JP2010116510A - Modified polyolefin resin composition - Google Patents
Modified polyolefin resin composition Download PDFInfo
- Publication number
- JP2010116510A JP2010116510A JP2008291942A JP2008291942A JP2010116510A JP 2010116510 A JP2010116510 A JP 2010116510A JP 2008291942 A JP2008291942 A JP 2008291942A JP 2008291942 A JP2008291942 A JP 2008291942A JP 2010116510 A JP2010116510 A JP 2010116510A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin resin
- vinyl monomer
- weight
- resin composition
- modified polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 107
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 112
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 79
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 58
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- -1 polypropylene Polymers 0.000 claims description 27
- 229920000098 polyolefin Polymers 0.000 claims description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 239000007870 radical polymerization initiator Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 description 40
- 239000005977 Ethylene Substances 0.000 description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 25
- 238000004898 kneading Methods 0.000 description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 150000001993 dienes Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 7
- 229920005604 random copolymer Polymers 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical class OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 2
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 2
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 2
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 2
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 101000837805 Homo sapiens Testis-expressed protein 44 Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 102100028514 Testis-expressed protein 44 Human genes 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- SVHAMPNLOLKSFU-UHFFFAOYSA-N 1,2,2-trichloroethenylbenzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1 SVHAMPNLOLKSFU-UHFFFAOYSA-N 0.000 description 1
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 description 1
- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 description 1
- ZENYUPUKNXGVDY-UHFFFAOYSA-N 1,4-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=C(C(C)=C)C=C1 ZENYUPUKNXGVDY-UHFFFAOYSA-N 0.000 description 1
- UNJDAYYZWZJNNT-UHFFFAOYSA-N 1,5,5-tris(ethenyl)cyclohexa-1,3-diene Chemical compound C=CC1=CC=CC(C=C)(C=C)C1 UNJDAYYZWZJNNT-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- XJCQFMIXTZNXMF-UHFFFAOYSA-N 1-chloro-3-(2-chloroethenyl)benzene Chemical compound ClC=CC1=CC=CC(Cl)=C1 XJCQFMIXTZNXMF-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- YNQXOOPPJWSXMW-UHFFFAOYSA-N 1-ethenyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C=C YNQXOOPPJWSXMW-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- VKVLTUQLNXVANB-UHFFFAOYSA-N 1-ethenyl-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C=C VKVLTUQLNXVANB-UHFFFAOYSA-N 0.000 description 1
- ZJSKEGAHBAHFON-UHFFFAOYSA-N 1-ethenyl-3-fluorobenzene Chemical compound FC1=CC=CC(C=C)=C1 ZJSKEGAHBAHFON-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- SYZVQXIUVGKCBJ-UHFFFAOYSA-N 1-ethenyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C=C)=C1 SYZVQXIUVGKCBJ-UHFFFAOYSA-N 0.000 description 1
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 1
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
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- FLHHXRRHNQZUGO-UHFFFAOYSA-N 2,2-dinitroethenylbenzene Chemical compound [O-][N+](=O)C([N+]([O-])=O)=CC1=CC=CC=C1 FLHHXRRHNQZUGO-UHFFFAOYSA-N 0.000 description 1
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- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- LQZDDWKUQKQXGC-UHFFFAOYSA-N 2-(2-methylprop-2-enoxymethyl)oxirane Chemical compound CC(=C)COCC1CO1 LQZDDWKUQKQXGC-UHFFFAOYSA-N 0.000 description 1
- CRQSAKXMWFFXJG-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methyl]oxirane Chemical compound C1=CC(C=C)=CC=C1CC1OC1 CRQSAKXMWFFXJG-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-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
- QSOMQGJOPSLUAZ-UHFFFAOYSA-N 2-ethenylbuta-1,3-dienylbenzene Chemical compound C=CC(C=C)=CC1=CC=CC=C1 QSOMQGJOPSLUAZ-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical class [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- MBGHHXWAKSEHMA-UHFFFAOYSA-N 2-phenylethene-1,1,2-triol Chemical compound OC(O)=C(O)C1=CC=CC=C1 MBGHHXWAKSEHMA-UHFFFAOYSA-N 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本発明は、ポリオレフィン樹脂にエポキシ基含有ビニル単量体及び芳香族ビニル単量体を、またはさらに（メタ）アクリル酸エステル単量体をグラフト反応させた樹脂組成物であって、変性ポリオレフィン樹脂組成物のグラフト鎖の重量平均分子量が特定の範囲にある組成物及び該樹脂を含有する組成物に関する。さらに、難接着基材に対する優れた接着性を有するポリオレフィンシートまたはフィルム状成形体を提供することを目的とする。 The present invention relates to a resin composition obtained by graft-reacting an epoxy group-containing vinyl monomer and an aromatic vinyl monomer or a (meth) acrylic acid ester monomer to a polyolefin resin, the modified polyolefin resin composition The present invention relates to a composition having a weight average molecular weight of a graft chain in a specific range and a composition containing the resin. Furthermore, it aims at providing the polyolefin sheet | seat or film-form molded object which has the outstanding adhesiveness with respect to a difficult-to-adhere base material.
ポリオレフィン樹脂、例えばポリプロピレン樹脂は、その成形性、剛性、耐熱性、耐薬品性、電気絶縁性などに優れ、また安価であることから、フィルム、繊維、そのほか様々な形状の成形品として汎用的に使用されている。一方で、ポリプロピレンは分子内に極性基を持たず、非極性で化学的に極めて不活性な高分子である。そのため、接着性、塗装密着性、耐油性等が低いという課題がある。この課題を改善するために、ポリオレフィン樹脂へ極性官能基を有する重合可能なモノマーをグラフト重合させて、変性樹脂を製造する方法が試みられ、以下のような方法が提案されている。
（ｉ）水中に分散させたポリオレフィン樹脂粒子にビニル単量体を含浸させ、過酸化物の存在下で加熱して変性ポリオレフィンを製造する方法（特許文献１）。
（ｉｉ）ポリオレフィン樹脂、無水マレイン酸と有機過酸化物とを溶融混練し、変性ポリオレフィンを製造する方法（特許文献２）。
Polyolefin resins, such as polypropylene resins, are excellent in moldability, rigidity, heat resistance, chemical resistance, electrical insulation, etc., and are inexpensive, so they are widely used as molded products in films, fibers, and other various shapes. in use. On the other hand, polypropylene has no polar group in the molecule, and is a nonpolar, chemically extremely inert polymer. Therefore, there exists a subject that adhesiveness, coating adhesion, oil resistance, etc. are low. In order to improve this problem, a method for producing a modified resin by graft polymerization of a polymerizable monomer having a polar functional group to a polyolefin resin has been proposed, and the following method has been proposed.
(I) A method in which a polyolefin resin particle dispersed in water is impregnated with a vinyl monomer and heated in the presence of a peroxide to produce a modified polyolefin (Patent Document 1).
(Ii) A method for producing a modified polyolefin by melt-kneading a polyolefin resin, maleic anhydride and an organic peroxide (Patent Document 2).
（ｉ）の方法では様々なビニル単量体をポリオレフィン樹脂にグラフトさせることができる。しかし、エポキシ基などの極性の高い官能基を持つモノマーは、非極性であるポリオレフィン樹脂に含浸しにくく、共重合できる量に限界があった。また、該モノマーの水への溶解抑制剤を必要とするため、反応後の変性ポリオレフィン組成物中に溶解抑制剤が残存し、印刷性、インキ密着性、接着性を阻害するという問題点があった。 In the method (i), various vinyl monomers can be grafted onto the polyolefin resin. However, a monomer having a highly polar functional group such as an epoxy group is difficult to impregnate a nonpolar polyolefin resin, and the amount of copolymerization is limited. In addition, since a dissolution inhibitor for the monomer in water is required, the dissolution inhibitor remains in the modified polyolefin composition after the reaction, which impairs printability, ink adhesion, and adhesion. It was.
（ｉｉ）の方法では、ポリオレフィン樹脂に共重合できるモノマーの種類は限られている。例えば無水マレイン酸の代わりにメタクリル酸グリシジルを用いると、モノマーが未反応のまま揮発したり、モノマー同士の重合が起こるだけでポリオレフィン樹脂にグラフトしなかったり、余剰の過酸化物によりポリオレフィンの主鎖が切断されて低分子量化するため、機械的特性が低下し、接着性への充分な要求に応えるレベルに達しているとは言えないのが現状である。
本発明は、簡素な装置を用い、容易な方法により、難接着基材に対し優れた接着性を有する変性ポリオレフィン樹脂、該樹脂を含有する組成物およびその製造方法を提供することを目的とする。 An object of the present invention is to provide a modified polyolefin resin having excellent adhesion to a difficult-to-adhere substrate by a simple method using a simple apparatus, a composition containing the resin, and a method for producing the same. .
