量体のうちから選ばれる少なくとも１種の単
量体と、当該単量体と共重合し得る他のビニル系
単量体の１種以上とを共重合して得られる多元共
重合体である。
有用な官能性単量体であるエポキシ基含有ビニ
ル単量体としては、例えば、グリシジルアクリレ
ート、グリシジルメタクリレート、β―メチルグ
リシジルアクリレート、β―メチルグリシジルメ
タクリレート、アリルグリシジルエテル、イタコ
ン酸モノグリシジルエステル、ブテントリカルボ
ン酸モノグリシジルエステル、ブテントリカルボ
ン酸ジグリシジルエステル、ブテントリカルボン
酸トリグリシジルエステル、スチレン―ｐ―グリ
シジルエーテル、３，４―エポキシブテン、３，
４―エポキシ―３―メチル―１―ブテン、３，４
―エポキシ―１―ペンテン、３，４―エポキシ―
３―メチルペンテン、５，６―エポキシ―１―ヘ
キセン、ビニルシクロヘキセンモノオキシド、ｐ
―グリシジルスチレンなどを挙げることができ
る。
また、有用な官能性単量体であるアミノ基含有
ビニル単量体としては、例えば、アクリルアミ
ド、メタクリルアミド、Ｎ―メチルアクリルアミ
ド、Ｎ―エチルアクリルアミド、Ｎ―プロピルア
クリルアミド、Ｎ―ブチルアクリルアミド、Ｎ，
Ｎ―ジメチルアクリルアミド、Ｎ，Ｎ―ジエチル
アクリルアミド、Ｎ，Ｎ―ジブチルアクリルアミ
ド、Ｎ―メチルメタクリルアミド、Ｎ―エチルメ
タクリルアミド、Ｎ―tert―ブチルメタクリルア
ミド、Ｎ，Ｎ―ジエチルメタクリルアミド、Ｎ，
Ｎ―ジプロピルメタクリルアミド、Ｎ，Ｎ―ジブ
チルメタクリルアミド、Ｎ―メチロールアクリル
アミド、Ｎ―ブトキシメチルアミド、Ｎ―イソブ
トキシメチルアクリルアミド、ダイアセトンアク
リルアミド、ｐ―（２―ビス（エチルアミノ）ア
ミノエチル）スチレン、ｐ―（２―イソプロピル
アミノエチル）スチレン、ｐ―（２―ジエチルア
ミノエチル）スチレン、ｍ―（２―ジエチルアミ
ノエチル）スチレン、２―Ｎ，Ｎ―ジメチルアミ
ノエチルアクリレート、２―Ｎ，Ｎ―ジエチルア
ミノエチルアクリレート、２―Ｎ，Ｎ―ジブチル
アミノエチルアクリレート、３―Ｎ，Ｎ―ジエチ
ルアミノプロピルアクリレート、２―Ｎ，Ｎ―ジ
ブチルアミノプロピルアクリレート、３―Ｎ，Ｎ
―ジブチルアミノプロピルアクリレート、２―
Ｎ，Ｎ―ジメチルアミノエチルメタクリレート、
２―Ｎ，Ｎ―ジエチルアミノエチルメタクリレー
ト、２―Ｎ，Ｎ―ジブチルアミノエチルメタクリ
レート、３―Ｎ，Ｎ―ジエチルアミノプロピルメ
タクリレート、２―Ｎ，Ｎ―ジブチルアミノプロ
ピルメタクリレートなどを挙げることができる。
さらに、これら官能性ビニル単量体と共重合し
得るその他のビニル単量体としては、例えば、エ
チレン、塩化ビニル、酢酸ビニル、ビニルトルエ
ン、α―メチルスチレン、スチレン、アクリロニ
トリル、ラウリルメタクリレート、ラウリルアク
リレート、シクロヘキシルメタクリレート、シク
ロヘキシルアクリレート、２―エチルヘキシルメ
タクリレート、２―エチルヘキシルアクリレー
ト、オクチルアクリレート、オクチルメタクリレ
ート、ターシヤリーブチルメタクリレート、ター
シヤリーブチルアクリレート、イソブチルアクリ
レート、イソブチルメタクリレート、ｎ―ブチル
メタクリレート、ｎ―ブチルアクリレート、イソ
プロピルメタクリレート、イソプロピルアクリレ
ート、プロピルアクリレート、プロピルメタクリ
レート、エチルメタクリレート、エチルアクリレ
ート、メチルメタクリレート、メチルアクリレー
トなどが挙げられ、さらに所望により、これらの
ビニル単量体の２種またはそれ以上の混合物も使
用することができる。
これら(A)成分の多元共重合体の製造方法は公知
の重合方法、例えば、溶液重合法、乳化重合法、
塊状重合法、塊状―懸濁重合法、懸濁重合法等に
よるラジカル重合方法が工業的に有利に用いられ
る。
このようにして得られるエポキシ基含有ビニル
単量体、アミノ基含有ビニル単量体のうちから選
ばれる少なくとも１種の単量体と、当該単量体と
共重合し得る他のビニル系単量体の１種以上とを
共重合して得られる多元共重合体は、低分子量の
共重合体も使用できるが、一般には分子量が5000
〜1000000、好ましくは10000〜800000、さらに好
ましくは20000〜500000のものが使用される。共
重合体中のエポキシ基またはアミノ基含有ビニル
単量体の含量は１〜50重量％が好ましく、さらに
好ましくは５〜30重量％である。
つぎに、本発明で用いられる(B)成分は、ビニル
芳香族化合物を主体とする重合体ブロツク１個以
上と共役ジエン化合物を主体とする重合体ブロツ
ク１個以上とを含有し、ビニル芳香族化合物と共
役ジエン化合物の重量比が５／95〜95／５である
ブロツク共重合体に、不飽和ジカルボン酸または
その誘導体が付加した変性ブロツク共重合体であ
る。
ここで、ビニル芳香族化合物を主体とする重合
体ブロツクとは、ビニル芳香族化合物重合体ブロ
ツクまたはビニル芳香族化合物の含有量が50重量
％を超え、好ましくは70重量％以上であるビニル
芳香族化合物と共役ジエン化合物との共重合体ブ
ロツクであり、共役ジエン化合物を主体とする重
合体ブロツクとは、共役ジエン化合物重合体ブロ
ツクまたは共役ジエン化合物の含有量が50重量％
を超え、好ましくは70重量％以上であるビニル芳
香族化合物と共役ジエン化合物との共重合体ブロ
ツクである。
上記変性ブロツク共重合体の基体となるビニル
芳香族化合物―共役ジエン化合物ブロツク共重合
体（以下単に「ブロツク共重合体」という）は、
ビニル芳香族化合物を主体とする重合体ブロツク
１個以上、好ましくは２個以上と、共役ジエン化
合物を主体とする重合体ブロツク１個以上とを含
有するものである。該ブロツク共重合体におい
て、ビニル芳香族化合物と共役ジエン化合物の重
量比は５／95〜95／５、好ましくは10／90〜90／
10、さらに好ましくは15／85〜85／15の組成範囲
である。
該ブロツク共重合体はビニル芳香族化合物の含
有量が60重量％以下、好ましくは55重量％未満の
場合はエラストマー的な性質を示し、６重量％を
超える場合、好ましくは70重量％以上の場合は樹
脂的な性質を示す。
また、ブロツク共重合体のビニル芳香族化合物
を主体とする重合体ブロツクおよび共役ジエン化
合物を主体とする重合体ブロツクのうち、ビニル
芳香族化合物と共役ジエン化合物との共重合体ブ
ロツクにおける分子鎖中のビニル芳香族化合物の
分布は、ランダム、テーパード（分子鎖に沿つて
モノマー成分が増加または減少するもの）、一部
ブロツク状またはこれらの任意の組合せで成つて
いてもよい。ビニル芳香族化合物を主体とする重
合体ブロツクが２個以上である場合は、各ブロツ
クは同一構造であつてもよく、異なる構造であつ
てもよい。また、共役ジエン化合物を主体とする
重合体ブロツクを２個以上含有する場合は、各ブ
ロツクは同一の構造であつてもよく、異なる構造
であつてもよい。
ブロツク共重合体を構成するビニル芳香族化合
物としては、例えば、スチレン、α―メチルスチ
レン、ビニルトルエン、ｐ―tert―ブチルスチレ
ン等のうちから１種または２種以上が選ばれ、中
でもスチレンが特に好ましい。また、共役ジエン
化合物としては、例えば、ブタジエン、イソプレ
ン、１，３―ペンタジエン、２，３―ジメチル―
１，３―ブタジエン等のうちから１種または２種
以上が選ばれ、中でもブタジエンまたはブタジエ
ンを主体とする共役ジエン化合物の組合わせが好
ましく、特にブタジエンが好ましい。
該ブロツク共重合体の数平均分子量は5000〜
1000000、好ましくは10000〜800000、さらに好ま
しくは30000〜500000の範囲であり、分子量分布
（重量平均分子量と数平均分子量の比）は10以下
である。
さらに、ブロツク共重合体の分子構造は、直鎖
状、分岐状、放射状あるいはこれらの任意の組合
わせのいずれであつてもよい。また、上記ブロツ
ク共重合体は、その特性を失わない限りにおいて
有機化合物あるいは無機化合物によつて若干の変
性が行われていてもよい。
本発明で用いるブロツク共重合体は、通常、ヘ
キサン、シクロヘキサン、ベンゼン、トルエン等
の不活性炭化水素溶媒中で、ブチルリチウム等の
有機リチウム化合物を重合触媒として、ビニル芳
香族化合物と共役ジエン化合物をアニオン共重合
することによつて得られ、この際、モノマーの添
加方法や添加順序を変えたり、多官能性のリチウ
ム化合物を使用することにより、各種構造のブロ
ツク共重合体が得られる。また、上記方法で得ら
れるリチウム活性末端を有するブロツク共重合体
を多官能カツプリング剤、例えば、四塩化炭素、
四塩化ケイ素等に反応させることにより、分岐
状、放射状のブロツク共重合体とすることが可能
である。その他いかなる製造方法で得られたビニ
ル芳香族化合物―共役ジエン化合物ブロツク共重
合体であつても、前記限定の範囲内であれば使用
できる。
上記ブロツク共重合体は、１種だけでなく、２
種類以上のものを組合わせたものでもよく、これ
らの組合わせの例としては、スチレン―ブタジエ
ンブロツク共重合体とスチレン―イソプレンブロ
ツク共重合体の組合わせ、分子量の異なる２種の
スチレン―ブタジエンブロツクの共重合体の組合
わせ、スチレン含量の異なる２種のスチレン―ブ
タジエンブロツク共重合体の組合わせ、ブロツク
構造がスチレン―ブタジエン―ステレンの三つの
セグメントからなるものと、ブタジエン―スチレ
ン―ブタジエン―ステレンの四つのセグメントか
らなるもの等のブロツク構造の異なるスチレン―
ブタジエンブロツク共重合体の組合わせなどがあ
る。
つぎに、ブロツク共重合体にグラフトした不飽
和ジカルボン酸またはその誘導体について説明す
る。これら不飽和ジカルボン酸またはその誘導体
は、ブロツク共重合体に付加している。これらは
ブロツク共重合体100重量部あたり0.05〜20重量
部、好ましくは0.05〜10重量部、さらに好ましく
は0.1〜５重量部付加していることが、グラフト
共重合体樹脂組成物の目的の特性を引き出すため
に必要である。付加量が0.05重量部未満では未変
性のブロツク共重合体に比してほとんど改良効果
