JP2014111687A - Thermoplastic resin composition - Google Patents
Thermoplastic resin composition Download PDFInfo
- Publication number
- JP2014111687A JP2014111687A JP2012266289A JP2012266289A JP2014111687A JP 2014111687 A JP2014111687 A JP 2014111687A JP 2012266289 A JP2012266289 A JP 2012266289A JP 2012266289 A JP2012266289 A JP 2012266289A JP 2014111687 A JP2014111687 A JP 2014111687A
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- JP
- Japan
- Prior art keywords
- mass
- ethylene
- propylene copolymer
- polymer
- monomer
- 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
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- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 110
- 229920001971 elastomer Polymers 0.000 claims abstract description 86
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 239000005060 rubber Substances 0.000 claims abstract description 56
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 47
- 239000004816 latex Substances 0.000 description 37
- 229920000126 latex Polymers 0.000 description 37
- 238000000034 method Methods 0.000 description 34
- 238000000465 moulding Methods 0.000 description 24
- 239000002245 particle Substances 0.000 description 24
- 238000004945 emulsification Methods 0.000 description 22
- 150000001993 dienes Chemical class 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 238000004581 coalescence Methods 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- -1 ethylene, propylene Chemical group 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- VTCSNDCDIZADBA-UHFFFAOYSA-N 2,5-dichloro-5-ethenylcyclohexa-1,3-diene Chemical compound ClC1=CCC(Cl)(C=C)C=C1 VTCSNDCDIZADBA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SXPVZPQNFIDDPP-UHFFFAOYSA-N 3-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1C1=CC(=O)NC1=O SXPVZPQNFIDDPP-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- UUVOWFWRTLPGBP-UHFFFAOYSA-N 5,6-dichloro-5-ethenylcyclohexa-1,3-diene Chemical compound ClC1C=CC=CC1(Cl)C=C UUVOWFWRTLPGBP-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 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
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 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
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、自動車外装部品等に使用される熱可塑性樹脂組成物に関する。 The present invention relates to a thermoplastic resin composition used for automobile exterior parts and the like.
ＡＢＳ樹脂を成形した成形品は耐衝撃性や機械的性質のバランスのとれた部材として、自動車部品やＯＡ機器、その他の雑貨製品など各種分野で幅広く使用されている。
しかし、ＡＢＳ樹脂はゴム成分であるポリブタジエンが主鎖に炭素−炭素不飽和結合を多く有する樹脂であるために、その成形品は酸素、オゾンまたは紫外線などによって劣化しやすく耐候性に劣ることが知られている。このため屋外で長期にわたり使用される分野、特に自動車外装部品などに使用することが困難であった。
Molded products made of ABS resin are widely used in various fields such as automobile parts, OA equipment, and other miscellaneous goods as members having a balance between impact resistance and mechanical properties.
However, since ABS resin is a resin in which polybutadiene, which is a rubber component, has many carbon-carbon unsaturated bonds in the main chain, the molded product is prone to deterioration due to oxygen, ozone, ultraviolet rays, etc., and is inferior in weather resistance. It has been. For this reason, it has been difficult to use in fields that are used outdoors for a long period of time, particularly automobile exterior parts.
ＡＢＳ樹脂の耐候性を改良する方法としては、主鎖に炭素−炭素不飽和結合を有さないゴム成分を使用する方法が提案されており、その代表としてエチレン・プロピレン・非共役ジエン共重合体やエチレン・α−オレフィン共重合体を使用するＡＥＳ樹脂が知られている。
例えば特許文献１には、特定の架橋度のエチレン・プロピレン・非共役ジエンをゴム質重合体として使用したＡＥＳ樹脂が開示されている。
As a method for improving the weather resistance of an ABS resin, a method using a rubber component having no carbon-carbon unsaturated bond in the main chain has been proposed, and an ethylene / propylene / non-conjugated diene copolymer is a representative example. And AES resins using ethylene / α-olefin copolymers are known.
For example, Patent Document 1 discloses an AES resin using ethylene / propylene / non-conjugated diene having a specific degree of crosslinking as a rubbery polymer.
ところで、自動車外装部品などの分野では、耐衝撃性や各種機械物性に優れることはもちろんのこと、コスト削減の面から無塗装で使用されることも多く、成形品には平面平滑性などの成形外観に優れることも求められる。さらには、走行時の震動や衝突時などの衝撃で成形品が破壊したときに破片が周囲に飛び散る場合があるため、成形品が破壊するときの破壊形態としては、十分に塑性変形した後に破壊が生じる延性破壊が望まれる。 By the way, in fields such as automobile exterior parts, not only is it excellent in impact resistance and various mechanical properties, it is often used without coating from the viewpoint of cost reduction. The appearance is also required to be excellent. Furthermore, when the molded product breaks due to shocks such as vibrations or collisions during travel, the fragments may scatter around. Ductile fracture that causes the occurrence of is desired.
しかしながら、一般的に、ＡＥＳ樹脂を成形した成形品は、ＡＢＳ樹脂を成形した成形品に比べて耐衝撃性、特に低温環境下における耐衝撃性（低温耐衝撃性）に劣るものであった。しかも、ＡＥＳ樹脂を成形した成形品は、低温環境下における破壊形態が塑性変形をほとんど伴わずに破壊する脆性破壊となりやすかった。
特許文献１に記載のＡＥＳ樹脂は、特定の架橋度のエチレン・プロピレン・非共役ジエンをゴム質重合体として使用することで低温耐衝撃性には優れるものの、低温環境下における破壊形態を延性破壊とするには至っておらず、さらなる改良が求められていた。
However, in general, a molded product obtained by molding an AES resin is inferior in impact resistance, particularly impact resistance in a low temperature environment (low temperature impact resistance), compared to a molded product obtained by molding an ABS resin. Moreover, the molded product obtained by molding the AES resin is likely to be brittle fracture in which the fracture mode in a low-temperature environment breaks with little plastic deformation.
The AES resin described in Patent Document 1 is excellent in low-temperature impact resistance by using ethylene, propylene, and non-conjugated dienes having a specific degree of crosslinking as a rubbery polymer, but has a ductile fracture in a low-temperature environment. However, further improvement has been demanded.