本発明者らは、上述の現状に鑑み、鋭意検討した結果、ポリオレフィン樹脂にエポキシ基含有ビニル単量体及び芳香族ビニル単量体を、またはさらに（メタ）アクリル酸エステル単量体をグラフト反応させた樹脂組成物であって、変性ポリオレフィン樹脂組成物のグラフト鎖の重量平均分子量が特定の範囲にある組成物が、上記の物性を付与することが可能となることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above-described present situation, the present inventors have grafted a polyolefin resin with an epoxy group-containing vinyl monomer and an aromatic vinyl monomer, or further with a (meth) acrylic acid ester monomer. The present invention was completed by finding that a resin composition having a weight average molecular weight of a graft chain of a modified polyolefin resin composition in a specific range can impart the above-mentioned physical properties. It came to do.
すなわち、本発明は、下記１）〜６）に関する。 That is, the present invention relates to the following 1) to 6).
１）（Ａ）ポリオレフィン樹脂に（Ｂ）少なくとも２種以上のビニル単量体をグラフト反応させた樹脂組成物であって、（Ｂ）ビニル単量体が（Ａ）ポリオレフィン樹脂１００重量部あたり（Ｂ−１）エポキシ基含有ビニル単量体０．１〜１００重量部、（Ｂ−２）芳香族ビニル単量体０．１〜５０重量部、（Ｂ−３）（メタ）アクリル酸エステル単量体０〜５０重量部を含有し、（Ｂ）ビニル単量体からなるグラフト鎖の重量平均分子量が１００００〜１０００００であることを特徴とする変性ポリオレフィン樹脂組成物。 1) (A) A resin composition obtained by graft-reacting (B) at least two or more types of vinyl monomers to a polyolefin resin, wherein (B) the vinyl monomer is (A) per 100 parts by weight of the polyolefin resin ( B-1) 0.1-100 parts by weight of an epoxy group-containing vinyl monomer, (B-2) 0.1-50 parts by weight of an aromatic vinyl monomer, (B-3) (meth) acrylic acid ester A modified polyolefin resin composition comprising 0 to 50 parts by weight of a monomer and (B) a graft chain comprising a vinyl monomer having a weight average molecular weight of 10,000 to 100,000.
２）（Ａ）ポリオレフィン樹脂と（Ｃ）ラジカル重合開始剤を溶融混練した後、次いで（Ｂ）ビニル単量体を加え溶融混練することを特徴とする１）に記載の変性ポリオレフィン樹脂組成物の製造方法。 2) The modified polyolefin resin composition according to 1), wherein (A) a polyolefin resin and (C) a radical polymerization initiator are melt-kneaded, and then (B) a vinyl monomer is added and melt-kneaded. Production method.
３）（Ａ）ポリオレフィン樹脂と（Ｃ）ラジカル重合開始剤を溶融混練した後、次いでバレル温度２５〜１００℃で（Ｂ）ビニル単量体を加え溶融混練することを特徴とする２）に記載の変性ポリオレフィン樹脂組成物の製造方法。 3) (2) characterized in that (A) a polyolefin resin and (C) a radical polymerization initiator are melt-kneaded, and then (B) a vinyl monomer is added and melt-kneaded at a barrel temperature of 25 to 100 ° C. Of the modified polyolefin resin composition.
４）（Ａ）ポリオレフィン樹脂が、プロピレン単位が過半量であるポリプロピレン樹脂である、２）〜３）のいずれか１項に記載の変性ポリオレフィン樹脂組成物の製造方法。 4) The method for producing a modified polyolefin resin composition according to any one of 2) to 3), wherein (A) the polyolefin resin is a polypropylene resin having a majority of propylene units.
５）１）に記載の変性ポリオレフィン樹脂組成物を含有し、熱溶着性を有するポリオレフィンシートまたはフィルム状成形体。 5) A polyolefin sheet or film-like molded article containing the modified polyolefin resin composition described in 1) and having heat-weldability.
６）１）に記載の変性ポリオレフィン樹脂組成物で接着されてなる接着体。 6) An adhesive body bonded with the modified polyolefin resin composition according to 1).
本発明の変性ポリオレフィン樹脂組成物は、単独使用のみならず、ポリオレフィン樹脂に添加剤として使用しても、難接着基材に対し優れた接着力を確保することができ、文具、雑貨、食品などの包装材、自動車用部品、家電などの電気電子部品、各種産業用資材などの幅広い分野に好適に用いられる。 The modified polyolefin resin composition of the present invention can be used not only alone but also as an additive to polyolefin resins, and can ensure excellent adhesion to difficult-to-adhere substrates, such as stationery, miscellaneous goods, foods, etc. It is suitably used in a wide range of fields such as packaging materials, automotive parts, electrical and electronic parts such as home appliances, and various industrial materials.
以下に本発明の詳細について述べる。
（（Ａ）ポリオレフィン樹脂）
前記（Ａ）ポリオレフィン樹脂としては、例えばポリエチレン、ポリプロピレン、ポリ−１−ブテン、ポリイソブチレン、プロピレンとエチレンおよび／または１−ブテンとのあらゆる比率でのランダム共重合体またはブロック共重合体、エチレンとプロピレンとのあらゆる比率においてジエン成分が５０重量％以下であるエチレン−プロピレン−ジエン三元共重合体、ポリメチルペンテン、シクロペンタジエンとエチレンおよび／またはプロピレンとの共重合体などの環状ポリオレフィン、エチレンまたはプロピレンと５０重量％以下のビニル化合物などとのランダム共重合体、ブロック共重合体などが挙げられる。
Details of the present invention will be described below.
((A) polyolefin resin)
Examples of the (A) polyolefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymer or block copolymer in any ratio of propylene and ethylene and / or 1-butene, and ethylene. Cyclic polyolefins such as ethylene-propylene-diene terpolymers, polymethylpentene, copolymers of cyclopentadiene and ethylene and / or propylene having a diene component of 50% by weight or less in any proportion to propylene, ethylene or Random copolymers, block copolymers, and the like of propylene and 50% by weight or less of a vinyl compound are exemplified.
中でも、ポリプロピレン、ポリエチレン、ポリイソブチレンが好ましく、ポリプロピレンが特に好ましい。 Among these, polypropylene, polyethylene, and polyisobutylene are preferable, and polypropylene is particularly preferable.
また、極性基を有するビニル単量体と相溶し易い点で、極性基が導入されたポリオレフィン樹脂も使用できる。極性基が導入されたポリオレフィン樹脂の具体例としては、無水マレイン酸変性ポリプロピレン、マレイン酸変性ポリプロピレン、アクリル酸変性ポリプロピレンなどの酸変性ポリプロピレン；エチレン／塩化ビニル共重合体、エチレン／塩化ビニリデン共重合体、エチレン／アクリロニトリル共重合体、エチレン／メタクリロニトリル共重合体、エチレン／酢酸ビニル共重合体、エチレン／アクリルアミド共重合体、エチレン／メタクリルアミド共重合体、エチレン／アクリル酸共重合体、エチレン／メタクリル酸共重合体、エチレン／マレイン酸共重合体、エチレン／アクリル酸メチル共重合体、エチレン／アクリル酸エチル共重合体、エチレン／アクリル酸イソプロピル共重合体、エチレン／アクリル酸ブチル共重合体、エチレン／アクリル酸イソブチル共重合体、エチレン／アクリル酸２−エチルヘキシル共重合体、エチレン／メタクリル酸メチル共重合体、エチレン／メタクリル酸エチル共重合体、エチレン／メタクリル酸イソプロピル共重合体、エチレン／メタクリル酸ブチル共重合体、エチレン／メタクリル酸イソブチル共重合体、エチレン／メタクリル酸２−エチルヘキシル共重合体、エチレン／無水マレイン酸共重合体、エチレン／アクリル酸エチル／無水マレイン酸共重合体、エチレン／アクリル酸金属塩共重合体、エチレン／メタクリル酸金属塩共重合体、エチレン／酢酸ビニル共重合体、又はその鹸化物、エチレン／プロピオン酸ビニル共重合体、エチレン／メタクリル酸グリシジル共重合体エチレン／アクリル酸エチル／メタクリル酸グリシジル共重合体、エチレン／酢酸ビニル／メタクリル酸グリシジル共重合体などのエチレンまたはα−オレフィン／ビニル単量体共重合体；塩素化ポリプロピレン塩素化ポリエチレンなどの塩素化ポリオレフィンなどが挙げられる。これらの極性基導入ポリオレフィンは混合しても使用できる。 In addition, a polyolefin resin into which a polar group is introduced can also be used because it is easily compatible with a vinyl monomer having a polar group. Specific examples of polyolefin resins having polar groups introduced include acid-modified polypropylenes such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymers, ethylene / vinylidene chloride copolymers , Ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylamide copolymer, ethylene / acrylic acid copolymer, ethylene / Methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer, Ethylene / A Isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / butyl methacrylate Copolymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / acrylic acid Metal salt copolymer, ethylene / methacrylic acid metal salt copolymer, ethylene / vinyl acetate copolymer or saponified product thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer ethylene / acrylic acid Ethyl / glycidyl methacrylate copolymer , Ethylene or α- olefin / vinyl monomer copolymers such as ethylene / vinyl acetate / glycidyl methacrylate copolymer; and chlorinated polyolefins such as chlorinated polypropylene chlorinated polyethylene. These polar group-introduced polyolefins can be used even if mixed.