がなく、付加量を20重量部以上にしても改善効果
はそれ以上向上しない。
上記不飽和ジカルボン酸またはその誘導体の例
としては、マレイン酸、フマル酸、イタコン酸、
ジクロロマレイン酸、シス―４―シクロヘキセン
―１，２―ジカルボン酸、エンド―シス―ビシク
ロ〔２，２，１〕―５―ヘプテン―２，３―ジカ
ルボン酸などや、これらジカルボン酸の酸無水
物、エステル、アミド、ジカルボン酸イミドなど
があげられる。ジカルボン酸の各種誘導体は、誘
導体のままブロツク共重合体に付加させてもよ
く、また、不飽和ジカルボン酸をブロツク共重合
体に付加させた後、しかるべき反応によつてカル
ボン酸基を対応する誘導体に変換してもよい。
上記のブロツク共重合体を変性する不飽和ジカ
ルボン酸またはその誘導体の中では、マレイン
酸、フマル酸、無水マレイン酸が好ましい。
本発明の変性ブロツク共重合体は、前記ブロツ
ク共重合体に、不飽和ジカルボン酸またはその誘
導体を溶融状態または溶液状態において、ラジカ
ル開始剤を使用あるいは使用することなくグラフ
ト反応させることにより得られる。これら変性ブ
ロツク共重合体の製造方法に関しては、本発明で
は特に限定しないが、得られた変性ブロツク共重
合体中にゲル等の好ましくない成分が含まれてい
たり、その流動性が低下して加工性が悪化するよ
うな製造方法は好ましくない。好ましい方法とし
ては、例えば、押出機中で、パーオキサイドを添
加せずにブロツク共重合体を不飽和ジカルボン酸
またはその誘導体と反応させる方法がある。押出
機を使用した反応においては、一般に使用されて
いるゲル化防止剤を使用することが好ましい。
つぎに、本発明で用いられる(C)成分は、エチレ
ン系不飽和ジカルボン酸無水物を重合体構成成分
として含まない熱可塑性樹脂であり、例えば、ス
チレン―無水マレイン酸共重合体等のエチレン系
不飽和ジカルボン酸無水物またはその誘導体を構
成単量体としてラジカル共重合した熱可塑性樹脂
は本発明外である。
本発明の範囲内にある熱可塑性樹脂、すなわ
ち、(C)成分は、スチレン系樹脂、ポリオレフイン
系樹脂、アクリロニトリル系樹脂、メタクリル樹
脂、ポリカーボネート、ポリスルフオン、塩化ビ
ニル系樹脂、ポリエステル樹脂、ポリアミド樹
脂、ポリフエニレンサルフアイド、ポリイミド、
ポリフエニレンオキシド、ふつ素樹脂、塩化ビニ
リデン樹脂であり、具体的には、ポリスチレン、
耐衝撃性ポリスチレン、スチレン―アクリロニト
リル共重合体、ABS樹脂、スチレン―アクリル
酸共重合体、スチレン―アクリル酸エステル共重
合体、スチレン―メタクリル酸共重合体、スチレ
ン―メタクリル酸エステル共重合体、MBS樹脂、
ポリエチレン、塩素化ポリエチレン、ポリプロピ
レン、エチレン共重合体、プロピレン共重合体、
ポリブテン―１、ポリ―４―メチルペンテン―
１、ポリ―３―メチル―１―ペンテン、ポリ―３
―メチル―１―ブテン、アクリロニトリル―アク
リル酸共重合体、、アクリロニトリル―アクリル
酸エステル共重合体、ポリメタクリル酸エステ
ル、ポリ塩化ビニル、ポリエチレンテレフタレー
ト、ポリブチレンテレフタレート、ポリヘキサメ
チレンアジパミド、ポリカプロラクタム、ポリヘ
キサメチレンセバカミド、ポリヘキサメチレンイ
ソフタルアミド、ポリヘキサメチレンテレフタル
アミドイソフタルアミドなどがあげられるが、こ
れらに限られるものではない。
本発明のグラフト共重合体樹脂組成物は、上記
に掲げた(A)成分、(B)成分、(C)成分から構成される
ものであり、本発明の趣旨を損なわない限りさら
に所望により他の熱可塑性樹脂を混合してもかま
わない。
本発明で用いる(B)成分のジカルボン酸基または
その誘導体基は、(A)成分が有するエポキシ基、ア
ミノ基と反応し、本発明で意義深いグラフト物
（Ａ―Ｂグラフト物）を提供し、(C)成分の熱可塑
性樹脂中に任意に分散させることにより、(C)成分
の耐衝撃性等の機械的強度を向上させることがで
きる。
ここで用いる(A)成分、(C)成分の関係は、(A)成分
の多元共重合体と(C)成分の熱可塑性樹脂の溶解度
パラメータの差（Δδ）がΔδ≦３（δは溶解度パ
ラメーターであり、構成元素の凝集エネルギー密
度と分子容の比の平方根で表され、Hildebrand
とScottによつて定義されたものである。溶解度
パラメーターの値は、例えば、Polymer
Handbookの第四章341〜368に記載されており、
さらにJournal of Applied Chemistry第３巻第
71〜80頁、1953年のSmallの報文データを用いて
構成要素から計算することができる。）、好ましく
はΔδ≦1.5、さらに好ましくはΔδ≦1.0であり、
これがＡ―Ｂグラフト物と(C)成分の相溶性を良く
する上で望ましい。特に好ましい実施態様は、(A)
成分の多元共重合体が、エポキシ基含有ビニル単
量体、アミノ基含有ビニル単量体から選ばれる少
なくとも１種の単量体と、(C)成分の熱可塑性樹脂
を構成している少なくとも１種以上の同種の単量
体と当該単量体とを共重合した多元共重合体であ
ることが望ましい。
本発明のグラフト共重合体樹脂組成物は、エポ
キシ基含有ビニル単量体、アミノ基含有ビニル単
量体のうちから選ばれる少なくとも１種の単量体
と、当該単量体と共重合し得る他のビニル系単量
体１種以上とを共重合して成る多元共重合体(A)
と、少なくとも１個のビニル芳香族化合物を主体
とする重合体ブロツクと少なくとも１個の共役ジ
エン化合物を主体とする重合体ブロツクから成る
ブロツク共重合体に、エチレン系不飽和ジカルボ
ン酸基またはその誘導体基を享む分子単位を結合
せしめて成る変性ブロツク共重合体(B)と、エチレ
ン系不飽和ジカルボン酸無水物を重合体構成成分
として含まない熱可塑性樹脂(C)とをブレンドする
ことによつて得られるグラフト共重合体樹脂組成
物である。
本発明のグラフト共重合体樹脂組成物は、上記
に示した(A)成分、(B)成分、(C)成分の各組成および
配合量を選ぶことにより、熱可塑性樹脂組成物と
して得ることができる。すなわち、本発明の熱可
塑性樹脂組成物は、例えば、(C)成分が熱可塑性樹
脂組成物のマトリツクスを形成するような配合量
の領域で(A)成分、(B)成分から成るグラフト共重合
体を(C)成分中に分散させて得ることができる。(B)
成分の変性ブロツク共重合体のビニル芳香族化合
物の含有量が５〜60重量％の場合、その配合組成
比として(A)＋(B)／(C)＝５〜50／95〜50、好ましく
は10〜40／90〜60（重量％）を選定することがで
きる。さらに、グラフト共重合体を構成する(B)成
分の変性ブロツク共重合体のビニル芳香族化合物
の含有量が60重量％を超え95重量％以下の場合、
好ましくは70重量％以上90重量％以下の場合は、
(C)成分がマトリツクスを形成する配合量でもある
いは形成しない配合量のどちらの領域でも熱可塑
性樹脂組成物として得ることができる。その配合
組成比として(A)＋(B)／(C)＝５〜99／95〜１、好ま
しくは10〜90／90〜10（重量％）を選定すること
ができる。
本発明のグラフト共重合体樹脂組成物におい
て、(A)成分と(B)成分の配合量比は、一般に(A)／(B)
＝３〜90／97〜10、好ましくは５〜70／95〜30、
さらに好ましくは10〜50／90〜50（重量％）の範
囲から選定される。
このように本発明のグラフト共重合体樹脂組成
物は、(A)成分と(B)成分および(C)成分から成る熱可
塑性樹脂組成物であり、得られるグラフト共重合
体樹脂組成物は、各種成形材料用途に好適に使用
できる。
本発明のグラフト共重合体樹脂組成物は、一般
の高分子物質の混合に用いられる各種混合装置に
より、溶融状態で混合することによつて調製でき
る。それらの混合装置として好適なものは、例え
ば、一軸または多軸のスクリユー型押出機、ミキ
シングロール、バンバリーミキサー、ニーダー、
ブラベンダー等の混合装置が挙げられる。
本発明の組成物を調製するにあたり、(A)成分、
(B)成分を前もつて混合しＡ―Ｂグラフト共重合体
を得、次いで、(C)成分を添加し混合する方法が好
ましいが、その他本発明の効果が発揮できるよう
な任意の混合方法を選んでもかまわない。また、
本発明の組成物を調製するための混合条件は、本
発明の構成成分(A)，(B)各成分が本発明の主旨であ
る官能基によるグラフト反応を十分達成するよう
な混合温度、混合時間が選ばれる。(A)，(B)，(C)各
成分の通常混合温度は、一般に各成分の融点以上
で行われ、混合時間は、各成分が相互に分散する
まで行われるが、変性ブロツク共重合体がゲル化
するような高い温度ないし長時間混合を続けるこ
とは好ましくない。
この混合の際、必要に応じてグラフト反応を促
進させるため、第３級アミン、アンモニウム塩、
有機酸塩、有機キレート化合物等の触媒を添加し
てもよい。
また、本発明の組成物は、上記に示した混合装
置による混合の他に、本発明の構成成分および必
要に応じて触媒を適当な溶媒中で混合して得るこ
とも可能である。
該グラフト共重合体樹脂組成物はさらに他のゴ
ム状物質、例えば、天然ゴム、ポリブタジエン、
ポリ（スチレン／ブタジエン）、ポリ（エチレ
ン／プロピレン／非共役ジエン）等をその性質を
損なわない程度に混合してもよく、また、添加剤
として、例えば、酸化防止剤、熱安定剤、紫外線
吸収剤、着色剤、滑剤、難燃剤、顔料等を添加す
ることも可能である。
本発明で得られるグラフト共重合体樹脂組成物
は、耐衝撃性、機械的特性、成形加工性に優れる
ため、従来からのスチレン系樹脂、ポリオレフイ
ン系樹脂等の成形に用いられている圧縮成形、射
出成形、押出成形（インフレーシヨン法やＴダイ
法によるシートおよびフイルム、共押出しラミネ
ーシヨンや一軸延伸方法あるいは二軸延伸方法に
よるフイルムおよびシートの製造や、ストレート
ダイ、オフセツトダイ、クロスヘツドダイによる
パイプ押出し等）や、薄物シートの成形方法のカ
レンダー成形、円筒金型内に粉末状樹脂を入れ、
加熱、回転して成形する回転成形、発泡体ペレツ