本発明は、表面平滑性などの成形外観および低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である成形品を得ることができる熱可塑性樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a thermoplastic resin composition that is excellent in molding appearance such as surface smoothness and low-temperature impact resistance, and that can obtain a molded product having a ductile fracture in a low-temperature environment. .
本発明者らは鋭意検討した結果、２種類以上のエチレン・プロピレン共重合体、具体的には、メルトフローレート（ＭＦＲ）が低いエチレン・プロピレン共重合体と、ＭＦＲが高く、特定量のエチレン単位およびプロピレン単位を含むエチレン・プロピレン共重合体を含むゴム質重合体にビニル系単量体混合物が乳化グラフト重合したグラフト重合体を必須成分とする熱可塑性樹脂組成物が上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have determined that two or more types of ethylene / propylene copolymers, specifically, an ethylene / propylene copolymer having a low melt flow rate (MFR), a high MFR, and a specific amount of ethylene. A thermoplastic resin composition comprising, as an essential component, a graft polymer obtained by emulsion graft polymerization of a vinyl monomer mixture to a rubbery polymer containing an ethylene / propylene copolymer containing a unit and a propylene unit can solve the above-mentioned problems. The headline and the present invention were completed.
すなわち、本発明は以下の態様を包含する。
［１］ ２３０℃、２１．２Ｎで測定したメルトフローレートが０．１ｇ／１０分以上、１ｇ／１０分未満であるエチレン・プロピレン共重合体（ａ）１０〜６０質量％と、２３０℃、２１．２Ｎで測定したメルトフローレートが１〜３５ｇ／１０分であり、エチレン単位を４０〜６５質量％、プロピレン単位を３５〜６０質量％含むエチレン・プロピレン共重合体（ｂ）４０〜９０質量％とを含むゴム質重合体（Ａ）に、芳香族ビニル系単量体とシアン化ビニル系単量体とを含む単量体混合物を乳化グラフト重合したグラフト重合体（Ｂ）と、芳香族ビニル系単量体とシアン化ビニル系単量体とを含む単量体混合物を重合した共重合体（Ｃ）とを含有することを特徴とする熱可塑性樹脂組成物。
That is, the present invention includes the following aspects.
[1] 10 to 60% by mass of an ethylene / propylene copolymer (a) having a melt flow rate measured at 230 ° C. and 21.2 N of 0.1 g / 10 min or more and less than 1 g / 10 min, 230 ° C., An ethylene / propylene copolymer (b) having a melt flow rate measured at 21.2 N of 1 to 35 g / 10 min and containing 40 to 65% by mass of ethylene units and 35 to 60% by mass of propylene units (b) 40 to 90% A graft polymer (B) obtained by emulsion graft polymerization of a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer to a rubbery polymer (A) containing A thermoplastic resin composition comprising a copolymer (C) obtained by polymerizing a monomer mixture containing a vinyl monomer and a vinyl cyanide monomer.
本発明の熱可塑性樹脂組成物は、表面平滑性などの成形外観および低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である成形品を得ることができる。 The thermoplastic resin composition of the present invention is excellent in molding appearance such as surface smoothness and low-temperature impact resistance, and can provide a molded product having a fracture mode of ductile fracture in a low-temperature environment.
以下、本発明を詳細に説明する。
［熱可塑性樹脂組成物］
本発明の熱可塑性樹脂組成物は、ゴム質重合体（Ａ）に単量体混合物を乳化グラフト重合したグラフト重合体（Ｂ）と、共重合体（Ｃ）とを含有する。
以下、本発明の熱可塑性樹脂組成物を構成する各成分について説明する。なお、以下において、「成形品」とは、本発明の熱可塑性樹脂組成物を成形したものである。また、室温環境下における耐衝撃性を「耐衝撃性」といい、低温環境下における耐衝撃性を「低温耐衝撃性」という。ここで、「室温」とは０〜４０℃を意味し、「低温」とは０℃未満を意味する。
Hereinafter, the present invention will be described in detail.
[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains a graft polymer (B) obtained by emulsion graft polymerization of a monomer mixture to a rubbery polymer (A), and a copolymer (C).
Hereafter, each component which comprises the thermoplastic resin composition of this invention is demonstrated. In the following, the “molded product” is a product obtained by molding the thermoplastic resin composition of the present invention. Moreover, the impact resistance in a room temperature environment is called “impact resistance”, and the impact resistance in a low temperature environment is called “low temperature impact resistance”. Here, “room temperature” means 0 to 40 ° C., and “low temperature” means less than 0 ° C.
＜ゴム質重合体（Ａ）＞
ゴム質重合体（Ａ）は、２３０℃、２１．２Ｎで測定したメルトフローレート（ＭＦＲ）が０．１ｇ／１０分以上、１ｇ／１０分未満であるエチレン・プロピレン共重合体（ａ）と、２３０℃、２１．２Ｎで測定したＭＦＲが１〜３５ｇ／１０分であるエチレン・プロピレン共重合体（ｂ）とを含む。
<Rubber polymer (A)>
The rubber polymer (A) is an ethylene / propylene copolymer (a) having a melt flow rate (MFR) measured at 230 ° C. and 21.2 N of 0.1 g / 10 min or more and less than 1 g / 10 min. And an ethylene / propylene copolymer (b) having an MFR measured at 21.2 N at 230 ° C. of 1 to 35 g / 10 min.
エチレン・プロピレン共重合体（ａ）のＭＦＲは、０．１ｇ／１０分以上、１ｇ／１０分未満である。エチレン・プロピレン共重合体（ａ）のＭＦＲが０．１ｇ/１０分以上であれば、乳化しやすくなる。一方、エチレン・プロピレン共重合体（ａ）のＭＦＲが１ｇ/１０分未満であれば、耐衝撃性および低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である成形品が得られる。 The MFR of the ethylene / propylene copolymer (a) is 0.1 g / 10 min or more and less than 1 g / 10 min. If the MFR of the ethylene / propylene copolymer (a) is 0.1 g / 10 min or more, emulsification is facilitated. On the other hand, if the MFR of the ethylene / propylene copolymer (a) is less than 1 g / 10 min, a molded article having excellent impact resistance and low temperature impact resistance and ductile fracture in a low temperature environment can be obtained. .