前記原料ポリオレフィン樹脂には、必要に応じて、ほかの樹脂またはゴムを本発明の効果を損なわない範囲内で添加してもよい。 If necessary, another resin or rubber may be added to the raw material polyolefin resin as long as the effects of the present invention are not impaired.
前記ほかの樹脂またはゴムとしては、たとえばポリペンテン−１、ポリメチルペンテン−１などのポリα−オレフィン；プロピレン含有量が７５重量％未満のプロピレン／ブテン−１共重合体などのエチレンまたはα−オレフィン／α−オレフィン共重合体；プロピレン含有量が７５重量％未満のエチレン／プロピレン／５−エチリデン−２−ノルボルネン共重合体などのエチレンまたはα−オレフィン／α−オレフィン／ジエン単量体共重合体；ポリブタジエン、ポリイソプレンなどのポリジエン共重合体；スチレン／ブタジエンランダム共重合体などのビニル単量体／ジエン単量体ランダム共重合体；スチレン／ブタジエン／スチレンブロック共重合体などのビニル単量体／ジエン単量体／ビニル単量体ブロック共重合体；水素化（スチレン／ブタジエンランダム共重合体）などの水素化（ビニル単量体／ジエン単量体ランダム共重合体）；水素化（スチレン／ブタジエン／スチレンブロック共重合体）などの水素化（ビニル単量体／ジエン単量体／ビニル単量体ブロック共重合体）；アクリロニトリル／ブタジエン／スチレングラフト共重合体、メタクリル酸メチル／ブタジエン／スチレングラフト共重合体などのビニル単量体／ジエン単量体／ビニル単量体グラフト共重合体；ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアクリロニトリル、ポリ酢酸ビニル、ポリアクリル酸エチル、ポリアクリル酸ブチル、ポリメタクリル酸メチル、ポリスチレンなどのビニル重合体；塩化ビニル／アクリロニトリル共重合体、塩化ビニル／酢酸ビニル共重合体、アクリロニトリル／スチレン共重合体、メタクリル酸メチル／スチレン共重合体などのビニル共重合体などがあげられる。 Examples of the other resin or rubber include poly α-olefins such as polypentene-1 and polymethylpentene-1; ethylene or α-olefins such as a propylene / butene-1 copolymer having a propylene content of less than 75% by weight. / Α-olefin copolymer; ethylene or α-olefin / α-olefin / diene monomer copolymer such as ethylene / propylene / 5-ethylidene-2-norbornene copolymer having a propylene content of less than 75% by weight A polydiene copolymer such as polybutadiene and polyisoprene; a vinyl monomer / diene monomer random copolymer such as a styrene / butadiene random copolymer; a vinyl monomer such as a styrene / butadiene / styrene block copolymer; / Diene monomer / Vinyl monomer block copolymer; Hydrogenation (styrene) Hydrogenation (vinyl monomer / diene monomer random copolymer); hydrogenation (styrene / butadiene / styrene block copolymer), etc. (vinyl monomer / Diene monomer / vinyl monomer block copolymer); vinyl monomer / diene monomer / vinyl monomer such as acrylonitrile / butadiene / styrene graft copolymer, methyl methacrylate / butadiene / styrene graft copolymer Polymer graft copolymer; Vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polystyrene; vinyl chloride / acrylonitrile copolymer Polymer, vinyl chloride / vinyl acetate copolymer, acrylonitrile / styrene Polymers, vinyl copolymers such as methyl methacrylate / styrene copolymer.
ポリオレフィン樹脂に対するこれらほかの樹脂またはゴムの添加量は、この樹脂の種類またはゴムの種類により異なり、前述のように本発明の効果を損なわない範囲内にあればよいものであるが、通常、２５重量％程度以下であることが好ましい。 The amount of other resin or rubber added to the polyolefin resin varies depending on the type of the resin or the type of the rubber and may be within the range not impairing the effects of the present invention as described above. It is preferable that it is about wt% or less.
また、これらポリオレフィン樹脂（各種の添加材料を含むばあいもある）は粒子状のものであってもペレット状のものであってもよく、その大きさや形はとくに制限されるものではない。 Further, these polyolefin resins (which may contain various additive materials) may be in the form of particles or pellets, and the size and shape are not particularly limited.
また、前記の添加材料（ほかの樹脂、およびゴム）を用いるばあいは、この添加材料は予めポリオレフィン樹脂に添加されているものであっても、ポリオレフィン樹脂を溶融するときに添加されるものであってもよく、また変性ポリオレフィン樹脂を製造したのちに適宜の方法でこの変性ポリオレフィン樹脂に添加されるものであってもよい。 In addition, when the above additive materials (other resins and rubbers) are used, this additive material is added when the polyolefin resin is melted, even if it is previously added to the polyolefin resin. Alternatively, the modified polyolefin resin may be added to the modified polyolefin resin by an appropriate method after the modified polyolefin resin is produced.
ポリオレフィン樹脂におけるプロピレン成分に関しては、ポリオレフィン樹脂に対しラジカルが発生し易くなる点で、プロピレン単位が過半量であることが好ましい。ここでいう過半量とはポリオレフィン樹脂に対するプロピレン成分が５０重量％以上のことを意味する。 Regarding the propylene component in the polyolefin resin, it is preferable that the propylene unit is a majority amount in that radicals are easily generated in the polyolefin resin. The majority amount here means that the propylene component with respect to the polyolefin resin is 50% by weight or more.
（（Ｂ）ビニル単量体）
本発明に用いる（Ｂ）ビニル単量体は、必須成分として（Ｂ−１）エポキシ基含有ビニル単量体および（Ｂ−２）芳香族ビニル単量体を含有する。任意成分としてさらに（Ｂ−３）（メタ）アクリル酸エステル単量体を含有してもよい。さらに、本発明の効果を損なわない範囲で、（Ｂ−１）、（Ｂ−２）、（Ｂ−３）成分以外の単量体を少量含有してもよい。
((B) Vinyl monomer)
The (B) vinyl monomer used in the present invention contains (B-1) an epoxy group-containing vinyl monomer and (B-2) an aromatic vinyl monomer as essential components. You may contain the (B-3) (meth) acrylic acid ester monomer further as an arbitrary component. Furthermore, you may contain a small amount of monomers other than (B-1), (B-2), and (B-3) component in the range which does not impair the effect of this invention.
（Ｂ−１）エポキシ基含有ビニル単量体は、変性ポリオレフィン樹脂に極性を付与するための成分である。（Ｂ−２）芳香族ビニル単量体は、（Ｂ−１）エポキシ基含有ビニル単量体のグラフト効率を向上させるための成分である。（Ｂ−１）成分および（Ｂ−２）成分を併用することにより、優れた接着性を有する変性ポリオレフィン樹脂が得られる。 (B-1) The epoxy group-containing vinyl monomer is a component for imparting polarity to the modified polyolefin resin. (B-2) The aromatic vinyl monomer is a component for improving the graft efficiency of the (B-1) epoxy group-containing vinyl monomer. By using the component (B-1) and the component (B-2) in combination, a modified polyolefin resin having excellent adhesiveness can be obtained.