トを金型内に充填し加熱発泡させて成形する注型
成形、シート類の真空成形、二軸延伸シート等の
圧空成形等、各種成形方法を用いることも可能で
ある。これらの成形物は、フイルム、シート、成
形品等の形態で、接着材料、包装材料、雑貨玩
具、電気部品、機械部品、自動車部品、その他各
種用途において広い利用範囲があり、有用な組成
物である。
また、本発明のグラフト共重合体樹脂組成物に
補強充填剤、例えば、ガラス繊維、ガラスフレー
ク、炭素繊維、チタン酸カリウム、二酸化チタ
ン、チタン酸ホイスカー、無水マイカ、ケイ酸カ
ルシウム、無水ケイ酸、ワラステナイト、炭酸カ
ルシウム、ガラス球、アスベスト、アルミナ、ア
ルミニウム、鉄、ニツケル等を添加し、補強充填
剤を含んだ樹脂組成物とすることができる。なか
でも、ガラス繊維、炭素繊維が補強充填剤として
好ましい。ガラス繊維を用いる場合、使用するガ
ラス繊維は、一般のガラス繊維強化樹脂で用いら
れるものでよく、通常その直径が２〜20μであ
り、長さは加工性、実用物性上最も適当とされる
長さに切断されたものを使用するのが好ましく、
ガラス繊維の表面をシラン系処理剤またはクロム
系処理剤で表面処理されたものが使用される。
さらに、本発明のグラフト共重合体樹脂組成物
に発泡剤、例えば、物理発泡剤、（ｎ―プロパン、
ｎ―ブタン、ｎ―ペンタン等の炭化水素類）や、
化学発泡剤（アゾ系発泡剤、ニトロソ系発泡剤、
スルホニルヒドラジド系発泡剤）や、無機系の発
泡剤としての重炭酸塩等を混入または圧入し、発
泡させた発泡体とすることができる。
このようにして得られるグラフト共重合体樹脂
組成物の補強充填剤を含んだ組成物および発泡体
組成物は、ともに機械的強度、耐衝撃性に優れる
ため、機械部品、電気部品、自動車部品等の各種
用途において利用範囲があり、有用な組成物であ
る。
以下、若干の実施例を示すが、これは本発明を
より具体的に説明するものであり、本発明の範囲
をこれらの例に限定するものないことは言うまで
もない。
なお、以下の実施例では、(A)成分と(C)成分の溶
解度パラメータの差（Δδ）が３未満のものを用
いた。
参考例
〔変性ブロツク共重合体の調製〕
スチレン―ブタジエンブロツク共重合体の熱可
塑性エラストマーである試料ｐを用いて、以下に
示す方法により無水マレイン酸がグラフトした変
性ブロツク共重合体（試料Ｐ）を得た。なお、試
料ｐはヘキサン溶液中においてｎ―ブチルリチウ
ムを触媒として得られたものであり、以下にその
基本特性を示す。
ポリマー構造；Ｂ―Ｓ―Ｂ―Ｓ（直鎖状）
（Ｂ；ブタジエン、Ｓ；スチレン）
スチレン含有量；42重量％
ブロツク・スチレン含有量；36重量％
重量平均分子量（Mw）；79000
数平均分子量（Mn）；61000
メルトインデツクス；12.0ｇ／10min
（JIS―Ｋ―6870、荷重５Kg、200℃）
試料ｐの100重量部に対し、４重量部の無水マ
レイン酸、ゲル化防止剤として0.3重量部のBHT
（ブチルヒドロキシトルエン）と0.3重量部のフエ
ノチアジンを添加し、これらをミキサーを用いて
均一に混合した。
この混合物を窒素雰囲気下で、40mm押出機（単
軸、フルフライト型スクリユー、Ｌ／Ｄ＝24）に
供給し、シリンダー温度190〜260℃で変性反応を
行つた。得られたポリマーは、未反応の無水マレ
イン酸を減圧乾燥により除去した。変性ブロツク
共重合（試料Ｐ）の分析結果は、メルトインデツ
クスが8.5ｇ／10min、トルエン不溶分が0.05重量
％、ナトリウムメチラートによる滴定で測定した
無水マレイン酸の付加量がブロツク共重合体100
重量部あたり2.3重量部であつた。
さらに、試料ｐとポリマー構造が異なるスチレ
ン―ブタジエン共重合体（試料ｑ，ｒ，ｓ，ｔ）
を試作し、上記と同様な方法で、表１に示す不飽
和カルボン酸を付加し、試料Ｑ，Ｒ，Ｓ，Ｔ、す
なわち、変性ブロツク共重合性である本発明の(B)
成分を得た。
得られた試料の結果を表１に示した。
The present invention relates to a thermoplastic resin composition having excellent impact resistance, mechanical properties, and moldability, which is made of a graft copolymer produced by blending two or more types of polymers having reactive functional groups. More specifically, at least one monomer selected from epoxy group-containing vinyl monomers and amino group-containing vinyl monomers and one other vinyl monomer that can be copolymerized with the monomer. A multicomponent copolymer obtained by copolymerizing the above, a block copolymer obtained by modifying a vinyl aromatic compound-conjugated diene compound copolymer with an ethylenically unsaturated dicarboxylic acid or its derivative, and an ethylenically unsaturated dicarboxylic acid. The present invention relates to a thermoplastic resin composition having excellent impact resistance and mechanical strength, which contains a thermoplastic resin that does not contain anhydride as a polymer constituent. Conventionally, rubber-like substances such as polybutadiene and styrene-butadiene copolymers are well known as impact modifiers for thermoplastic resins. These rubbery substances can be used by directly blending them into a thermoplastic resin to disperse the rubbery substances in the resin, or by radically polymerizing vinyl monomers in the presence of a rubbery substance and using the generated heat. A method of microdispersing a rubbery substance modified by radical grafting into a plastic resin is known. However, the former method of directly blending a rubbery substance with a thermoplastic resin cannot necessarily be expected to improve impact resistance;
The effect varies greatly depending on the blend composition, blending method, blend molding conditions, etc. For example, styrene-butadiene block copolymer/
Blends made of polystyrene can be expected to have improved impact resistance, but the impact resistance tends to vary greatly depending on the blending method and molding conditions of the blend. Furthermore, blends of styrene-butadiene block copolymer/styrene-acrylonitrile copolymer (AS resin) have extremely poor compatibility, making it difficult to improve mechanical strength such as impact resistance. This is the current situation. On the other hand, in recent years, many attempts have been made to improve the impact resistance of grafted products (rubber-reinforced resins; for example, high-impact polystyrene) obtained by graft polymerizing vinyl monomers in the presence of rubber-like substances. However, there are problems such as limited solubility of rubbery substances in vinyl monomers and extremely complicated methods required to control polymerization.