エチレン・プロピレン共重合体（ａ）は、エチレン単位およびプロピレン単位のみで構成されていてもよいし、非共役ジエン単位を含んでいてもよい。
非共役ジエンとしては特に制限はないが、１，４−ヘキサジエン、５−エチリデン−２−ノルボルネン、５−ビニルノルボルネンおよびジシクロペンタジエン等が好ましい。
エチレン・プロピレン共重合体（ａ）を構成する各単量体単位の含有量は、後述するエチレン・プロピレン共重合体（ｂ）との相溶性の点から、エチレン単位が４０〜８５質量％であることが好ましく、プロピレン単位が１５〜６０質量％であることが好ましく、非共役ジエン単位が０〜２０質量％であることが好ましい。
The ethylene / propylene copolymer (a) may be composed of only ethylene units and propylene units, or may contain non-conjugated diene units.
The non-conjugated diene is not particularly limited, but 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, dicyclopentadiene and the like are preferable.
The content of each monomer unit constituting the ethylene / propylene copolymer (a) is 40 to 85% by mass of ethylene units from the viewpoint of compatibility with the ethylene / propylene copolymer (b) described later. It is preferable that the propylene unit is 15 to 60% by mass, and the non-conjugated diene unit is preferably 0 to 20% by mass.
一方、エチレン・プロピレン共重合体（ｂ）のＭＦＲは、１〜３５ｇ／１０分であり、好ましくは１〜１０ｇ/１０分である。エチレン・プロピレン共重合体（ｂ）のＭＦＲが１ｇ/１０分以上であれば、ゴム質重合体（Ａ）の分散性が良好となり、ブツ等の不良現象を抑制でき、表面平滑性などの成形外観に優れた成形品が得られる。一方、エチレン・プロピレン共重合体（ｂ）のＭＦＲが３５ｇ／１０分以下であれば、低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である成形品が得られる。 On the other hand, the MFR of the ethylene / propylene copolymer (b) is 1 to 35 g / 10 min, and preferably 1 to 10 g / 10 min. If the MFR of the ethylene / propylene copolymer (b) is 1 g / 10 min or more, the dispersibility of the rubber polymer (A) is improved, and defective phenomena such as blisters can be suppressed, and molding such as surface smoothness is achieved. A molded product having an excellent appearance can be obtained. On the other hand, when the MFR of the ethylene / propylene copolymer (b) is 35 g / 10 min or less, a molded article having excellent low temperature impact resistance and a ductile fracture in a low temperature environment can be obtained.
エチレン・プロピレン共重合体（ｂ）は、エチレン単位およびプロピレン単位のみで構成されていてもよいし、非共役ジエン単位を含んでいてもよい。
非共役ジエンとしては特に制限されず、エチレン・プロピレン共重合体（ａ）の説明において先に例示した非共役ジエンが挙げられる。
エチレン・プロピレン共重合体（ｂ）を構成する各単量体単位の含有量は、エチレン単位が４０〜６５質量％であり、プロピレン単位が３５〜６０質量％である。エチレン単位およびプロピレン単位の含有量が上記範囲内であれば、低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である成形品が得られる。
なお、エチレン・プロピレン共重合体（ｂ）が非共役ジエン単位を含む場合、非共役ジエン単位の含有量は０〜２０質量％であることが好ましい。
The ethylene / propylene copolymer (b) may be composed of only ethylene units and propylene units, or may contain non-conjugated diene units.
The non-conjugated diene is not particularly limited, and examples thereof include the non-conjugated dienes exemplified above in the explanation of the ethylene / propylene copolymer (a).
Content of each monomer unit which comprises an ethylene propylene copolymer (b) is 40-65 mass% of ethylene units, and is 35-60 mass% of propylene units. When the content of the ethylene unit and the propylene unit is within the above range, a molded article having excellent low temperature impact resistance and a ductile fracture in a low temperature environment can be obtained.
In addition, when ethylene-propylene copolymer (b) contains a nonconjugated diene unit, it is preferable that content of a nonconjugated diene unit is 0-20 mass%.
エチレン・プロピレン共重合体（ａ）、（ｂ）の融点や結晶化温度等は特に制限されないが、低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である成形品が得られやすくなる傾向にあることから、示差走査熱測定において、２３℃から２００℃まで１０℃／分で昇温したときの融解ピーク（融点（Ｔｍ））はそれぞれ６０℃以下であることが好ましく、融解熱量（ΔＨｍ）はそれぞれ２５Ｊ／ｇ以下であることが好ましい。次いで、２００℃から−１００℃まで−１０℃／分で降温したときの結晶化ピーク（結晶化温度（Ｔｃ））はそれぞれ２５℃以下であることが好ましく、結晶化熱量（ΔＨｃ）はそれぞれ５０Ｊ/ｇ以下であることが好ましい。 The melting points and crystallization temperatures of the ethylene / propylene copolymers (a) and (b) are not particularly limited, but they are excellent in low-temperature impact resistance, and it is easy to obtain a molded product having a ductile fracture in a low-temperature environment. Therefore, in differential scanning calorimetry, the melting peak (melting point (Tm)) when the temperature is increased from 23 ° C. to 200 ° C. at 10 ° C./min is preferably 60 ° C. or less, and the heat of fusion (ΔHm) is preferably 25 J / g or less. Next, the crystallization peak (crystallization temperature (Tc)) when the temperature is lowered from 200 ° C. to −100 ° C. at −10 ° C./min is preferably 25 ° C. or less, and the crystallization heat quantity (ΔHc) is 50 J each. / g or less is preferable.
エチレン・プロピレン共重合体（ａ）、（ｂ）は、通常、チーグラー・ナッタ触媒、またはメタロセン触媒を用いて製造される。
チーグラー・ナッタ触媒としては、高活性触媒が好ましく、特にマグネシウム、チタン、ハロゲン、電子供与体を必須成分とする固体触媒成分と、有機アルミニウム化合物とを組み合わせた高活性触媒が好ましい。
一方、メタロセン触媒としては、ジルコニウム、ハフニウム、チタンなどの遷移金属に、シクロペンタジエニル骨格を有する有機化合物、ハロゲン原子などが配位したメタロセン錯体と、アルモキサン化合物、イオン交換性珪酸塩、有機アルミニウム化合物などを組み合わせた触媒が使用できる。
The ethylene / propylene copolymers (a) and (b) are usually produced using a Ziegler-Natta catalyst or a metallocene catalyst.