（Ｂ−３）（メタ）アクリル酸エステル単量体は、（Ｂ−１）エポキシ基含有ビニル単量体のグラフト効率をより向上させたり、変性ポリオレフィン樹脂の物性を調整するための成分である。 (B-3) The (meth) acrylic acid ester monomer is a component for further improving the grafting efficiency of the (B-1) epoxy group-containing vinyl monomer or adjusting the physical properties of the modified polyolefin resin. .
（（Ｂ−１）エポキシ基含有ビニル単量体）
例示するならば、メタクリル酸グリシジル、アクリル酸グリシジル、マレイン酸モノグリシジル、マレイン酸ジグリシジル、イタコン酸モノグリシジル、イタコン酸ジグリシジル、アリルコハク酸モノグリシジル、アリルコハク酸ジグリシジル、ｐ−スチレンカルボン酸グリシジル、アリルグリシジルエーテル、メタアリルグリシジルエーテル、スチレン−ｐ−グリシジルエーテル、ｐ−グリシジルスチレン、３，４−エポキシ−１−ブテン、３，４−エポキシ−３−メチル−１−ブテンなどのエポキシオレフィン、ビニルシクロヘキセンモノオキシドなどの１種または２種以上が挙げられる。これらのうち、メタクリル酸グリシジル、アクリル酸グリシジルが安価という点で好ましい。
((B-1) epoxy group-containing vinyl monomer)
For example, glycidyl methacrylate, glycidyl acrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, glycidyl p-styrenecarboxylate, allyl glycidyl ether , Epoxy olefins such as methallyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, vinylcyclohexene monooxide 1 type or 2 types or more, such as, are mentioned. Of these, glycidyl methacrylate and glycidyl acrylate are preferable in that they are inexpensive.
前記（Ｂ−１）エポキシ基含有ビニル単量体の添加量は、（Ａ）ポリオレフィン樹脂１００重量部に対して、０．１〜１００重量部であることが好ましく、０．５〜５０重量部であることがさらに好ましく、１〜１０重量部であることが特に好ましい。また、（Ａ）ポリオレフィン樹脂、（Ｂ−１）エポキシ基含有ビニル単量体、（Ｂ−２）芳香族ビニル単量体、（Ｂ−３）（メタ）アクリル酸エステル単量体の合計量１００重量％における（Ｂ−１）エポキシ基含有ビニル単量体の割合が、０．１〜５０重量％の範囲であることが好ましく、０．５〜４０重量％の範囲であることがより好ましく、１〜３０重量％の範囲であることが特に好ましい。添加量が少なすぎると接着性が充分に改善されない傾向があり、添加量が多すぎると好適な形状や外観を有する樹脂組成物として取得できない傾向がある。 The addition amount of the (B-1) epoxy group-containing vinyl monomer is preferably 0.1 to 100 parts by weight, and 0.5 to 50 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin. More preferably, it is 1 to 10 parts by weight. The total amount of (A) polyolefin resin, (B-1) epoxy group-containing vinyl monomer, (B-2) aromatic vinyl monomer, (B-3) (meth) acrylic acid ester monomer The proportion of the (B-1) epoxy group-containing vinyl monomer in 100% by weight is preferably in the range of 0.1 to 50% by weight, more preferably in the range of 0.5 to 40% by weight. 1 to 30% by weight is particularly preferable. If the addition amount is too small, the adhesiveness tends not to be sufficiently improved, and if the addition amount is too large, there is a tendency that it cannot be obtained as a resin composition having a suitable shape and appearance.
（（Ｂ−２）芳香族ビニル単量体）
例示するならば、スチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、β−メチルスチレン、ジメチルスチレン、トリメチルスチレンなどのメチルスチレン；ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン、α−クロロスチレン、β−クロロスチレン、ジクロロスチレン、トリクロロスチレンなどのクロロスチレン；ｏ−ブロモスチレン、ｍ−ブロモスチレン、ｐ−ブロモスチレン、ジブロモスチレン、トリブロモスチレンなどのブロモスチレン；ｏ−フルオロスチレン、ｍ−フルオロスチレン、ｐ−フルオロスチレン、ジフルオロスチレン、トリフルオロスチレンなどのフルオロスチレン；ｏ−ニトロスチレン、ｍ−ニトロスチレン、ｐ−ニトロスチレン、ジニトロスチレン、トリニトロスチレンなどのニトロスチレン；ｏ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｐ−ヒドロキシスチレン、ジヒドロキシスチレン、トリヒドロキシスチレンなどのビニルフェノール；ｏ−ジビニルスチレン、ｍ−ジビニルスチレン、ｐ−ジビニルスチレンなどのジビニルスチレン；ｏ−ジイソプロペニルベンゼン、ｍ−ジイソプロペニルベンゼン、ｐ−ジイソプロペニルベンゼンなどのジイソプロペニルベンゼン；などの１種または２種以上が挙げられる。これらのうちスチレン、α−メチルスチレン、ｐ−メチルスチレンなどのメチルスチレン、ジビニルベンゼン単量体またはジビニルベンゼン異性体混合物が安価であるという点で好ましい。
((B-2) aromatic vinyl monomer)
For example, styrene; methyl styrene such as o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene, dimethyl styrene, trimethyl styrene; o-chloro styrene, m-chloro Chlorostyrene such as styrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene; o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, tribromostyrene, etc. Bromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m-nitrostyrene, p-nitrostyrene, dinitrostyrene, Nitrostyrenes such as renitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene; o-divinylstyrene, m-divinylstyrene, p-divinylstyrene, etc. 1 type, or 2 or more types, such as divinyl styrene; diisopropenylbenzene, such as o-diisopropenylbenzene, m-diisopropenylbenzene, p-diisopropenylbenzene; Of these, methylstyrene such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene monomer or divinylbenzene isomer mixture is preferable in that it is inexpensive.
前記（Ｂ−２）芳香族ビニル単量体の添加量は、（Ａ）ポリオレフィン樹脂１００重量部に対して、０．１〜５０重量部であることが好ましく、０．５〜４０重量部であることがさらに好ましく、１〜３０重量部であることが特に好ましい。添加量が少なすぎるとポリオレフィン樹脂に対するエポキシ基含有ビニル単量体のグラフト率が劣る傾向がある。一方、添加量が多すぎるとエポキシ基含有ビニル単量体のグラフト効率が飽和域に達するので、５０重量部を上限とすることが好ましい。 The amount of the (B-2) aromatic vinyl monomer added is preferably 0.1 to 50 parts by weight, and 0.5 to 40 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin. More preferably, it is 1 to 30 parts by weight. If the amount added is too small, the graft ratio of the epoxy group-containing vinyl monomer to the polyolefin resin tends to be poor. On the other hand, if the addition amount is too large, the grafting efficiency of the epoxy group-containing vinyl monomer reaches the saturation range, so it is preferable that the upper limit is 50 parts by weight.
（（Ｂ−３）（メタ）アクリル酸エステル単量体）
（メタ）アクリル酸エステルとしては、特に制限されないが、好ましくは炭素数４〜２０、より好ましくは４〜１０の（メタ）アクリル酸エステルである。具体的には、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェニルエチル、（メタ）アクリル酸ナフチル等が挙げられ、なかでも（メタ）アクリル酸メチルが安価である点で好ましい。
((B-3) (meth) acrylic acid ester monomer)
Although it does not restrict | limit especially as a (meth) acrylic acid ester, Preferably it is C4-C20, More preferably, it is a C4-10 (meth) acrylic acid ester. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic Examples thereof include tert-butyl acid, benzyl (meth) acrylate, phenylethyl (meth) acrylate, naphthyl (meth) acrylate, and the like. Among these, methyl (meth) acrylate is preferable because it is inexpensive.
前記（Ｂ−３）（メタ）アクリル酸エステル単量体の添加量は、（Ａ）ポリオレフィン樹脂１００重量部に対して、０．０１〜５０重量部であることが好ましく、０．０５〜４０重量部であることがさらに好ましく、０．１〜３０重量部であることが特に好ましい。添加量が少なすぎるとポリオレフィン樹脂に対するエポキシ基含有ビニル単量体のグラフト率が劣る傾向がある。一方、添加量が多すぎるとグラフトに寄与しないフリーポリマーの副生する傾向があるので、芳香族ビニル単量体と同重量部を上限とすることが好ましい。 The addition amount of the (B-3) (meth) acrylic acid ester monomer is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin, and 0.05 to 40 More preferably, it is 0.1 part by weight, and particularly preferably 0.1 part by weight. If the amount added is too small, the graft ratio of the epoxy group-containing vinyl monomer to the polyolefin resin tends to be poor. On the other hand, if the amount added is too large, a free polymer that does not contribute to grafting tends to be produced as a by-product.