Furthermore, since the types of vinyl monomers used on an industrial scale are limited, the rubber reinforcing resins that can be obtained are also currently limited. Against this background, the present inventors have conducted extensive research to improve the above-mentioned problems, and have already disclosed in Japanese Patent Application No. 147552/1982 that ethylenically unsaturated dicarboxylic acid anhydride and the monomer are We proposed improvements in the impact resistance, mechanical strength, and heat resistance of multicomponent copolymers obtained by copolymerizing copolymerizable vinyl monomers. Subsequently, as a result of further research into blends of functional polymers, a graft composition obtained by blending two or more types of polymers having reactive functional groups has been developed, in which ethylenically unsaturated dicarboxylic acid anhydride is used as a polymer component. The present inventors have discovered that the composition exhibits excellent impact resistance without impairing the desired properties of the thermoplastic resin, and is suitable for use as a molding material, and has thus arrived at the present invention. That is, the present invention provides component (A); at least one monomer selected from epoxy group-containing vinyl monomers and amino group-containing vinyl monomers; Component (B); a polymer block mainly composed of at least one vinyl aromatic compound; A modified block consisting of 0.05 to 20 parts by weight of a molecular unit containing an ethylenically unsaturated dicarboxylic acid group or its derivative group bonded to 100 parts by weight of a block copolymer consisting of a polymer block mainly composed of a conjugated diene compound. Copolymer and component (C); styrene resin, polyolefin resin, acrylonitrile resin, methacrylic resin, which does not contain ethylenically unsaturated dicarboxylic acid anhydride as a polymer component;
Consists of one or more thermoplastic resins selected from polycarbonate, polysulfone, vinyl chloride resin, polyester resin, polyamide resin, polyphenylene sulfide, polyimide, polyphenylene oxide, fluororesin, and vinylidene chloride resin. , the vinyl aromatic compound content of the modified block copolymer of component (B) is 5 to 60% by weight.
In the case of , the blending composition ratio is (A) + (B) / (C) = 5 ~ 50 / 95 ~
50 (wt%) and the content of the vinyl aromatic compound in the modified block copolymer of component (B) is more than 60 wt% and 95 wt% or less, the blending composition ratio is (A)
The present invention relates to a graft copolymer resin composition characterized in that +(B)/(C)=5 to 99/95 to 1 (wt%). Hereinafter, the present invention will be explained in detail. In order to achieve the object of the present invention, components (A), (B), and (C), which are the constituent components of the present invention, are essential, and even if any one of these components is missing, the present invention cannot be achieved. The purpose cannot be achieved. That is, the present invention
Unlike conventional blend compositions, this is based on the technically significant idea of obtaining a graft composition by blending two or more functional polymers by utilizing the reactivity of the functional groups. , is a graft copolymer resin composition that can be achieved only by including component (A), component (B), and component (C) of the present invention as essential components. The multicomponent copolymer of component (A) used in the present invention is
At least one monomer selected from epoxy group-containing vinyl monomers and amino group-containing vinyl monomers, and one or more other vinyl monomers that can be copolymerized with the monomer. It is a multicomponent copolymer obtained by copolymerizing. Epoxy group-containing vinyl monomers that are useful functional monomers include, for example, glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, allyl glycidyl ether, itaconic acid monoglycidyl ester, and butene. Tricarboxylic acid monoglycidyl ester, butene tricarboxylic acid diglycidyl ester, butene tricarboxylic acid triglycidyl ester, styrene-p-glycidyl ether, 3,4-epoxybutene, 3,
4-epoxy-3-methyl-1-butene, 3,4
-Epoxy-1-pentene, 3,4-epoxy-
3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, p
- Examples include glycidyl styrene. In addition, examples of amino group-containing vinyl monomers that are useful functional monomers include acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-butylacrylamide,
N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dibutylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-tert-butylmethacrylamide, N,N-diethylmethacrylamide, N,
N-dipropylmethacrylamide, N,N-dibutylmethacrylamide, N-methylolacrylamide, N-butoxymethylamide, N-isobutoxymethylacrylamide, diacetone acrylamide, p-(2-bis(ethylamino)aminoethyl) Styrene, p-(2-isopropylaminoethyl)styrene, p-(2-diethylaminoethyl)styrene, m-(2-diethylaminoethyl)styrene, 2-N,N-dimethylaminoethyl acrylate, 2-N,N- Diethylaminoethyl acrylate, 2-N,N-dibutylaminoethyl acrylate, 3-N,N-diethylaminopropyl acrylate, 2-N,N-dibutylaminopropyl acrylate, 3-N,N
-Dibutylaminopropyl acrylate, 2-
N,N-dimethylaminoethyl methacrylate,
Examples include 2-N,N-diethylaminoethyl methacrylate, 2-N,N-dibutylaminoethyl methacrylate, 3-N,N-diethylaminopropyl methacrylate, and 2-N,N-dibutylaminopropyl methacrylate. Further, other vinyl monomers that can be copolymerized with these functional vinyl monomers include, for example, ethylene, vinyl chloride, vinyl acetate, vinyl toluene, α-methylstyrene, styrene, acrylonitrile, lauryl methacrylate, lauryl acrylate. , cyclohexyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, octyl acrylate, octyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl acrylate, isopropyl Examples include methacrylate, isopropyl acrylate, propyl acrylate, propyl methacrylate, ethyl methacrylate, ethyl acrylate, methyl methacrylate, methyl acrylate, and if desired, a mixture of two or more of these vinyl monomers may also be used. can. The method for producing the multi-component copolymer of component (A) is a known polymerization method, such as solution polymerization method, emulsion polymerization method,
Radical polymerization methods such as bulk polymerization, bulk-suspension polymerization, and suspension polymerization are advantageously used industrially. At least one monomer selected from the epoxy group-containing vinyl monomer and amino group-containing vinyl monomer obtained in this way, and other vinyl monomers that can be copolymerized with the monomer. The multicomponent copolymer obtained by copolymerizing one or more of
~1,000,000, preferably 10,000 to 800,000, more preferably 20,000 to 500,000 are used. The content of the epoxy group- or amino group-containing vinyl monomer in the copolymer is preferably 1 to 50% by weight, more preferably 5 to 30% by weight. Next, the component (B) used in the present invention contains one or more polymer blocks mainly composed of a vinyl aromatic compound and one or more polymer blocks mainly composed of a conjugated diene compound. This is a modified block copolymer in which an unsaturated dicarboxylic acid or a derivative thereof is added to a block copolymer in which the weight ratio of the compound to the conjugated diene compound is 5/95 to 95/5. Here, the polymer block mainly composed of a vinyl aromatic compound refers to a vinyl aromatic compound polymer block or a vinyl aromatic compound in which the content of vinyl aromatic compounds is more than 50% by weight, preferably 70% by weight or more. It is a copolymer block of a compound and a conjugated diene compound, and a polymer block mainly composed of a conjugated diene compound is a conjugated diene compound polymer block or a copolymer block with a conjugated diene compound content of 50% by weight.
It is a copolymer block of a vinyl aromatic compound and a conjugated diene compound in an amount of more than 70% by weight, preferably 70% by weight or more. The vinyl aromatic compound-conjugated diene compound block copolymer (hereinafter simply referred to as "block copolymer") that serves as the base of the above-mentioned modified block copolymer is:
It contains one or more, preferably two or more, polymer blocks mainly composed of a vinyl aromatic compound, and one or more polymer blocks mainly composed of a conjugated diene compound. In the block copolymer, the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 5/95 to 95/5, preferably 10/90 to 90/5.
The composition range is 10, more preferably 15/85 to 85/15. The block copolymer exhibits elastomeric properties when the vinyl aromatic compound content is 60% by weight or less, preferably less than 55% by weight, and when it exceeds 6% by weight, preferably 70% by weight or more. shows resin-like properties. In addition, among the polymer blocks mainly composed of vinyl aromatic compounds and the polymer blocks mainly composed of conjugated diene compounds of block copolymers, in the molecular chain of the copolymer blocks of vinyl aromatic compounds and conjugated diene compounds, The distribution of the vinyl aromatic compound may be random, tapered (increasing or decreasing monomer content along the molecular chain), partially block-like, or any combination thereof. When there are two or more polymer blocks mainly composed of vinyl aromatic compounds, each block may have the same structure or may have different structures. Further, when two or more polymer blocks mainly composed of a conjugated diene compound are contained, each block may have the same structure or may have a different structure. As the vinyl aromatic compound constituting the block copolymer, for example, one or more kinds are selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Among them, styrene is particularly preferred. preferable. In addition, examples of conjugated diene compounds include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-
One or more types are selected from 1,3-butadiene and the like, and among them, butadiene or a combination of conjugated diene compounds mainly composed of butadiene is preferred, and butadiene is particularly preferred. The number average molecular weight of the block copolymer is 5000~
The range is 1,000,000, preferably 10,000 to 800,000, more preferably 30,000 to 500,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is 10 or less. Further, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. Further, the above block copolymer may be slightly modified with an organic compound or an inorganic compound as long as its properties are not lost. The block copolymer used in the present invention is usually produced by polymerizing a vinyl aromatic compound and a conjugated diene compound in an inert hydrocarbon solvent such as hexane, cyclohexane, benzene, or toluene using an organolithium compound such as butyllithium as a polymerization catalyst. It is obtained by anionic copolymerization, and at this time, block copolymers with various structures can be obtained by changing the method or order of addition of monomers or by using a polyfunctional lithium compound. In addition, the block copolymer having lithium active terminals obtained by the above method may be combined with a polyfunctional coupling agent such as carbon tetrachloride.
By reacting with silicon tetrachloride or the like, it is possible to form a branched or radial block copolymer. Any other vinyl aromatic compound-conjugated diene compound block copolymer obtained by any other manufacturing method may be used as long as it falls within the range of the above limitations. The above block copolymer is not only one type but also two types.