As the Ziegler-Natta catalyst, a highly active catalyst is preferable, and a highly active catalyst in which a solid catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components and an organoaluminum compound is particularly preferable.
On the other hand, metallocene catalysts include transition metal such as zirconium, hafnium and titanium, organic compounds having a cyclopentadienyl skeleton, metallocene complexes in which halogen atoms and the like are coordinated, alumoxane compounds, ion-exchange silicates, and organic aluminums. A catalyst in which compounds are combined can be used.
また、エチレン・プロピレン共重合体（ａ）、（ｂ）の重合方法としては特に制限されず、スラリー重合法、気相重合法、バルク重合法、溶液重合法、またはこれらを組み合わせた多段重合法などが挙げられる。 Further, the polymerization method of the ethylene / propylene copolymer (a) or (b) is not particularly limited, and is a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, or a multistage polymerization method combining these. Etc.
ゴム質重合体（Ａ）は、エチレン・プロピレン共重合体（ａ）を１０〜６０質量％と、エチレン・プロピレン共重合体（ｂ）を４０〜９０質量％（ただし、エチレン・プロピレン共重合体（ａ）とエチレン・プロピレン共重合体（ｂ）の合計が１００質量％）とを含む。ゴム質重合体（Ａ）中のエチレン・プロピレン共重合体（ａ）の含有量が１０質量％以上、エチレン・プロピレン共重合体（ｂ）の含有量が９０質量％以下であれば、低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である成形品が得られる。一方、ゴム質重合体（Ａ）中のエチレン・プロピレン共重合体（ａ）の含有量が６０質量％以下、エチレン・プロピレン共重合体（ｂ）の含有量が４０質量％以上であれば、表面平滑性などの成形外観に優れた成形品が得られる。
耐衝撃性にも優れる成形品が得られやすくなることから、ゴム質重合体（Ａ）は、エチレン・プロピレン共重合体（ａ）を４０〜６０質量％と、エチレン・プロピレン共重合体（ｂ）を４０〜６０質量％（ただし、エチレン・プロピレン共重合体（ａ）とエチレン・プロピレン共重合体（ｂ）の合計が１００質量％）とを含むことが好ましい。
The rubber polymer (A) is composed of 10 to 60% by mass of the ethylene / propylene copolymer (a) and 40 to 90% by mass of the ethylene / propylene copolymer (b) (however, the ethylene / propylene copolymer). (A) and ethylene / propylene copolymer (b) total is 100 mass%). If the content of the ethylene / propylene copolymer (a) in the rubber polymer (A) is 10% by mass or more and the content of the ethylene / propylene copolymer (b) is 90% by mass or less, the low temperature resistance A molded article having excellent impact properties and ductile fracture under a low temperature environment can be obtained. On the other hand, if the content of the ethylene / propylene copolymer (a) in the rubber polymer (A) is 60% by mass or less and the content of the ethylene / propylene copolymer (b) is 40% by mass or more, A molded product having excellent molded appearance such as surface smoothness can be obtained.
Since it becomes easy to obtain a molded article having excellent impact resistance, the rubber polymer (A) is composed of 40 to 60% by mass of the ethylene / propylene copolymer (a) and the ethylene / propylene copolymer (b). ) In an amount of 40 to 60% by mass (provided that the total of the ethylene / propylene copolymer (a) and the ethylene / propylene copolymer (b) is 100% by mass).
ゴム質重合体（Ａ）の製造方法は、エチレン・プロピレン共重合体（ａ）、（ｂ）が均一に混合される方法であれば、特に限定されるものではない。例えば、エチレン・プロピレン共重合体（ａ）、（ｂ）を均一溶液に溶解させる方法、予めエチレン・プロピレン共重合体（ａ）、（ｂ）を溶融混練したものを溶液に溶解させる方法、これらを再乳化する方法、エチレン・プロピレン共重合体（ａ）、（ｂ）を同時に機械乳化する方法（機械乳化法）などが挙げられる。これらの中でも、生産性の点から機械乳化法が好ましい。 The method for producing the rubber polymer (A) is not particularly limited as long as the ethylene / propylene copolymers (a) and (b) are uniformly mixed. For example, a method of dissolving the ethylene / propylene copolymer (a), (b) in a uniform solution, a method of dissolving a pre-melted ethylene / propylene copolymer (a), (b) in a solution, these And a method of mechanically emulsifying the ethylene / propylene copolymers (a) and (b) simultaneously (mechanical emulsification method). Among these, the mechanical emulsification method is preferable from the viewpoint of productivity.
ここで、「機械乳化法」とは、乳化剤およびワックス状重合体の存在下で、塊状またはペレット状のエチレン・プロピレン共重合体（ａ）、（ｂ）に機械的剪断力を与え、水中に微細に分散安定化させる方法である。必要に応じて、機械乳化法により得られたラテックスに架橋剤および重合開始剤を加えた後、熱処理してもよく、この方法により架橋されたゴム質重合体（Ａ）が得られる。架橋されたゴム質重合体（Ａ）を用いた場合、得られる成形品の耐衝撃性、特に低温耐衝撃性がより向上する傾向にある。 Here, the “mechanical emulsification method” is a method in which a mechanical shearing force is applied to a block-shaped or pellet-shaped ethylene / propylene copolymer (a) or (b) in the presence of an emulsifier and a wax-like polymer. This is a fine dispersion stabilization method. If necessary, a crosslinker and a polymerization initiator may be added to the latex obtained by the mechanical emulsification method, followed by heat treatment, and a rubbery polymer (A) crosslinked by this method is obtained. When the crosslinked rubbery polymer (A) is used, the impact resistance, particularly low temperature impact resistance, of the obtained molded product tends to be further improved.