（（Ｃ）ラジカル開始剤）
（Ａ）ポリオレフィン樹脂に対して、（Ｂ−１）エポキシ基含有ビニル単量体、（Ｂ−２）芳香族ビニル単量体、（Ｂ−３）（メタ）アクリル酸エステル単量体をグラフト共重合する際、反応を開始するため、（Ｃ）ラジカル重合開始剤を添加する。
((C) radical initiator)
(A) Grafting (B-1) epoxy group-containing vinyl monomer, (B-2) aromatic vinyl monomer, (B-3) (meth) acrylate monomer to polyolefin resin When copolymerizing, in order to start reaction, (C) radical polymerization initiator is added.
（Ｃ）ラジカル重合開始剤としては、一般に過酸化物またはアゾ化合物などがあげられる。前記ラジカル重合開始剤としては、メチルエチルケトンパーオキサイド、メチルアセトアセテートパーオキサイドなどのケトンパーオキサイド；１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、ｎ−ブチル−４，４−ビス（ｔ−ブチルパーオキシ）バレレート、２，２−ビス（ｔ−ブチルパーオキシ）ブタンなどのパーオキシケタール；パーメタンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、クメンハイドロパーオキサイドなどのハイドロパーオキサイド；ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、α，α´−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、ｔ−ブチルクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３などのジアルキルパーオキサイド；ベンゾイルパーオキサイドなどのジアシルパーオキサイド；ジ（３−メチル−３−メトキシブチル）パーオキシジカーボネート、ジ−２−メトキシブチルパーオキシジカーボネートなどのパーオキシジカーボネート；ｔ−ブチルパーオキシオクテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシイソプロピルカーボネート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレートなどのパーオキシエステルなどの有機過酸化物の１種または２種以上があげられる。 (C) The radical polymerization initiator generally includes peroxides or azo compounds. Examples of the radical polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis Peroxyketals such as (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; permethane hydroper Hydroperoxide such as oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di ( t-Butylperoxy) hexane α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide) Dialkyl peroxides such as oxy) hexyne-3; diacyl peroxides such as benzoyl peroxide; peroxys such as di (3-methyl-3-methoxybutyl) peroxydicarbonate and di-2-methoxybutylperoxydicarbonate Dicarbonate: t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy Isopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylpa Oxy) hexane, t- butyl peroxy acetate, t- butyl peroxybenzoate, one or more organic peroxides such as peroxy esters such as di -t- butyl peroxy isophthalate and the like.
これらのうち、とくに水素引き抜き能が高いものが好ましく、そのようなラジカル重合開始剤としては、たとえば１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、ｎ−ブチル−４，４−ビス（ｔ−ブチルパーオキシ）バレレート、２，２−ビス（ｔ−ブチルパーオキシ）ブタンなどのパーオキシケタール；ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、α，α´−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、ｔ−ブチルクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３などのジアルキルパーオキサイド；ベンゾイルパーオキサイドなどのジアシルパーオキサイド；ｔ−ブチルパーオキシオクテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシイソプロピルカーボネート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレートなどのパーオキシエステルなどの１種または２種以上があげられる。 Of these, those having a particularly high hydrogen abstraction ability are preferred. Examples of such radical polymerization initiators include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1. Peroxyketals such as bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; dicumyl Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di Dialkyl peroxides such as t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diacyl peroxides such as nzoyl peroxide; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butylperoxy-3,5,5-trimethylhexano Ate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyiso 1 type, or 2 or more types, such as peroxyesters, such as phthalate, are mention | raise | lifted.
前記（Ｃ）ラジカル重合開始剤の添加量は、ポリオレフィン樹脂１００重量部に対して、０．０１〜１０重量部の範囲内にあることが好ましく、０．２〜５重量部の範囲内にあることがさらに好ましい。０．０１重量部未満では変性が充分に進行せず、１０重量部を超えると流動性、機械的特性の低下を招く。 The addition amount of the (C) radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight and in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. More preferably. If the amount is less than 0.01 part by weight, the modification does not proceed sufficiently, and if it exceeds 10 parts by weight, the fluidity and mechanical properties are lowered.
（変性ポリオレフィン樹脂組成物）
本発明の変性ポリオレフィン樹脂組成物は、（Ａ）ポリオレフィン樹脂に対し、（Ｂ−１）エポキシ基含有ビニル単量体を含む２種類以上の単量体からなるグラフト鎖をグラフトさせた樹脂組成物である。単量体として、（Ｂ−１）エポキシ基含有ビニル単量体及び（Ｂ−２）芳香族ビニル単量体を必須成分として使用し、任意でさらに（Ｂ−３）（メタ）アクリル酸エステル単量体を使用してもよい。さらに、グラフト鎖の重量平均分子量を１００００〜１０００００の範囲にすることにより、本発明の効果が得られる。
(Modified polyolefin resin composition)
The modified polyolefin resin composition of the present invention is a resin composition obtained by grafting (A) a polyolefin resin with a graft chain composed of two or more types of monomers including (B-1) an epoxy group-containing vinyl monomer. It is. (B-1) an epoxy group-containing vinyl monomer and (B-2) an aromatic vinyl monomer are used as essential components, and optionally (B-3) (meth) acrylic acid ester Monomers may be used. Furthermore, the effect of this invention is acquired by making the weight average molecular weight of a graft chain into the range of 10,000-100,000.
本発明に用いるグラフト重合反応としては、特に制限されないが、溶液重合、含浸重合、溶融重合などを用いることができる。特に、溶融重合が簡便で好ましい。 The graft polymerization reaction used in the present invention is not particularly limited, and solution polymerization, impregnation polymerization, melt polymerization and the like can be used. In particular, melt polymerization is simple and preferable.
溶融混練時の添加順序及び方法については、ポリオレフィン樹脂とラジカル重合開始剤を溶融混練した混合物に、エポキシ基含有ビニル単量体、芳香族ビニル単量体を加え溶融混練する添加順序がよく、この添加順序で行うことでグラフトに寄与しない低分子量体の生成を抑制することができる。なお、そのほか必要に応じ添加される材料の混合や溶融混練の順序及び方法はとくに制限されるものではない。 Regarding the addition order and method at the time of melt kneading, the addition order of melt kneading by adding an epoxy group-containing vinyl monomer and aromatic vinyl monomer to a mixture obtained by melt kneading a polyolefin resin and a radical polymerization initiator is good. By performing in the order of addition, it is possible to suppress the formation of a low molecular weight substance that does not contribute to grafting. In addition, the order and method of mixing and melt-kneading the materials added as necessary are not particularly limited.
溶融混練の時間（ラジカル重合開始剤を混合してからの時間）は、通常３０秒間〜６０分間である。 The melt kneading time (the time after mixing the radical polymerization initiator) is usually 30 seconds to 60 minutes.
ビニル単量体を添加する前の、ポリオレフィン樹脂とラジカル重合開始剤を溶融混練する際のバレル温度としては、８０〜２００℃が好ましく、より好ましくは９０〜１６０℃である。これより低い温度であると、ポリオレフィン樹脂が可塑化不足となり、この範囲より高い温度では、ラジカル重合開始剤が失活しやすくなる。 The barrel temperature at the time of melt-kneading the polyolefin resin and the radical polymerization initiator before adding the vinyl monomer is preferably 80 to 200 ° C, more preferably 90 to 160 ° C. If the temperature is lower than this, the polyolefin resin becomes insufficiently plasticized, and if the temperature is higher than this range, the radical polymerization initiator tends to be deactivated.
溶融状態のポリオレフィンとラジカル開始剤に対して、ビニル単量体を添加する際には、通常ポリオレフィンを溶融混練するバレル温度よりも低い方が、前記単量体類の重合が進行しやすい。ビニル単量体を添加する際のバレル温度、又は添加する部分のバレル温度は、好ましくは１０〜１５０℃、さらに好ましくは２５〜１００℃であり、ビニル単量体の解重合を抑制するという点、及びラジカル開始剤が失活しにくく、ラジカル寿命が延びる点で前述の温度範囲が好ましい。 When adding a vinyl monomer to a molten polyolefin and a radical initiator, the polymerization of the monomers is more likely to proceed at a temperature lower than the barrel temperature at which the polyolefin is usually melt-kneaded. The barrel temperature at the time of adding the vinyl monomer, or the barrel temperature of the portion to be added is preferably 10 to 150 ° C., more preferably 25 to 100 ° C., which suppresses the depolymerization of the vinyl monomer. In addition, the above-mentioned temperature range is preferable in that the radical initiator is hardly deactivated and the radical lifetime is extended.