It may be a combination of more than one type, and examples of these combinations include a combination of a styrene-butadiene block copolymer and a styrene-isoprene block copolymer, and a combination of two types of styrene-butadiene blocks with different molecular weights. A combination of two types of styrene-butadiene block copolymers with different styrene contents, a combination of two types of styrene-butadiene block copolymers with different styrene contents, a combination of two types of styrene-butadiene block copolymers with a block structure consisting of three segments of styrene-butadiene-sterene, and a combination of butadiene-styrene-butadiene-sterene. Styrene with different block structures, such as those consisting of four segments.
Examples include combinations of butadiene block copolymers. Next, the unsaturated dicarboxylic acid or its derivative grafted onto the block copolymer will be explained. These unsaturated dicarboxylic acids or derivatives thereof are added to the block copolymer. These are added in an amount of 0.05 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight per 100 parts by weight of the block copolymer. It is necessary to bring out the When the amount added is less than 0.05 parts by weight, there is almost no improvement effect compared to the unmodified block copolymer, and even when the amount added is 20 parts by weight or more, the improvement effect is not further improved. Examples of the unsaturated dicarboxylic acids or derivatives thereof include maleic acid, fumaric acid, itaconic acid,
Dichloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid, etc., and acid anhydrides of these dicarboxylic acids , ester, amide, dicarboxylic acid imide, etc. Various derivatives of dicarboxylic acids may be added to block copolymers as derivatives, or after adding unsaturated dicarboxylic acids to block copolymers, carboxylic acid groups may be added through appropriate reactions. It may be converted into a derivative. Among the unsaturated dicarboxylic acids or derivatives thereof that modify the above-mentioned block copolymers, maleic acid, fumaric acid, and maleic anhydride are preferred. The modified block copolymer of the present invention can be obtained by subjecting the block copolymer to a graft reaction with an unsaturated dicarboxylic acid or a derivative thereof in a molten state or a solution state, with or without the use of a radical initiator. The method for producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gel, or may have poor fluidity and be processed. A manufacturing method that deteriorates properties is not preferred. A preferred method is, for example, to react the block copolymer with an unsaturated dicarboxylic acid or a derivative thereof in an extruder without adding peroxide. In the reaction using an extruder, it is preferable to use a commonly used anti-gelling agent. Next, the component (C) used in the present invention is a thermoplastic resin that does not contain an ethylenically unsaturated dicarboxylic acid anhydride as a polymer constituent, such as an ethylene-based resin such as a styrene-maleic anhydride copolymer. Thermoplastic resins obtained by radical copolymerization of unsaturated dicarboxylic acid anhydrides or derivatives thereof as constituent monomers are outside the scope of the present invention. Thermoplastic resins within the scope of the present invention, that is, component (C), include styrene resins, polyolefin resins, acrylonitrile resins, methacrylic resins, polycarbonates, polysulfones, vinyl chloride resins, polyester resins, polyamide resins, and polycarbonate resins. enylene sulfide, polyimide,
Polyphenylene oxide, fluororesin, vinylidene chloride resin, specifically polystyrene,
Impact-resistant polystyrene, styrene-acrylonitrile copolymer, ABS resin, styrene-acrylic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid ester copolymer, MBS resin,
Polyethylene, chlorinated polyethylene, polypropylene, ethylene copolymer, propylene copolymer,
Polybutene-1, poly-4-methylpentene-
1, poly-3-methyl-1-pentene, poly-3
-Methyl-1-butene, acrylonitrile-acrylic acid copolymer, acrylonitrile-acrylic acid ester copolymer, polymethacrylate ester, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene adipamide, polycaprolactam , polyhexamethylene sebacamide, polyhexamethylene isophthalamide, polyhexamethylene terephthalamide isophthalamide, etc., but are not limited to these. The graft copolymer resin composition of the present invention is composed of the above-mentioned components (A), (B), and (C). Thermoplastic resins may be mixed. The dicarboxylic acid group or its derivative group of component (B) used in the present invention reacts with the epoxy group and amino group of component (A) to provide a graft product (A-B graft product) that is significant in the present invention. By optionally dispersing it in the thermoplastic resin of component (C), the mechanical strength such as impact resistance of component (C) can be improved. The relationship between components (A) and (C) used here is that the difference in solubility parameters (Δδ) between the multi-component copolymer of component (A) and the thermoplastic resin of component (C) is Δδ≦3 (δ is the solubility parameter, expressed as the square root of the ratio of the cohesive energy density of the constituent elements to the molecular volume, Hildebrand
It was defined by Scott. The value of the solubility parameter is e.g.
It is described in Chapter 4 341-368 of the Handbook,
Furthermore, Journal of Applied Chemistry Volume 3
It can be calculated from the constituent elements using Small's report data from 1953, pages 71-80. ), preferably Δδ≦1.5, more preferably Δδ≦1.0,
This is desirable in order to improve the compatibility between the AB graft product and component (C). Particularly preferred embodiments include (A)
The component multi-component copolymer contains at least one monomer selected from epoxy group-containing vinyl monomers and amino group-containing vinyl monomers, and at least one component constituting the thermoplastic resin (C). A multicomponent copolymer obtained by copolymerizing the monomer with more than one kind of monomer is desirable. The graft copolymer resin composition of the present invention can be copolymerized with at least one monomer selected from epoxy group-containing vinyl monomers and amino group-containing vinyl monomers. Multi-component copolymer (A) formed by copolymerizing with one or more other vinyl monomers
and a block copolymer consisting of a polymer block mainly composed of at least one vinyl aromatic compound and a polymer block mainly composed of at least one conjugated diene compound, and an ethylenically unsaturated dicarboxylic acid group or a derivative thereof. By blending a modified block copolymer (B), which is made by bonding molecular units that share a group, with a thermoplastic resin (C), which does not contain ethylenically unsaturated dicarboxylic acid anhydride as a polymer constituent. This is the graft copolymer resin composition obtained. The graft copolymer resin composition of the present invention can be obtained as a thermoplastic resin composition by selecting the compositions and blending amounts of the components (A), (B), and (C) shown above. can. That is, the thermoplastic resin composition of the present invention can be prepared by, for example, a graft copolymer consisting of components (A) and (B) in an amount such that component (C) forms a matrix of the thermoplastic resin composition. It can be obtained by dispersing the aggregate in component (C). (B)
When the content of the vinyl aromatic compound in the modified block copolymer component is 5 to 60% by weight, the blending composition ratio is (A) + (B) / (C) = 5 to 50/95 to 50, preferably can be selected from 10 to 40/90 to 60 (weight%). Furthermore, if the content of the vinyl aromatic compound in the modified block copolymer of component (B) constituting the graft copolymer is more than 60% by weight and less than 95% by weight,
Preferably, if it is 70% by weight or more and 90% by weight or less,
A thermoplastic resin composition can be obtained with component (C) in either a blending amount that forms a matrix or a blending amount that does not form a matrix. The blending composition ratio (A)+(B)/(C)=5-99/95-1, preferably 10-90/90-10 (wt%) can be selected. In the graft copolymer resin composition of the present invention, the blending ratio of component (A) and component (B) is generally (A)/(B).
=3-90/97-10, preferably 5-70/95-30,
More preferably, it is selected from the range of 10-50/90-50 (wt%). As described above, the graft copolymer resin composition of the present invention is a thermoplastic resin composition consisting of component (A), component (B), and component (C), and the resulting graft copolymer resin composition is It can be suitably used for various molding material applications. The graft copolymer resin composition of the present invention can be prepared by mixing in a molten state using various mixing apparatuses commonly used for mixing polymeric substances. Suitable mixing devices include, for example, single-screw or multi-screw extruders, mixing rolls, Banbury mixers, kneaders,
A mixing device such as a Brabender may be used. In preparing the composition of the present invention, component (A),
It is preferable to mix component (B) in advance to obtain an A-B graft copolymer, and then add and mix component (C), but any other mixing method that can exhibit the effects of the present invention is preferred. It doesn't matter if you choose. Also,
The mixing conditions for preparing the composition of the present invention include a mixing temperature and a mixing temperature such that each component (A) and (B) of the present invention sufficiently achieves the grafting reaction by the functional group, which is the gist of the present invention. Time is chosen. The mixing temperature of each component (A), (B), and (C) is generally above the melting point of each component, and the mixing time is until each component is mutually dispersed. It is undesirable to continue mixing at such high temperatures or for long periods of time that gelation occurs. During this mixing, tertiary amine, ammonium salt,
A catalyst such as an organic acid salt or an organic chelate compound may be added. Further, the composition of the present invention can be obtained by mixing the constituent components of the present invention and, if necessary, a catalyst in an appropriate solvent, in addition to mixing using the mixing apparatus shown above. The graft copolymer resin composition may further contain other rubbery substances such as natural rubber, polybutadiene,
Poly(styrene/butadiene), poly(ethylene/propylene/non-conjugated diene), etc. may be mixed to the extent that their properties are not impaired, and additives such as antioxidants, heat stabilizers, and ultraviolet absorbers may be added. It is also possible to add agents, colorants, lubricants, flame retardants, pigments, etc. The graft copolymer resin composition obtained in the present invention has excellent impact resistance, mechanical properties, and moldability, so it can be used in compression molding, which is conventionally used for molding styrene resins, polyolefin resins, etc. Injection molding, extrusion molding (sheets and films by inflation method or T-die method, films and sheets by coextrusion lamination, uniaxial stretching method or biaxial stretching method, pipes by straight die, offset die, crosshead die) extrusion, etc.), calender molding, which is a method of forming thin sheets, and placing powdered resin in a cylindrical mold.