機械乳化法で使用される乳化剤としては、例えば、長鎖アルキルカルボン酸塩、スルホコハク酸アルキルエステル塩、アルキルベンゼンスルホン酸塩等の公知の乳化剤が挙げられる。
乳化剤の使用量は、得られる熱可塑性樹脂組成物の熱変色性が抑えられ、また機械乳化の際の粒子径制御性に優れることから、エチレン・プロピレン共重合体（ａ）、（ｂ）の合計１００質量部に対して、１〜８質量部が好ましい。
Examples of the emulsifier used in the mechanical emulsification method include known emulsifiers such as long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
The amount of the emulsifier used is that of the ethylene-propylene copolymer (a) or (b) because the thermochromic property of the resulting thermoplastic resin composition is suppressed and the particle size controllability during mechanical emulsification is excellent. 1-8 mass parts is preferable with respect to a total of 100 mass parts.
機械乳化法で使用されるワックス状重合体としては、中和可能であることから、カルボン酸またはその無水物基を含む熱可塑性重合体が好ましい。該熱可塑性重合体としては、例えば、α−オレフィン系重合体にエチレン系不飽和カルボン酸またはその無水物をグラフト重合した酸変性α−オレフィン系重合体が挙げられる。
ワックス状重合体の質量平均分子量は、２，０００〜６，０００が好ましく、酸価は２２〜３０ｍｇＫＯＨ／ｇが好ましい。質量平均分子量および酸価がこの範囲にあると、得られる成形品の成形外観がより優れる。
ワックス状重合体の使用量は、機械乳化の際の粒子径制御性に優れることから、エチレン・プロピレン共重合体（ａ）、（ｂ）の合計１００質量部に対して、０．１〜３０質量部が好ましい。
The waxy polymer used in the mechanical emulsification method is preferably a thermoplastic polymer containing a carboxylic acid or an anhydride group thereof because it can be neutralized. Examples of the thermoplastic polymer include acid-modified α-olefin polymers obtained by graft polymerization of an ethylenically unsaturated carboxylic acid or an anhydride thereof to an α-olefin polymer.
The weight average molecular weight of the waxy polymer is preferably 2,000 to 6,000, and the acid value is preferably 22 to 30 mgKOH / g. When the mass average molecular weight and the acid value are in this range, the molded appearance of the obtained molded product is more excellent.
The amount of the waxy polymer used is 0.1 to 30 with respect to 100 parts by mass in total of the ethylene / propylene copolymer (a) and (b) because of excellent particle diameter controllability during mechanical emulsification. Part by mass is preferred.
架橋されたゴム質重合体（Ａ）を得る場合、架橋剤としては、例えば、ジビニルベンゼン、アリルメタクリレート、エチレングリコールジメタクリレート、１，３−ブチレンジメタクリレート、テトラエチレングリコールジアクリレート、トリアリルシアヌレート、トリアリルイソシアヌレート、ペンタエリスリトールテトラアクリレート等の多官能性単量体が挙げられる。これらの中でもジビニルベンゼン、トリアリルシアヌレート、トリアリルイソシアヌレートが好ましい。これら架橋剤は、１種を単独で用いてもよく、２種以上を併用してもよい。
架橋剤の使用量は、エチレン・プロピレン共重合体（ａ）、（ｂ）の合計１００質量部に対して、０．１〜１０質量部であることが好ましい。架橋剤の使用量が０．１質量部以上であれば、架橋剤を使用する効果が十分に発揮される。一方、架橋剤の使用量が１０質量部以下であれば、成形品の低温耐衝撃性を良好に維持できる。
When obtaining the crosslinked rubbery polymer (A), examples of the crosslinking agent include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate. And polyfunctional monomers such as triallyl isocyanurate and pentaerythritol tetraacrylate. Among these, divinylbenzene, triallyl cyanurate, and triallyl isocyanurate are preferable. These crosslinking agents may be used individually by 1 type, and may use 2 or more types together.
It is preferable that the usage-amount of a crosslinking agent is 0.1-10 mass parts with respect to a total of 100 mass parts of ethylene propylene copolymer (a), (b). If the usage-amount of a crosslinking agent is 0.1 mass part or more, the effect of using a crosslinking agent will fully be exhibited. On the other hand, if the usage-amount of a crosslinking agent is 10 mass parts or less, the low temperature impact resistance of a molded article can be maintained favorable.
ゴム質重合体（Ａ）のラテックスの質量平均粒子径は、目的とする熱可塑性樹脂組成物の成形性や、成形品の低温耐衝撃性に応じて調整することが好ましいが、得られる成形品の耐衝撃性の点からは、２００〜６００ｎｍであることが好ましい。
なお、本明細書において、「質量平均粒子径」とは、粒度分布測定器を用いて質量基準の粒子径分布を測定し、得られた粒子径分布より算出される値である。
The mass average particle diameter of the latex of the rubber polymer (A) is preferably adjusted according to the moldability of the desired thermoplastic resin composition and the low temperature impact resistance of the molded product, but the molded product obtained From the point of impact resistance, it is preferably 200 to 600 nm.
In the present specification, the “mass average particle size” is a value calculated from a particle size distribution obtained by measuring a mass-based particle size distribution using a particle size distribution measuring instrument.
熱可塑性樹脂組成物１００質量％中のゴム質重合体（Ａ）の含有量は、１３〜３０質量％が好ましく、１７〜３０質量％がより好ましい。ゴム質重合体（Ａ）の含有量が上記範囲内であれば、成形外観および低温耐衝撃性のバランスに優れ、低温環境下における破壊形態が延性破壊である成形品が得られやすくなる。 13-30 mass% is preferable and, as for content of the rubber-like polymer (A) in 100 mass% of thermoplastic resin compositions, 17-30 mass% is more preferable. When the content of the rubbery polymer (A) is within the above range, a molded product having an excellent balance between the molded appearance and the low temperature impact resistance and having a ductile fracture in a low temperature environment is easily obtained.
＜グラフト重合体（Ｂ）＞
グラフト重合体（Ｂ）は、ゴム質重合体（Ａ）に、芳香族ビニル系単量体とシアン化ビニル系単量体とを含む単量体混合物を乳化グラフト重合したものである。
<Graft polymer (B)>
The graft polymer (B) is obtained by emulsion graft polymerization of a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer to the rubber polymer (A).