単量体を添加した後、グラフト反応させる際のバレル温度としては、ポリオレフィン樹脂が充分に溶融し、かつ熱分解しないという点から１００〜２５０℃が好ましい。ビニル単量体を添加した付近のバレル温度は、可能な限りビニル単量体添加口を添加するバレル温度に近い方が、ビニル単量体の重合が進行しやすい。また、吐出口付近の温度を上げると、残留したラジカル重合開始剤を完全に失活させ、樹脂劣化を防ぐ目的で好ましい。ダイスヘッド、及びその隣のバレルについては、２００〜２５０℃とすることが好ましい。 The barrel temperature at the time of graft reaction after adding the monomer is preferably 100 to 250 ° C. from the viewpoint that the polyolefin resin is sufficiently melted and is not thermally decomposed. When the barrel temperature near the vinyl monomer added is as close as possible to the barrel temperature at which the vinyl monomer addition port is added, the polymerization of the vinyl monomer is likely to proceed. Moreover, it is preferable to raise the temperature near the discharge port for the purpose of completely deactivating the remaining radical polymerization initiator and preventing resin degradation. About a die head and its adjacent barrel, it is preferable to set it as 200-250 degreeC.
また、前記の溶融混練の装置としては、押出機、バンバリーミキサー、ミル、ニーダー、加熱ロールなどを使用することができる。生産性の面から単軸あるいは２軸の押出機を用いる方法が好ましい。また、各々の材料を充分に均一に混合するために、前記溶融混練を複数回繰返してもよい。 Further, as the melt kneading apparatus, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, or the like can be used. From the viewpoint of productivity, a method using a single-screw or twin-screw extruder is preferred. Moreover, in order to mix each material sufficiently uniformly, the melt kneading may be repeated a plurality of times.
本発明は、変性ポリオレフィン樹脂がグラフト構造を形成している。ポリオレフィン樹脂に対するエポキシ基含有ビニル単量体、芳香族ビニル単量体、（メタ）アクリル酸エステル単量体、ラジカル重合開始剤の仕込み量、加熱温度、溶融混練の時間等の反応条件によって、グラフト鎖の長さを制御することができる。エポキシ基含有ビニル単量体と芳香族ビニル単量体、またはさらに（メタ）アクリル酸エステル単量体からなるグラフト鎖の重量平均分子量が１００００〜１０００００であることが必須であり、１００００〜５００００であることが好ましく、１００００〜２００００であることがさらに好ましい。グラフト鎖の重量平均分子量がポリオレフィン成分の重量平均分子量より短いため、ポリオレフィン樹脂の相中に微小の相構造を形成することができ、効率よく接着性を向上させることができる。 In the present invention, the modified polyolefin resin forms a graft structure. Depending on reaction conditions such as epoxy group-containing vinyl monomer, aromatic vinyl monomer, (meth) acrylic acid ester monomer, radical polymerization initiator charge amount, heating temperature, melt kneading time for polyolefin resin The length of the chain can be controlled. It is essential that the weight average molecular weight of the graft chain composed of an epoxy group-containing vinyl monomer and an aromatic vinyl monomer, or a (meth) acrylic acid ester monomer is 10,000 to 100,000, It is preferable that it is preferably 10,000 to 20,000. Since the weight average molecular weight of the graft chain is shorter than the weight average molecular weight of the polyolefin component, a fine phase structure can be formed in the phase of the polyolefin resin, and the adhesiveness can be improved efficiently.
変性ポリオレフィン樹脂組成物には必要に応じて、酸化防止剤、金属不活性剤、燐系加工安定剤、紫外線吸収剤、紫外線安定剤、蛍光増白剤、金属石鹸、制酸吸着剤などの安定剤、または架橋剤、連鎖移動剤、核剤、滑剤、可塑剤、充填材、強化材、顔料、染料、難燃剤、帯電防止剤などの添加剤を本発明の効果を損なわない範囲内で添加してもよい。これらの安定剤および添加剤を用いる場合は、予め（Ａ）ポリオレフィン樹脂に添加されているものであってもよく、（Ａ）ポリオレフィン樹脂に（Ｂ−１）〜（Ｂ−３）成分をグラフトさせる際に添加されるものであってもよく、また変性ポリオレフィン樹脂を製造したのちに適宜の方法でこの変性ポリオレフィン樹脂に添加されるものであってもよい。 If necessary, the modified polyolefin resin composition may be stabilized with antioxidants, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, fluorescent brighteners, metal soaps, antacid adsorbents, etc. Additives or additives such as crosslinking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents, etc. within the range that does not impair the effects of the present invention May be. When these stabilizers and additives are used, they may be added to the (A) polyolefin resin in advance, and the components (B-1) to (B-3) are grafted to the (A) polyolefin resin. It may be added when the modified polyolefin resin is produced, or may be added to the modified polyolefin resin by an appropriate method after the modified polyolefin resin is produced.
本発明の変性ポリオレフィン樹脂は、単独で使用してもよく、他の樹脂と配合して使用してもよい。他の樹脂としては公知の樹脂を特に限定なく使用できるが、相溶性の観点から、ポリオレフィン樹脂に配合して用いることが好ましい。本発明の変性ポリオレフィン樹脂は接着性に優れるため、単独でも接着剤として使用できるし、ポリオレフィン樹脂など他の樹脂に配合して接着性を向上するための添加剤として使用することもできる。 The modified polyolefin resin of the present invention may be used alone or in combination with other resins. As other resins, known resins can be used without particular limitation, but from the viewpoint of compatibility, it is preferable to use them blended with polyolefin resins. Since the modified polyolefin resin of the present invention is excellent in adhesiveness, it can be used alone as an adhesive, or it can be used as an additive for improving adhesiveness by blending with other resins such as polyolefin resin.
本発明の変性ポリオレフィン樹脂が配合されるポリオレフィン樹脂としては、例えばポリプロピレン単独重合体、高密度ポリエチレン、低密度ポリエチレン、線状低密度ポリエチレン、ポリ−１−ブテン、ポリイソブチレン、プロピレンとエチレンおよび／または１−ブテンとのあらゆる比率でのランダム共重合体またはブロック共重合体、エチレンとプロピレンとのあらゆる比率においてジエン成分が５０重量％以下であるエチレン−プロピレン−ジエン三元共重合体、ポリメチルペンテン、シクロペンタジエンとエチレンおよび／またはプロピレンとの共重合体などの環状ポリオレフィン、エチレンまたはプロピレンと５０重量％以下のたとえば酢酸ビニル、メタクリル酸アルキルエステル、アクリル酸アルキルエステル、芳香族ビニルなどのビニル化合物などとのランダム共重合体、ポリ
オレフィン系熱可塑性エラストマーブロック共重合体、オレフィン系熱可塑性エラストマー（ポリプロピレンとエチレン／プロピレン共重合体又はエチレン−プロピレン−ジエン三元共重合体の単純混合物、その一部架橋物、又はその完全架橋物）などが挙げられ、これらは単独でまたは２種以上を混合して用いることができる。
Examples of the polyolefin resin with which the modified polyolefin resin of the present invention is blended include polypropylene homopolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene, polyisobutylene, propylene and ethylene and / or Random copolymer or block copolymer in any ratio with 1-butene, ethylene-propylene-diene terpolymer with 50% by weight or less of diene component in any ratio of ethylene and propylene, polymethylpentene , Cyclic polyolefin such as a copolymer of cyclopentadiene and ethylene and / or propylene, ethylene or propylene and 50% by weight or less of vinyl acetate, methacrylic acid alkyl ester, acrylic acid alkyl ester, aromatic vinyl Random copolymer with any vinyl compound, polyolefin-based thermoplastic elastomer block copolymer, olefin-based thermoplastic elastomer (simple mixture of polypropylene and ethylene / propylene copolymer or ethylene-propylene-diene terpolymer, The partially crosslinked product or the completely crosslinked product) can be used, and these can be used alone or in admixture of two or more.