Various molding methods are available, including rotary molding, which involves heating and rotating, casting molding, which involves filling a mold with foam pellets and heating and foaming them, vacuum forming of sheets, and pressure forming, such as biaxially stretched sheets. It is also possible to use These molded products, in the form of films, sheets, molded products, etc., have a wide range of uses in adhesive materials, packaging materials, miscellaneous toys, electrical parts, mechanical parts, automobile parts, and various other applications, and are useful compositions. be. The graft copolymer resin composition of the present invention may also contain reinforcing fillers, such as glass fibers, glass flakes, carbon fibers, potassium titanate, titanium dioxide, titanate whiskers, anhydrous mica, calcium silicate, silicic anhydride, A resin composition containing a reinforcing filler can be obtained by adding wollastenite, calcium carbonate, glass spheres, asbestos, alumina, aluminum, iron, nickel, etc. Among these, glass fibers and carbon fibers are preferred as reinforcing fillers. When using glass fibers, the glass fibers used may be those used in general glass fiber reinforced resins, and the diameter is usually 2 to 20μ, and the length is the most appropriate length in terms of processability and practical physical properties. It is preferable to use one that has been cut into
Glass fibers whose surfaces have been surface-treated with a silane-based treatment agent or a chromium-based treatment agent are used. Furthermore, the graft copolymer resin composition of the present invention may include a blowing agent, such as a physical blowing agent (n-propane,
hydrocarbons such as n-butane and n-pentane),
Chemical blowing agents (azo blowing agents, nitroso blowing agents,
A foamed product can be obtained by mixing or press-injecting a sulfonyl hydrazide foaming agent) or a bicarbonate as an inorganic foaming agent. The thus obtained graft copolymer resin composition containing a reinforcing filler and the foam composition both have excellent mechanical strength and impact resistance, so they can be used in mechanical parts, electrical parts, automobile parts, etc. It is a useful composition that can be used in a variety of applications. Hereinafter, some examples will be shown, but these are intended to explain the present invention more specifically, and it goes without saying that the scope of the present invention is not limited to these examples. In the following Examples, components in which the difference (Δδ) in solubility parameters between component (A) and component (C) was less than 3 were used. Reference Example [Preparation of Modified Block Copolymer] A modified block copolymer (Sample P) in which maleic anhydride was grafted by the method shown below using Sample P, which is a thermoplastic elastomer of styrene-butadiene block copolymer. I got it. Note that sample p was obtained using n-butyllithium as a catalyst in a hexane solution, and its basic characteristics are shown below. Polymer structure: B-S-B-S (linear) (B: butadiene, S: styrene) Styrene content: 42% by weight Block styrene content: 36% by weight Weight average molecular weight (Mw): 79000 Number average Molecular weight (Mn): 61000 Melt index: 12.0g/10min (JIS-K-6870, load 5Kg, 200℃) 4 parts by weight of maleic anhydride and 0.3 parts by weight as an anti-gelling agent for 100 parts by weight of sample P. BHT by weight
(butylated hydroxytoluene) and 0.3 parts by weight of phenothiazine were added, and these were mixed uniformly using a mixer. This mixture was supplied to a 40 mm extruder (single screw, full-flight screw, L/D=24) under a nitrogen atmosphere, and a modification reaction was carried out at a cylinder temperature of 190 to 260°C. The obtained polymer was dried under reduced pressure to remove unreacted maleic anhydride. The analysis results of the modified block copolymerization (sample P) show that the melt index is 8.5 g/10 min, the toluene insoluble content is 0.05% by weight, and the amount of maleic anhydride added by titration with sodium methylate is 100%.
It was 2.3 parts by weight per part by weight. Furthermore, styrene-butadiene copolymers (samples q, r, s, t) with different polymer structures from sample p
Samples Q, R, S, and T, i.e., (B) of the present invention which is a modified block copolymerizable
Got the ingredients. Table 1 shows the results of the obtained samples.
【表】【table】
【表】
実施例１〜３および比較例１〜３
(A)成分として、アセトン―トルエン混合溶媒中
でラジカル重合を行い、グリシジルメタクリレー
ト10重量％、スチレン65重量％、アクリロニトリ
ル25重量％よりなる官能性重合体；SAGコポリ
マー（分子量63000）を得た。この(A)成分と、(B)
成分として参考例で得た変性ブロツク共重合体
（試料Ｐ）および未変性のブロツク共重合体（試
料ｐ）とを用い、200℃のミキシングロールで５
分間混練し、(A)−(B)混合物を得た。その後さら
に、(C)成分としてスチレン―アクリロニトリル共
重合体であるAS樹脂、商品名「タイリル769」
（旭ダウ社製）を添加し、５分間200℃のミキシン
グロールで混練し、(A)，(B)，(C)成分からなるグラ
フト共重合体樹脂組成物を得た。組成物の特性を
知るべく、230℃で圧縮成形を行い、各種の物性
を測定し表２に示した。[Table] Examples 1 to 3 and Comparative Examples 1 to 3 As component (A), radical polymerization was carried out in an acetone-toluene mixed solvent to form a functional compound consisting of 10% by weight of glycidyl methacrylate, 65% by weight of styrene, and 25% by weight of acrylonitrile. A SAG copolymer (molecular weight 63,000) was obtained. This (A) component and (B)
The modified block copolymer (sample P) obtained in the reference example and the unmodified block copolymer (sample p) were used as components, and the mixture was heated on a mixing roll at 200°C for 5 minutes.
The mixture was kneaded for a minute to obtain a mixture of (A) and (B). After that, AS resin, which is a styrene-acrylonitrile copolymer as component (C), was added under the trade name "Tyryl 769".
(manufactured by Asahi Dow) and kneaded for 5 minutes using a mixing roll at 200°C to obtain a graft copolymer resin composition consisting of components (A), (B), and (C). In order to understand the properties of the composition, compression molding was performed at 230°C, and various physical properties were measured and are shown in Table 2.
【表】
表２に示す如く、本発明の範囲内にある実施例
１〜３の組成物は、本発明の範囲外にある比較例
１〜３と比して、顕著に耐衝撃性の改良が認めら
れ、かつ、引張強さ、曲げ弾性率も優れ、実用特
性上十分な強度を有する熱可塑性樹脂組成物であ
る。この効果は、(A)成分、(B)成分をそれぞれ単独
で(C)成分中に分散、もしくは未変性ブロツク共重
合体と(A)成分を(C)成分中に分散させた組成物であ
る比較例１〜３では想像もつかず、(A)成分、(B)成
分の２成分が混合されてＡ―Ｂグラフト物をつく
り、さらに、(C)成分中にＡ―Ｂグラフト物が分散
した場合において、上記に挙げた効果を発揮する
ことが明らかである。このように、本発明の構成
要素である(A)成分、(B)成分、(C)成分の３成分のう
ち、比較例１，３に示すように、(A)成分、(B)成分
のいずれか一つが欠けても本発明の効果を引き出
すことは不可能であり、さらに、実施例３と比較
例２が示すように、(B)成分が変性ブロツク共重合
体でなければ本発明の効果を引き出すことが不可
能であることが理解できる。
実施例４〜６および比較例４〜６
(B)成分として試料記号Ｑ，Ｒ，Ｔ，ｑ，ｒ，ｔ
を用いたほかは、実施例１〜３と同様の(A)成分、
(C)成分を用いて、40mmφ押出機で混練しペレツト
化した。その後、このペレツトを射出成型機
（IS80CN、東芝機械製）を用い、試験サンプル
を作成し、射出成型品の物性を測定した。各成分
の配合組成および試験結果を表３に示した。
表３に示す如く、基体となるブロツク共重合体
の構造の異なる変性ブロツク共重合体を(B)成分と
して用いた実施例４〜６は、対応する未変性のブ
ロツク共重合体を用いた批較例４〜６と比較し
て、耐衝撃性が著しく優れており、かつ、引張強
さ、曲げ弾性率にも優れた実用特性を有する熱可
塑性樹脂である。このように本発明の構成要素で
ある(B)成分が通常の未変性ブロツク共重合体で
は、本発明の効果を発揮することができず、(B)成
分の基体となるブロツク共重合体の構造が異なつ
ていても、(B)成分が変性ブロツク共重合体である
場合に限つて、本発明の効果を引き出すことが可
能であることが理解できる。[Table] As shown in Table 2, the compositions of Examples 1 to 3, which are within the scope of the present invention, have significantly improved impact resistance compared to Comparative Examples 1 to 3, which are outside the scope of the present invention. It is a thermoplastic resin composition which has excellent tensile strength and flexural modulus, and has sufficient strength for practical use. This effect can be obtained by dispersing components (A) and (B) individually in component (C), or by dispersing an unmodified block copolymer and component (A) in component (C). In some Comparative Examples 1 to 3, it was unimaginable that two components, component (A) and component (B), were mixed to create an A-B graft product, and further, an A-B graft product was dispersed in component (C). It is clear that the above-mentioned effects can be achieved in this case. As described above, among the three components of the present invention, component (A), component (B), and component (C), as shown in Comparative Examples 1 and 3, component (A) and component (B) It is impossible to bring out the effects of the present invention even if any one of these is lacking, and as shown in Example 3 and Comparative Example 2, the present invention cannot be achieved unless component (B) is a modified block copolymer. It is understandable that it is impossible to bring out the effect of Examples 4 to 6 and Comparative Examples 4 to 6 Sample symbols Q, R, T, q, r, t as (B) components
The same component (A) as in Examples 1 to 3 except that
Component (C) was kneaded and pelletized using a 40 mmφ extruder. Thereafter, test samples were prepared from the pellets using an injection molding machine (IS80CN, manufactured by Toshiba Machinery), and the physical properties of the injection molded products were measured. Table 3 shows the composition of each component and the test results. As shown in Table 3, Examples 4 to 6, in which modified block copolymers with different base block copolymer structures were used as component (B), were compared to those in which the corresponding unmodified block copolymers were used. It is a thermoplastic resin that has significantly superior impact resistance as compared to Comparative Examples 4 to 6, and also has excellent practical properties in terms of tensile strength and flexural modulus. As described above, if component (B), which is a constituent element of the present invention, is a normal unmodified block copolymer, it will not be possible to exhibit the effects of the present invention. It can be understood that even if the structure is different, the effects of the present invention can be brought out only when component (B) is a modified block copolymer.