グラフト重合体（Ｂ）を構成する単量体混合物は、芳香族ビニル系単量体およびシアン化ビニル系単量体を必須成分として含み、これら単量体と共重合可能な他のビニル系単量体を任意成分として含む混合物である。
芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、ビニルトルエン、ｏ−エチルスチレン、ｏ−ジクロロスチレン、ｐ−ジクロロスチレン等が挙げられる。これらの中でもスチレン、α−メチルスチレンが好ましい。
これら芳香族ビニル系単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。
The monomer mixture constituting the graft polymer (B) contains an aromatic vinyl monomer and a vinyl cyanide monomer as essential components, and other vinyl monomers that can be copolymerized with these monomers. It is a mixture containing a monomer as an optional component.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, o-dichlorostyrene, and p-dichlorostyrene. Of these, styrene and α-methylstyrene are preferable.
These aromatic vinyl monomers may be used alone or in combination of two or more.
シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル等が挙げられる。これらの中でもアクリロニトリルが好ましい。
これらシアン化ビニル系単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. Among these, acrylonitrile is preferable.
These vinyl cyanide monomers may be used alone or in combination of two or more.
他のビニル系単量体としては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル等のアクリル酸アルキルエステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル等のメタクリル酸アルキルエステル、マレイン酸、無水マレイン酸、フマル酸等のマレイン酸誘導体、マレイミド、Ｎ−メチルマレイミド、Ｎ−ブチルマレイミド、Ｎ−フェニルマレイミド、Ｎ−（２−メチルフェニル）マレイミド、Ｎ−（４−ヒドロキシフェニル）マレイミド、Ｎ−シクロヘキシルマレイミド等のＮ−置換マレイミドなどが挙げられる。
これら他のビニル系単量体は、それぞれ１種を単独で用いてもよいし、２種以上を併用してもよい。
Examples of other vinyl monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Methacrylic acid alkyl ester, maleic acid, maleic anhydride, maleic acid derivatives such as fumaric acid, maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- And N-substituted maleimides such as (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide.
Each of these other vinyl monomers may be used alone or in combination of two or more.
グラフト重合体（Ｂ）を構成する単量体混合物の組成は、熱可塑性樹脂組成物の流動性や、成形品の耐衝撃性、熱安定性などの物性バランスに優れることから、芳香族ビニル系単量体が５０〜９５質量％、シアン化ビニル系単量体が５〜５０質量％、他のビニル系単量体が０〜３０質量％（ただし、芳香族ビニル系単量体、シアン化ビニル系単量体、他のビニル系単量体の合計が１００質量％）であることが好ましい。 The composition of the monomer mixture constituting the graft polymer (B) is excellent in the balance of physical properties such as fluidity of the thermoplastic resin composition, impact resistance and thermal stability of the molded product. 50 to 95% by weight of monomer, 5 to 50% by weight of vinyl cyanide monomer, 0 to 30% by weight of other vinyl monomers (however, aromatic vinyl monomers and cyanide) The total of vinyl monomers and other vinyl monomers is preferably 100% by mass).
乳化グラフト重合は、例えば、エチレン・プロピレン共重合体（ａ）、（ｂ）を同時に機械乳化して得られたゴム質重合体（Ａ）を攪拌翼ジャケット付き反応容器に仕込み、次に、乳化グラフト重合させる単量体混合物の全量または一部を数回に分けて一括または連続して滴下し、攪拌しながら４０〜７０℃にて、５〜６０分間放置したのち、更にレドックス系開始剤を添加することにより行うことができる。これにより、添加した各単量体がゴム質重合体（Ａ）に含浸し、ゴム質重合体（Ａ）内および表面にて重合して、グラフト重合体（Ｂ）となる。 In the emulsion graft polymerization, for example, the rubber polymer (A) obtained by simultaneously mechanically emulsifying the ethylene / propylene copolymers (a) and (b) is charged into a reaction vessel equipped with a stirring blade jacket, and then emulsified. The whole or part of the monomer mixture to be graft-polymerized is dropped all at once in batches or continuously, and is allowed to stand at 40 to 70 ° C. for 5 to 60 minutes with stirring, and then a redox initiator is further added. This can be done by adding. Thereby, each added monomer impregnates the rubbery polymer (A), and polymerizes in the rubbery polymer (A) and on the surface to become a graft polymer (B).
レドックス系開始剤としては、油溶性有機過酸化物と硫酸第一鉄−キレート剤−還元剤とが組み合わされたものが好ましい。
油溶性有機過酸化物としては、クメン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、ｔ−ブチルハイドロパーオキサイドなどが挙げられる。
特に好ましいレドックス系開始剤としては、クメンハイドロパーオキサイドと、硫酸第一鉄と、ピロリン酸ナトリウムと、デキストロースとからなるものである。
As the redox initiator, a combination of an oil-soluble organic peroxide and a ferrous sulfate-chelating agent-reducing agent is preferable.
Examples of the oil-soluble organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, and t-butyl hydroperoxide.
Particularly preferred redox initiators are those composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.
グラフト重合体（Ｂ）は、熱可塑性樹脂組成物の流動性や、成形品の耐衝撃性、熱安定性などの物性バランスに優れ、さらに生産性にも優れることから、ゴム質重合体（Ａ）４０〜８０質量部に、単量体混合物２０〜６０質量部（ただし、ゴム質重合体（Ａ）と単量体混合物の合計が１００質量部）が乳化グラフト重合してなるものが好ましい。 The graft polymer (B) is excellent in the balance of physical properties such as the fluidity of the thermoplastic resin composition, the impact resistance and thermal stability of the molded product, and is also excellent in productivity. 40) to 80 parts by mass, and 20 to 60 parts by mass of the monomer mixture (however, the total of the rubber polymer (A) and the monomer mixture is 100 parts by mass) is preferably emulsion graft polymerized.
＜共重合体（Ｃ）＞
共重合体（Ｃ）は、芳香族ビニル系単量体とシアン化ビニル系単量体とを含む単量体混合物を重合したものである。
<Copolymer (C)>
The copolymer (C) is obtained by polymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer.