剛性が高く、安価であるという点からはポリプロピレン単独重合体が好ましく、剛性および耐衝撃性がともに高いという点からはプロピレンとほかの単量体とのブロック共重合体であることが好ましい。また、柔軟性が必要な場合にはポリオレフィン系熱可塑性エラストマーが好ましい。 A polypropylene homopolymer is preferable from the viewpoint of high rigidity and low cost, and a block copolymer of propylene and another monomer is preferable from the viewpoint of high rigidity and impact resistance. When flexibility is required, a polyolefin-based thermoplastic elastomer is preferable.
本発明の変性ポリオレフィン樹脂をポリオレフィン樹脂に配合する際にその配合量は特に限定はないが、ポリオレフィン樹脂１００重量部に対し、０．１〜１００重量部、更には０．１〜７０重量部を含有させることが好ましい。より好ましくは０．３〜５０重量部であり、更に好ましくは０．５〜２０重量部である。この範囲より少ないとポリオレフィン樹脂に対して本発明の改質効果が得られない傾向がある。逆に多すぎるとポリオレフィン樹脂本来の機械特性が低下し、また経済的な課題が生じてくる場合がある。 When the modified polyolefin resin of the present invention is blended with the polyolefin resin, the blending amount is not particularly limited, but is 0.1 to 100 parts by weight, more preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the polyolefin resin. It is preferable to contain. More preferably, it is 0.3-50 weight part, More preferably, it is 0.5-20 weight part. If the amount is less than this range, the modification effect of the present invention tends not to be obtained with respect to the polyolefin resin. On the other hand, if the amount is too large, the original mechanical properties of the polyolefin resin are lowered, and economic problems may occur.
（シートまたはフィルム状成形体について）
本発明の変性ポリオレフィン樹脂組成物は、熱溶着性を有するポリオレフィンシートまたはフィルム状成形体にすることができる。また、ポリオレフィン樹脂に本発明の変性ポリオレフィン樹脂組成物を添加してなるポリオレフィン樹脂組成物も、熱溶着性を有するポリオレフィンシートまたはフィルム状成形体にすることができる。本発明でいう熱溶着性とは、熱で溶けて被着体と接合する性質のことである。本発明のシートまたはフィルム状成形体とは、成形体の厚みとしては３μｍから３ｍｍが例示でき、好ましくは１０μｍ〜１ｍｍであり、シートあるいはフィルムとして利用することができるものである。一般的に、厚み０．２ｍｍ以上の成形体はシート、厚み０．２ｍｍ以下の成形体はフィルムと呼ばれているが、本発明の変性ポリオレフィン樹脂組成物およびこれを含有するポリオレフィン樹脂組成物は、シート状にもフィルム状にも成形できる。
(About sheet or film-shaped molded product)
The modified polyolefin resin composition of the present invention can be made into a polyolefin sheet or film-like molded product having heat-welding properties. A polyolefin resin composition obtained by adding the modified polyolefin resin composition of the present invention to a polyolefin resin can also be made into a polyolefin sheet or film-like molded article having heat-welding properties. The heat-weldability referred to in the present invention refers to the property of melting with heat and joining to the adherend. The sheet or film-like molded article of the present invention can be exemplified by a thickness of the molded article of 3 to 3 mm, preferably 10 to 1 mm, and can be used as a sheet or film. In general, a molded body having a thickness of 0.2 mm or more is called a sheet, and a molded body having a thickness of 0.2 mm or less is called a film. The modified polyolefin resin composition of the present invention and a polyolefin resin composition containing the same are It can be formed into a sheet or a film.
本発明の熱溶着性を有するポリオレフィンシートまたはフィルム状成形体の製造方法は、特に限定されるものではないが、例えば本発明のポリオレフィン樹脂と変性ポリオレフィン樹脂をドライブレンド、あるいは溶融混練した後に、各種の押出成形機、射出成形機、カレンダー成形機、インフレーション成形機、ロール成形機、あるいは加熱プレス成形機などを用いてシート状成形体に成形加工することが可能である。 The method for producing the heat-bondable polyolefin sheet or film-like molded product of the present invention is not particularly limited. For example, after dry blending or melt-kneading the polyolefin resin of the present invention and the modified polyolefin resin, It is possible to form a sheet-like molded body using an extrusion molding machine, an injection molding machine, a calendar molding machine, an inflation molding machine, a roll molding machine, or a hot press molding machine.
本発明で用いられる被着体の材料としては、例えば、本発明の接着性フィルムの接着樹脂層と接着し得る材料である。具体的には、例えば、金、銀、銅、鉄、錫、鉛、アルミニウム、シリコンなどの金属、ガラス、セラミックスなどの無機材料；紙、布などのセルロース系高分子材料、メラミン樹脂、アクリル・ウレタン樹脂、ウレタン樹脂、（メタ）アクリル樹脂、スチレン・アクリロニトリル共重合体、ポリカーボネート樹脂、フェノール樹脂、ポリエステル樹脂、エポキシ樹脂、シリコン樹脂などの合成高分子材料等が挙げられる。 The material of the adherend used in the present invention is, for example, a material that can adhere to the adhesive resin layer of the adhesive film of the present invention. Specifically, for example, metals such as gold, silver, copper, iron, tin, lead, aluminum, silicon, inorganic materials such as glass and ceramics; cellulosic polymer materials such as paper and cloth, melamine resin, acrylic Synthetic polymer materials such as urethane resin, urethane resin, (meth) acrylic resin, styrene / acrylonitrile copolymer, polycarbonate resin, phenol resin, polyester resin, epoxy resin, silicone resin, and the like.
被着体の材料として、異なる２種類以上の材料を混合、複合してもよい。また、積層体が本発明の接着性フィルムを介して、異なる２つの被着体が接着してなるものである場合、２つの被着体を構成する材料は、同じ種類の材料でも異なる種類の材料のいずれでもよい。被着体の性状としては特に限定されないが、例えば、フィルム状、シート状、板状、繊維状などが挙げられる。また、被着体には、必要に応じて、離型剤、メッキなどの被膜、塗料による塗膜、プラズマやレーザーなどによる表面改質、表面酸化、エッチングなどの表面処理等を実施してもよい。被着体の具体例としては、トリム類（ドアトリム、内装トリムなど）、成形天井、シート材（内装シート、インパネ表皮、装飾シートなど）等の自動車部材や、室内ドア、パーティション、内装壁板、家具、システムキッチン等の住宅資材で使用される化粧フィルムが挙げられるが、これらに限定されるものではない。 Two or more different materials may be mixed and combined as the material of the adherend. When the laminate is formed by adhering two different adherends via the adhesive film of the present invention, the materials constituting the two adherends may be the same type of material but different types. Any of the materials may be used. The property of the adherend is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, and a fiber shape. In addition, the adherend may be subjected to a surface treatment such as a release agent, a coating such as plating, a coating with a paint, surface modification with plasma or laser, surface oxidation, etching, etc., if necessary. Good. Specific examples of adherends include automotive parts such as trims (door trims, interior trims, etc.), molded ceilings, sheet materials (interior sheets, instrument panel skins, decorative sheets, etc.), indoor doors, partitions, interior wall panels, Examples include, but are not limited to, decorative films used in housing materials such as furniture and system kitchens.
以下に具体的な実施例を示すが、本発明は下記実施例に限定されるものではない。下記実施例および比較例中「部」および「％」は、それぞれ「重量部」および「重量％」を表す。 Specific examples are shown below, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
［グラフト鎖長の測定／重量平均分子量／ポリオレフィンへのグラフトの確認］
グラフト鎖長は、変性ポリオレフィン樹脂中のグラフトに寄与していないフリーポリマーの鎖長と同じとみなし、以下のように算出した。押出ペレットを約５０重量倍のｏ−ジクロロベンゼンを用いて１３０℃にて３時間加熱して溶解し、不溶分を除去した後、一晩放冷して晶析物をろ別して、ろ液を回収・濃縮乾固してフリーポリマーを得た。これをクロロホルムに溶かしＧＰＣ（ゲルパーミエーションクロマトグラフィ、島津製作所社製リサイクル分取装置）にて、重量平均分子量を測定した。重量平均分子量は、ポリスチレン換算の重量平均分子量を求めた。測定に使用したカラム（いずれもＳｈｏｄｅｘ製）は、ＧＰＣ Ｋ−Ｇ（ガードカラム）、に続いて２本のＧＰＣ Ｋ−８０６であり、この順に直列につないで使用した。
[Measurement of graft chain length / weight average molecular weight / confirmation of graft to polyolefin]
The graft chain length was regarded as the same as the chain length of the free polymer that did not contribute to grafting in the modified polyolefin resin, and was calculated as follows. The extrudate pellets were dissolved by heating at 130 ° C. for 3 hours using about 50 times by weight of o-dichlorobenzene, and after removing insolubles, the crystals were allowed to cool overnight and the crystallized product was filtered off. Collection and concentration to dryness gave a free polymer. This was dissolved in chloroform, and the weight average molecular weight was measured by GPC (gel permeation chromatography, recycle preparative device manufactured by Shimadzu Corporation). For the weight average molecular weight, a polystyrene equivalent weight average molecular weight was determined. The columns used for the measurement (both manufactured by Shodex) were GPC KG (guard column), followed by two GPC K-806, which were used in series in this order.