【表】
実施例７，８および比較例７，８
(A)成分としてスチレン25重量％、メチルメタク
リレート70重量％、グリシジルメタクリレート５
重量％よりなる官能性重合体；SMGコポリマー
（分子量55000）を用い、(B)成分として参考例で得
た試料記号Ｐ，ｐ，Ｓ，ｓを用い、(C)成分として
スチレン30重量％、メチルメタクリレート70重量
％よりなる熱可塑性樹脂（MS樹脂）を用いて、
(A)成分、(B)成分、(C)成分を40mmφ押出機で混練
し、ペレツト化した熱可塑性樹脂組成物を得た。
その後射出成型機（IS80CN東芝機械製）を用
い、試験サンプルを作成し、サンプルの特性を測
定した。各成分の配合組成および試験結果を表４
に示した。[Table] Examples 7 and 8 and Comparative Examples 7 and 8 Component (A): 25% by weight of styrene, 70% by weight of methyl methacrylate, 5% by weight of glycidyl methacrylate
SMG copolymer (molecular weight 55000) was used, the sample symbols P, p, S, and s obtained in the reference example were used as the component (B), and 30% by weight of styrene was used as the component (C). Using thermoplastic resin (MS resin) consisting of 70% by weight of methyl methacrylate,
Components (A), (B), and (C) were kneaded using a 40 mmφ extruder to obtain a pelletized thermoplastic resin composition.
Thereafter, a test sample was prepared using an injection molding machine (IS80CN manufactured by Toshiba Machine), and the characteristics of the sample were measured. Table 4 shows the composition and test results of each component.
It was shown to.
【表】
表４に示す如く、本発明の熱可塑性樹脂組成物
のマトリツクスとなる(C)成分が変わつても、(A)成
分、(B)成分、(C)成分が本発明の範囲内にあれば、
耐衝撃性などの機械的強度が優れたグラフト共重
合体樹脂組成物を得ることができる。また、(B)成
分の変性ブロツク共重合体の構造が異なつている
場合でも、本発明の効果を十分に引き出すことが
明らかである。また、本発明の実施態様の一例と
して示した実施例７，８、および本発明の範囲外
の組成で構成された比較例７，８のサンプルを透
過型電子顕微鏡でモルフオロジーの観察を行つた
ところ、実施例７，８はゴム粒径が0.5〜2.0μの
粒子であり、比較例７は３〜10μ、比較例８は５
〜20μのゴム粒子径であつた。このことより本発
明の組成物は、(B)成分が比較的小さく、(C)成分中
に分散するため、透明性にも効果が出現している
ことが理解できる。
実施例９，10および比較例９
(A)成分として、高温、高圧下でグリシジルメタ
クリレートを10重量％含有するエチレン―グリシ
ジルメタクリレート共重合体；EGコポリマー
（分子量21000）を得た。
この(A)成分と、(B)成分として参考例で得た変性
ブロツク共重合体（試料Ｐ）および未変性ブロツ
ク共重合体（試料ｐ）と、さらに、(C)成分として
ポリプロピレン樹脂（分子量120000、ｎ―ヘプタ
ン抽出で約95％の残留物を有する結晶性PP）と
を用いて、40mmφ押出機で220〜240℃で溶融混練
し、ペレツト化した熱可塑性樹脂組成物を得た。
その後、射出成型機を用いて試験サンプルを作成
し、物性測定を行つた。各成分の配合組成および
試験結果を表５に示した。[Table] As shown in Table 4, even if the (C) component that forms the matrix of the thermoplastic resin composition of the present invention changes, the (A) component, (B) component, and (C) component are within the scope of the present invention. If there is
A graft copolymer resin composition having excellent mechanical strength such as impact resistance can be obtained. Furthermore, it is clear that even when the modified block copolymer of component (B) has a different structure, the effects of the present invention can be fully brought out. In addition, the morphology of the samples of Examples 7 and 8, shown as examples of embodiments of the present invention, and Comparative Examples 7 and 8, which were configured with compositions outside the scope of the present invention, was observed using a transmission electron microscope. However, in Examples 7 and 8, the rubber particle diameter was 0.5 to 2.0μ, Comparative Example 7 was 3 to 10μ, and Comparative Example 8 was 5μ.
The rubber particle size was ~20μ. From this, it can be seen that in the composition of the present invention, the component (B) is relatively small and dispersed in the component (C), so that the composition also has an effect on transparency. Examples 9, 10 and Comparative Example 9 As component (A), an ethylene-glycidyl methacrylate copolymer containing 10% by weight of glycidyl methacrylate; EG copolymer (molecular weight 21,000) was obtained under high temperature and high pressure. This (A) component, the modified block copolymer (sample P) and unmodified block copolymer (sample p) obtained in the reference example as the (B) component, and the polypropylene resin (molecular weight 120,000 (crystalline PP having about 95% residue when extracted with n-heptane) was melt-kneaded at 220 to 240°C in a 40 mmφ extruder to obtain a pelletized thermoplastic resin composition.
Thereafter, test samples were prepared using an injection molding machine, and physical properties were measured. Table 5 shows the composition of each component and the test results.
【表】【table】
【表】
表５より、樹脂マトリツクスをポリプロピレン
樹脂に変えた場合でも、本発明の効果を引き出す
ことができ、耐衝撃性、引張強さに優れた熱可塑
性樹脂組成物を得ることができる。
実施例 11
(A)成分として、２―Ｎ，Ｎ―ジエチルアミノエ
チルメタクリレート５重量％、スチレン70重量
％、アクリロニトリル25重量％より成る官能性重
合体；SAAMコポリマー（分子量53000）を用い
たほかは、実施例１と同様の(B)成分、(C)成分を用
い、同様の組成および方法で熱可塑性樹脂を得
た。
テストピースを作成し物性を測定したところ、
アイゾツト衝撃強度、引張強さ、伸び、曲げ弾性
率は、それぞれ41.6（Kg・cm／cm・ノツチ）、460
（Kg／cm2）、28（％）、20600（Kg／cm2）、であつた
。
このことより、(A)成分をアミノ基含有の多元共
重合体にしても、本発明の効果が著しいことがて
わかる。
実施例12，13および比較例10〜12
(A)成分として実施例１で用いたSAGコポリマ
ーと、(B)成分として参考例で得た変性ブロツク共
重合体（試料Ｓ）および未変性のブロツク共重合
体（試料ｓ）、(C)成分としてポリカーボネート樹
脂である。４，4′―ジオキシジフエニル―２，
2′―プロパンポリカーボネートとを用い、270℃
で成型しテストピースを得た。各成分の配合組成
および試験結果を表６に示した。
表６より、(B)成分として変性ブロツク共重合体
を用いた場合は、耐衝撃強度が著しく向上し、他
の機械的特性も十分実用強度を有する熱可塑性樹
脂であつた。[Table] From Table 5, even when the resin matrix is changed to polypropylene resin, the effects of the present invention can be brought out, and a thermoplastic resin composition with excellent impact resistance and tensile strength can be obtained. Example 11 As component (A), a functional polymer consisting of 5% by weight of 2-N,N-diethylaminoethyl methacrylate, 70% by weight of styrene, and 25% by weight of acrylonitrile; SAAM copolymer (molecular weight 53000) was used. Using the same components (B) and (C) as in Example 1, a thermoplastic resin was obtained using the same composition and method. When we created a test piece and measured its physical properties, we found that
Izotsu impact strength, tensile strength, elongation, and flexural modulus are 41.6 (Kg・cm/cm・notch) and 460, respectively.
(Kg/cm 2 ), 28 (%), and 20600 (Kg/cm 2 ). This shows that even when component (A) is an amino group-containing multi-component copolymer, the effects of the present invention are remarkable. Examples 12, 13 and Comparative Examples 10 to 12 The SAG copolymer used in Example 1 as the (A) component, the modified block copolymer (sample S) obtained in Reference Example as the (B) component, and the unmodified block Copolymer (sample s), component (C) is polycarbonate resin. 4,4′-dioxydiphenyl-2,
2'-propane polycarbonate at 270℃
A test piece was obtained by molding. Table 6 shows the composition of each component and the test results. Table 6 shows that when the modified block copolymer was used as component (B), the impact strength was significantly improved, and the thermoplastic resin had sufficient practical strength in other mechanical properties.
【表】【table】
【表】
実施例14，15および比較例13〜15
(A)成分として、有機過酸化物を用い、加圧加熱
下で共重合したグリシジルメタクリレート７重量
％、エチレン64重量％、酢酸ビニル29重量％より
なる官能性重合体；EVGコポリマー、(B)成分と
して参考例で得た試料記号Ｐ，ｐ，(C)成分として
ナイロン６、ナイロン66を用いて、これら(A)成
分、(B)成分、(C)成分を40mmφベント押出機で混練
してペレツト化したポリアミド樹脂組成物を得
た。その後、射出成型機（IS80CN東芝機械製）
を用い、樹脂温度260〜270℃、金型温度80℃で試
験サンプルを作成した。各成分の配合組成および
試験結果を表７に示した。
表７より、(B)成分として変性ブロツク共重合体
を用いた場合は、耐衝撃強度が著しく改良された
ポリアミド樹脂であつた。[Table] Examples 14, 15 and Comparative Examples 13-15 (A) Components: 7% by weight glycidyl methacrylate, 64% by weight ethylene, 29% by weight vinyl acetate copolymerized under pressure and heat using an organic peroxide. A functional polymer consisting of % EVG copolymer, sample symbols P and p obtained in the reference example as the (B) component, nylon 6 and nylon 66 as the (C) component, and these (A) components, (B) A polyamide resin composition was obtained by kneading the components (C) and pelletizing them in a 40 mm diameter vented extruder. After that, injection molding machine (IS80CN made by Toshiba Machine)
A test sample was prepared using a resin temperature of 260 to 270°C and a mold temperature of 80°C. Table 7 shows the composition of each component and the test results. Table 7 shows that when the modified block copolymer was used as component (B), the polyamide resin had significantly improved impact strength.