共重合体（Ｃ）を構成する単量体混合物は、芳香族ビニル系単量体およびシアン化ビニル系単量体を必須成分として含み、これら単量体と共重合可能な他のビニル系単量体を任意成分として含む混合物である。
芳香族ビニル系単量体、シアン化ビニル系単量体、他のビニル系単量体の具体例としては、グラフト重合体（Ｂ）の説明において先に例示した各単量体と同様のものが挙げられる。
The monomer mixture constituting the copolymer (C) contains an aromatic vinyl monomer and a vinyl cyanide monomer as essential components, and other vinyl monomers copolymerizable with these monomers. It is a mixture containing a monomer as an optional component.
Specific examples of the aromatic vinyl monomer, vinyl cyanide monomer, and other vinyl monomers are the same as those exemplified above in the description of the graft polymer (B). Is mentioned.
共重合体（Ｃ）を構成する単量体混合物の組成は、熱可塑性樹脂組成物の流動性や、成形品の耐衝撃性、熱安定性などの物性バランスに優れることから、芳香族ビニル系単量体が５０〜９５質量％、シアン化ビニル系単量体が５〜５０質量％、他のビニル系単量体が０〜３０質量％（ただし、芳香族ビニル系単量体、シアン化ビニル系単量体、他のビニル系単量体の合計が１００質量％）であることが好ましい。 Since the composition of the monomer mixture constituting the copolymer (C) is excellent in the fluidity of the thermoplastic resin composition and the balance of physical properties such as impact resistance and thermal stability of the molded product, it is an aromatic vinyl type. 50 to 95% by weight of monomer, 5 to 50% by weight of vinyl cyanide monomer, 0 to 30% by weight of other vinyl monomers (however, aromatic vinyl monomers and cyanide) The total of vinyl monomers and other vinyl monomers is preferably 100% by mass).
共重合体（Ｃ）の製造方法としては特に制限されるものではなく、通常行われている方法を使用して製造することができる。一般的な方法としては、塊状重合、溶液重合、塊状懸濁重合、懸濁重合および乳化重合等が挙げられる。 It does not restrict | limit especially as a manufacturing method of a copolymer (C), It can manufacture using the method currently performed normally. Common methods include bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization and emulsion polymerization.
＜その他の成分＞
本発明の熱可塑性樹脂組成物には、グラフト重合体（Ｂ）および共重合体（Ｃ）の他に、その物性を損なわない範囲において、熱可塑性樹脂組成物の製造時（混合時）や成形時に慣用の他の添加剤、例えば滑材、顔料、染料、充填剤（カーボンブラック、シリカ、酸化チタン等）、耐熱剤、酸化劣化防止剤、耐候剤、離型剤、可塑剤、帯電防止剤を配合してもよい。
<Other ingredients>
In the thermoplastic resin composition of the present invention, in addition to the graft polymer (B) and the copolymer (C), the thermoplastic resin composition is produced (mixed) or molded as long as the physical properties thereof are not impaired. Other commonly used additives such as lubricants, pigments, dyes, fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, antioxidants, weathering agents, release agents, plasticizers, antistatic agents May be blended.
＜熱可塑性樹脂組成物の製造方法＞
熱可塑性樹脂組成物を製造する方法には特に制限はなく、通常行われている方法及び装置を使用して製造することができる。一般的に使用されている方法としては溶融混合法があり、その際に用いる装置の例としては押出機、バンバリーミキサー、ローラー、ニーダー等を挙げることができる。
熱可塑性樹脂組成物の製造は回分式、連続式のいずれでもよい。また、各成分の混合順序にも特に制限はなく、全ての成分が十分に均一混合されればよい。
<Method for producing thermoplastic resin composition>
There is no restriction | limiting in particular in the method of manufacturing a thermoplastic resin composition, It can manufacture using the method and apparatus currently performed normally. As a generally used method, there is a melt mixing method, and examples of an apparatus used at that time include an extruder, a Banbury mixer, a roller, and a kneader.
The production of the thermoplastic resin composition may be either a batch type or a continuous type. Moreover, there is no restriction | limiting in particular also in the mixing order of each component, All the components should just be fully mixed uniformly.
熱可塑性樹脂組成物は、その流動性や、成形品の低温耐衝撃性に優れることから、グラフト重合体（Ｂ）と共重合体（Ｃ）の合計１００質量部に対し、グラフト重合体（Ｂ）の含有量が１５〜４５質量部、共重合体（Ｃ）の含有量が５５〜８５質量部であることが好ましく、グラフト重合体（Ｂ）の含有量が２５〜４０質量部、共重合体（Ｃ）の含有量が６０〜７５質量部であることがより好ましい。特に、グラフト重合体（Ｂ）の含有量が増えると成形品の耐衝撃性や低温耐衝撃性が向上する傾向にあり、共重合体（Ｃ）の含有量が増えると熱可塑性樹脂組成物の流動性が向上する傾向にある。 The thermoplastic resin composition is excellent in fluidity and low-temperature impact resistance of the molded product. Therefore, the graft polymer (B) is added to 100 parts by mass of the graft polymer (B) and the copolymer (C). ) Is preferably 15 to 45 parts by mass, the content of the copolymer (C) is preferably 55 to 85 parts by mass, and the content of the graft polymer (B) is 25 to 40 parts by mass, It is more preferable that the content of the coalescence (C) is 60 to 75 parts by mass. In particular, when the content of the graft polymer (B) increases, the impact resistance and low-temperature impact resistance of the molded product tend to improve, and when the content of the copolymer (C) increases, the thermoplastic resin composition It tends to improve fluidity.
＜作用効果＞
本発明の熱可塑性樹脂組成物は、エチレン・プロピレン共重合体（ａ）とエチレン・プロピレン共重合体（ｂ）を含むゴム質重合体（Ａ）にビニル系単量体混合物が乳化グラフト重合したグラフト重合体（Ｂ）と、共重合体（Ｃ）とを含有するので、表面平滑性などの成形外観および低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である成形品を得ることができる。
<Effect>
In the thermoplastic resin composition of the present invention, a vinyl monomer mixture is emulsion-grafted to a rubbery polymer (A) containing an ethylene / propylene copolymer (a) and an ethylene / propylene copolymer (b). Since the graft polymer (B) and the copolymer (C) are contained, a molded product having excellent molding appearance such as surface smoothness and low-temperature impact resistance and a ductile fracture in a low-temperature environment is obtained. be able to.