また以下の方法により、ポリオレフィン樹脂にエポキシ基含有ビニル単量体と芳香族ビニル単量体が共重合していることを確認した。押出ペレットをｏ−ジクロロベンゼンを用いて加熱溶解し、不溶分を除去した後、一晩放冷して再沈物を取得した。再沈物について、エポキシ価測定を行い、エポキシ基含有ビニル単量体のグラフトを確認した。さらに、再沈物のプレスシートのＩＲスペクトル測定を行い、７００ｃｍ-1（芳香環）のピークから、芳香族ビニル単量体のグラフトを確認した。 Further, it was confirmed that the epoxy group-containing vinyl monomer and the aromatic vinyl monomer were copolymerized with the polyolefin resin by the following method. The extruded pellet was heated and dissolved using o-dichlorobenzene to remove insolubles, and then allowed to cool overnight to obtain a reprecipitate. About the reprecipitation, the epoxy value measurement was performed and the graft | grafting of the epoxy group containing vinyl monomer was confirmed. Furthermore, IR spectrum measurement of the re-precipitation press sheet was performed, and the grafting of the aromatic vinyl monomer was confirmed from the peak at 700 cm −1 (aromatic ring).
［Ｔ字剥離評価］
Ｔ字剥離評価は、島津製作所製ＡＧ−２０００Ａを用い、２３℃にて引張テストスピード２００ｍｍ／ｍｉｎで行った。テストサンプルは、以下の方法で作成した。２枚の鋼板プレート（２５ｍｍ×１５０ｍｍ、厚さ０．１５ｍｍ）の間にフィルムを挟み、プレス機（神藤金属工業所、型式ＮＳＦ−５０、プレス温度２２０℃、無圧・予熱４分、２ＭＰａ・プレス３０秒、無圧・冷却プレス３ｍｉｎ）にて接着し、テストサンプルを得た。
[T-shaped peeling evaluation]
T-peel evaluation was performed using AG-2000A manufactured by Shimadzu Corporation at 23 ° C. and a tensile test speed of 200 mm / min. The test sample was created by the following method. A film is sandwiched between two steel plate plates (25 mm x 150 mm, thickness 0.15 mm), and a press machine (Shinfuji Metal Industry Co., Ltd., model NSF-50, press temperature 220 ° C., no pressure / preheating 4 minutes, 2 MPa · A test sample was obtained by bonding with a press for 30 seconds and a pressureless / cooling press for 3 minutes.
（実施例１）
ポリプロピレン（（株）プライムポリマー製Ｊ１０５Ｇ、ＭＦＲ＝９）１００重量部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（日本油脂(株)製：パーブチルＰ、１分間半減期１７５℃）０．５重量部を図１の構成を有する２軸押出機（ＴＥＸ４４：Ｌ／Ｄ＝３８、日本製鋼所製）に供給して溶融混練した後、次いで、シリンダー途中よりメタクリル酸グリシジル５重量部、スチレン５重量部、メタクリル酸メチル０．１重量部を加え溶融混練して変性ポリオレフィン樹脂ペレットを得た。ここで、押出機のバレル温度は、表１中に示したように設定し、モノマー添加口のバレル温度を５０℃とした。メタクリル酸グリシジル、スチレン、メタクリル酸メチルから成るグラフト鎖の重量平均分子量は１１０２１であった。得られた樹脂組成物をＴダイに供給し３０μｍ厚みのフィルムを得た。このフィルムで接着させた鋼板の剥離結果を表２に示す。
Example 1
100 parts by weight of polypropylene (J105G manufactured by Prime Polymer Co., Ltd., MFR = 9), 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, half-life 175 ° C. for 1 minute) After supplying 0.5 part by weight to a twin-screw extruder (TEX44: L / D = 38, manufactured by Nippon Steel Works) having the configuration shown in FIG. 1, 5 parts by weight of glycidyl methacrylate is then fed from the middle of the cylinder. Then, 5 parts by weight of styrene and 0.1 parts by weight of methyl methacrylate were added and melt kneaded to obtain modified polyolefin resin pellets. Here, the barrel temperature of the extruder was set as shown in Table 1, and the barrel temperature of the monomer addition port was 50 ° C. The weight average molecular weight of the graft chain consisting of glycidyl methacrylate, styrene, and methyl methacrylate was 11021. The obtained resin composition was supplied to a T die to obtain a film having a thickness of 30 μm. Table 2 shows the peeling results of the steel plates adhered with this film.
（比較例１）
ポリプロピレン（（株）プライムポリマー製Ｊ１０５Ｇ、ＭＦＲ＝９）１００重量部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（日本油脂(株)製：パーブチルＰ、１分間半減期１７５℃）０．５重量部を図１の構成を有する２軸押出機（ＴＥＸ４４：Ｌ／Ｄ＝３８、日本製鋼所製）に供給して溶融混練した後、次いで、シリンダー途中よりメタクリル酸グリシジル５重量部、スチレン５重量部、メタクリル酸メチル０．１重量部を加え溶融混練して変性ポリオレフィン樹脂ペレットを得た。ここで、押出機のバレル温度は、表１中に示したように設定し、モノマー添加口のバレル温度を２００℃とした。メタクリル酸グリシジル、スチレン、メタクリル酸メチルから成るグラフト鎖の重量平均分子量は５９１２であった。得られた樹脂組成物をＴダイに供給し３０μｍ厚みのフィルムを得た。このフィルムで接着させた鋼板の剥離結果を表２に示す。
(Comparative Example 1)
100 parts by weight of polypropylene (J105G manufactured by Prime Polymer Co., Ltd., MFR = 9), 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, half-life 175 ° C. for 1 minute) After supplying 0.5 part by weight to a twin-screw extruder (TEX44: L / D = 38, manufactured by Nippon Steel Works) having the configuration shown in FIG. 1, 5 parts by weight of glycidyl methacrylate is then fed from the middle of the cylinder. Then, 5 parts by weight of styrene and 0.1 parts by weight of methyl methacrylate were added and melt kneaded to obtain modified polyolefin resin pellets. Here, the barrel temperature of the extruder was set as shown in Table 1, and the barrel temperature of the monomer addition port was 200 ° C. The weight average molecular weight of the graft chain composed of glycidyl methacrylate, styrene, and methyl methacrylate was 5912. The obtained resin composition was supplied to a T die to obtain a film having a thickness of 30 μm. Table 2 shows the peeling results of the steel plates adhered with this film.
実施例１、比較例１は溶融混練で製造された本発明の変性ポリオレフィン樹脂である。モノマーを添加する部分のバレル温度を低く設定すると、モノマーの解重合が抑制され数平均分子量が大きくなることが分かる。また、数平均分子量の大きい変性ポリオレフィンの接着性は、その小さいものよりも優れることが分かる。 Example 1 and Comparative Example 1 are modified polyolefin resins of the present invention produced by melt kneading. It can be seen that when the barrel temperature of the portion to which the monomer is added is set low, the depolymerization of the monomer is suppressed and the number average molecular weight increases. Moreover, it turns out that the adhesiveness of modified polyolefin with a large number average molecular weight is superior to the small thing.
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| JP2002338778A (en) * | 2001-05-16 | 2002-11-27 | Nof Corp | Graft copolymer composition, thermoplastic resin composition containing the same, and molded item thereof |
| JP2003268051A (en) * | 2002-03-18 | 2003-09-25 | Mitsui Chemicals Inc | Adhesive resin for polyphenylene sulfide and adhesive resin composition |
| JP2004292561A (en) * | 2003-03-26 | 2004-10-21 | Sumitomo Chem Co Ltd | Method for producing modified polyolefin resin and modified polyolefin resin |
| JP2009126920A (en) * | 2007-11-22 | 2009-06-11 | Kaneka Corp | Modified polyolefin-based resin composition |
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