【表】
実施例16〜19および比較例16〜19
(C)成分として、ポリブチレンテレフタレート
（Valox 310、GE社製）、ポリフエニレンオキシ
ド（PPO：GE社製）、ポリスルホン（ポリスル
ホンＰ―1700；UCC社製）、ポリフエニレンスル
フイド（ライトンＲ―６；フイリツプス社製）
を、表８に示す種々の配合比で40mmφベント押出
機で混練し、ペレツト化した種々の樹脂組成物を
得た。その後、射出成型機を用いテストピースを
得て、各種の物性試験を行つた。
本発明のグラフト共重合体樹脂組成物は、基体
ポリマーとなる(C)成分の特性を実用上好ましく改
善できる。[Table] Examples 16 to 19 and Comparative Examples 16 to 19 (C) component: polybutylene terephthalate (Valox 310, manufactured by GE), polyphenylene oxide (PPO: manufactured by GE), polysulfone (polysulfone P-1700) ; manufactured by UCC), polyphenylene sulfide (Ryton R-6; manufactured by Philips)
were kneaded in a 40 mm diameter vented extruder at various compounding ratios shown in Table 8 to obtain various pelletized resin compositions. Thereafter, test pieces were obtained using an injection molding machine, and various physical property tests were conducted. The graft copolymer resin composition of the present invention can improve the properties of component (C), which is the base polymer, in a practical manner.
【表】
使用例 １〜４
本発明のグラフト共重合体樹脂組成物を構成す
る各成分と表面処理したガラスチヨツプドストラ
ンドを、表９に示した組成配合で40mmφベント型
単軸押出機にて混練押出して、ガラス繊維で強化
した組成物を得た。
その結果、本発明のガラス繊維で強化した組成
物は、極めて耐衝撃性に優れることがわかる。[Table] Usage Examples 1 to 4 Each component constituting the graft copolymer resin composition of the present invention and the surface-treated glass chopped strands were mixed in a 40 mmφ bent uniaxial extruder with the composition shown in Table 9. The mixture was kneaded and extruded to obtain a glass fiber-reinforced composition. The results show that the glass fiber-reinforced composition of the present invention has extremely excellent impact resistance.
【表】【table】
【表】
使用例 ５〜８
実施例２，９，14，19で得たグラフト共重合体
樹脂組成物各々100重量部当たり15重量部のｎ―
ブタンを主成分とする発泡剤を、40mmφ押出機の
先端に接続した混合機に圧入し、よく混和して混
合機先端の細孔を有する口金より押出し、ただち
に20℃に保たれた水中に導き急冷固化し、ペレタ
イザーに導き粒径約１mmの発泡AS樹脂組成物
（使用例５）、発泡ポリプロピレン樹脂組成物（使
用例６）、発泡ナイロン６樹脂組成粉（使用例
７）、発泡ポリスチレン樹脂組成物（使用例８）
を得た。
その結果、本発明のグラフト共重合体樹脂組成
物の発泡性粒子は、型成形性、発泡剤の保持性に
優れ、これらから得られた発泡体は緩衝性に優れ
るものであつた。[Table] Usage Examples 5 to 8 15 parts by weight of n- per 100 parts by weight of each of the graft copolymer resin compositions obtained in Examples 2, 9, 14, and 19
A blowing agent whose main component is butane is press-fitted into a mixer connected to the tip of a 40mmφ extruder, mixed well, extruded through a nozzle with pores at the tip of the mixer, and immediately introduced into water kept at 20℃. A foamed AS resin composition (use example 5), a foamed polypropylene resin composition (use example 6), a foamed nylon 6 resin composition powder (use example 7), and a foamed polystyrene resin composition that is rapidly solidified and fed into a pelletizer with a particle size of approximately 1 mm. Things (Use example 8)
I got it. As a result, the expandable particles of the graft copolymer resin composition of the present invention had excellent moldability and foaming agent retention, and the foam obtained from them had excellent cushioning properties.
Claims (1)
ノ基含有ビニル単量体のうちから選ばれる少なく
とも１種の単量体と、当該単量体と共重合し得る
他のビニル系単量体の１種以上とを共重合して得
られる多元共重合体と (B)成分；少なくとも１個のビニル芳香族化合物を
主体とする重合体ブロツクと、少なくとも１個の
共役ジエン化合物を主体とする重合体ブロツクと
から成るブロツク共重合体100重量部あたりに、
エチレン系不飽和ジカルボン酸基またはその誘導
体基を含む分子単位を0.05〜20重量部結合せしめ
て成る変性ブロツク共重合体と (C)成分；エチレン系不飽和ジカルボン酸無水物を
重合体構成成分として含まないスチレン系樹脂、
ポリオレフイン系樹脂、アクリロニトリル系樹
脂、メタクリル樹脂、ポリカーボネート、ポリス
ルフオン、塩化ビニル系樹脂、ポリエステル樹
脂、ポリアミド樹脂、ポリフエニレンサルフアイ
ド、ポリイミド、ポリフエニレンオキシド、ふつ
素樹脂、塩化ビニリデン樹脂から選ばれた熱可塑
性樹脂１種または２種以上 から成り、かかる(B)成分の変性ブロツク共重合体
のビニル芳香族化合物の含有量５〜60重量％の場
合、配合組成比が(A)＋(B)／(C)＝５〜50／95〜50
（重量％）であり、かかる(B)成分の変性ブロツク
共重合体のビニル芳香族化合物の含有量が60重量
％を超え95重量％以下の場合、配合組成比が(A)＋
(B)／(C)＝５〜99／95〜１（重量％）であることを
特徴とするグラフト共重合体樹脂組成物。 ２ (A)成分の多元共重合体と(C)成分の熱可塑性樹
脂の溶解度パラメーターの差（Δδ）がΔδ≦３で
ある特許請求の範囲第１項記載の組成物。 ３ (A)成分のエポキシ基含有ビニル単量体が不飽
和グリシジルエステルまたは不飽和グリシジルエ
ーテルまたはエポキシアルケンまたはｐ―グリシ
ジルスチレンであり、アミノ基含有ビニル単量体
がアクリルアミドまたはアクリルアミド置換体ま
たは不飽和脂肪酸アミノエステルまたはその誘導
体またはアミノスチレンである特許請求の範囲第
１項記載の組成物。[Scope of Claims] 1 Component (A); at least one monomer selected from epoxy group-containing vinyl monomers and amino group-containing vinyl monomers, which can be copolymerized with the monomer. A multicomponent copolymer obtained by copolymerizing one or more other vinyl monomers and component (B); a polymer block mainly composed of at least one vinyl aromatic compound; Per 100 parts by weight of a block copolymer consisting of a polymer block mainly composed of a conjugated diene compound,
A modified block copolymer in which 0.05 to 20 parts by weight of molecular units containing an ethylenically unsaturated dicarboxylic acid group or its derivative group are bonded, and component (C); an ethylenically unsaturated dicarboxylic acid anhydride as a polymer constituent component. Contains no styrene resin,
Selected from polyolefin resin, acrylonitrile resin, methacrylic resin, polycarbonate, polysulfone, vinyl chloride resin, polyester resin, polyamide resin, polyphenylene sulfide, polyimide, polyphenylene oxide, fluororesin, vinylidene chloride resin When the vinyl aromatic compound content of the modified block copolymer of component (B) is 5 to 60% by weight, the composition ratio is (A) + (B). /(C)=5~50/95~50
(wt%), and if the content of the vinyl aromatic compound in the modified block copolymer of component (B) is more than 60 wt% and 95 wt% or less, the blending composition ratio is (A) +
A graft copolymer resin composition characterized in that (B)/(C)=5 to 99/95 to 1 (wt%). 2. The composition according to claim 1, wherein the difference (Δδ) in solubility parameters between the multi-component copolymer as component (A) and the thermoplastic resin as component (C) is Δδ≦3. 3 The epoxy group-containing vinyl monomer of component (A) is an unsaturated glycidyl ester, an unsaturated glycidyl ether, an epoxy alkene, or p-glycidylstyrene, and the amino group-containing vinyl monomer is acrylamide or an acrylamide substituted product or an unsaturated The composition according to claim 1, which is a fatty acid amino ester or a derivative thereof or aminostyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9972381A JPS582336A (en) | 1981-06-29 | 1981-06-29 | Graft copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9972381A JPS582336A (en) | 1981-06-29 | 1981-06-29 | Graft copolymer composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29623589A Division JPH02167342A (en) | 1989-11-16 | 1989-11-16 | Graft copolymer elastomer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS582336A JPS582336A (en) | 1983-01-07 |
| JPH0253468B2 true JPH0253468B2 (en) | 1990-11-16 |
Family
ID=14254988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9972381A Granted JPS582336A (en) | 1981-06-29 | 1981-06-29 | Graft copolymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS582336A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6327563A (en) * | 1986-07-21 | 1988-02-05 | Nippon Oil & Fats Co Ltd | Primer composition |
| USH1405H (en) * | 1992-04-09 | 1995-01-03 | Shell Oil Company | Epoxy resin composition |
| JP2011094074A (en) * | 2009-10-30 | 2011-05-12 | Asahi Kasei Chemicals Corp | Modified block copolymer for foamed article and composition of the same |
| JP5562004B2 (en) * | 2009-10-30 | 2014-07-30 | 旭化成ケミカルズ株式会社 | Modified block copolymer and composition thereof |
-
1981
- 1981-06-29 JP JP9972381A patent/JPS582336A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS582336A (en) | 1983-01-07 |
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