［成形品］
本発明により得られる成形品は、上述した本発明の熱可塑性樹脂組成物を成形したものであり、表面平滑性などの成形外観および低温耐衝撃性に優れ、低温環境下における破壊形態が延性破壊である。
熱可塑性樹脂組成物の成形方法としては、例えば、射出成形法、射出圧縮成形機法、押出法、ブロー成形法、真空成形法、圧空成形法、カレンダー成形法、インフレーション成形法などが挙げられる。これらの中でも、量産性に優れ、高い寸法精度の成形品を得ることができるため、射出成形法、射出圧縮成形法が好ましい。
本発明により得られる成形品は、表面平滑性などの成形外観および低温耐衝撃性に優れる。しかも、低温環境下における破壊形態が延性破壊であるため、破壊しても破片が飛び散りにくい。よって、本発明により得られる成形品は、バンパー、ドアミラー、リアスポイラーなどの自動車外装部品等として特に好適であるが、それ以外の用途にも適用できる。
[Molding]
The molded product obtained by the present invention is obtained by molding the above-described thermoplastic resin composition of the present invention, has excellent molding appearance such as surface smoothness and low temperature impact resistance, and has a ductile fracture in a low temperature environment. It is.
Examples of the molding method of the thermoplastic resin composition include an injection molding method, an injection compression molding method, an extrusion method, a blow molding method, a vacuum molding method, a pressure molding method, a calendar molding method, an inflation molding method, and the like. Among these, the injection molding method and the injection compression molding method are preferable because they are excellent in mass productivity and can obtain a molded product with high dimensional accuracy.
The molded article obtained by the present invention is excellent in molding appearance such as surface smoothness and low temperature impact resistance. Moreover, since the fracture mode in a low-temperature environment is ductile fracture, even if the fracture occurs, the fragments are not easily scattered. Therefore, the molded product obtained by the present invention is particularly suitable as an automobile exterior part such as a bumper, a door mirror, and a rear spoiler, but can be applied to other uses.
以下、実施例および比較例を挙げて本発明を更に具体的に説明するが、本発明は、以下の実施例に限定されるものではない。
以下のゴム質重合体（Ａ）の製造に用いたエチレン・プロピレン共重合体を表１に示す。
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to a following example.
Table 1 shows the ethylene / propylene copolymers used for the production of the following rubber polymers (A).
なお、表１中の「エチレン／プロピレン／ジエン」は、「エチレン単位／プロピレン単位／非共役ジエン単位」のことである。
また、エチレン・プロピレン共重合体のメルトフローレート（ＭＦＲ）は、ＩＳＯ １１３３に準拠し、２３０℃、２１．２Ｎの条件にて測定した。
また、エチレン・プロピレン共重合体の融点（Ｔｍ）、融解熱量（ΔＨｍ）、結晶化温度（Ｔｃ）、結晶化熱量（ΔＨｃ）は以下のようにして測定した。
示差走査熱量計（ＤＳＣ）を使用して、２３℃から２００℃まで１０℃／分で昇温したときの融解ピークを測定し、これを融点（Ｔｍ）とした。また、融解ピークと同時に融解熱量（ΔＨｍ）を測定した。次いで、２００℃から−１００℃まで−１０℃／分で降温したときの結晶化ピークを測定し、これを結晶化温度（Ｔｃ）とした。また、結晶化ピークと同時に結晶化熱量（ΔＨｃ）を測定した。
In Table 1, “ethylene / propylene / diene” means “ethylene unit / propylene unit / non-conjugated diene unit”.
The melt flow rate (MFR) of the ethylene / propylene copolymer was measured under the conditions of 230 ° C. and 21.2 N in accordance with ISO 1133.
The melting point (Tm), heat of fusion (ΔHm), crystallization temperature (Tc), and heat of crystallization (ΔHc) of the ethylene / propylene copolymer were measured as follows.
Using a differential scanning calorimeter (DSC), a melting peak was measured when the temperature was raised from 23 ° C. to 200 ° C. at 10 ° C./min, and this was taken as the melting point (Tm). In addition, the heat of fusion (ΔHm) was measured simultaneously with the melting peak. Next, a crystallization peak was measured when the temperature was lowered from 200 ° C. to −100 ° C. at −10 ° C./min, and this was taken as the crystallization temperature (Tc). In addition, the crystallization heat (ΔHc) was measured simultaneously with the crystallization peak.
［ゴム質重合体（Ａ）の製造］
＜ゴム質重合体（Ａ１）＞
エチレン単位／プロピレン単位／非共役ジエン（１，４−ヘキサジエン）単位＝５１質量％／４９質量％／０質量％であり、２３０℃、２１．２Ｎで測定したＭＦＲが０．５ｇ/１０分であるエチレン・プロピレン共重合体（ａ１）５質量％と、エチレン単位／プロピレン単位／非共役ジエン（１，４−ヘキサジエン）単位＝５３質量％／４７質量％／０質量％であり、２３０℃、２１．２Ｎで測定したＭＦＲが５．２ｇ/１０分であるエチレン・プロピレン共重合体（ｂ１）９５質量％と、エチレン・プロピレン共重合体（ａ１）およびエチレン・プロピレン共重合体（ｂ１）の合計１００質量部に対し、ワックス状重合体として酸変性α−オレフィン系重合体（無水マレイン酸変性ポリエチレン）１２質量部と、乳化剤として長鎖アルキルカルボン酸塩（オレイン酸カリウム）２．５質量部とを加え、同時に機械乳化してラテックスを得た。得られたラテックスに、ｔ−ブチルクミルパーオキサイド０．７質量部およびジビニルベンゼン１．０質量部（いずれもラテックス中の固形分に対する量）を加え、１３０℃で５時間反応させ、ゴム質重合体（Ａ１）のラテックスを得た。得られたゴム質重合体（Ａ１）のラテックスの質量平均粒子径は４１０ｎｍであった。
なお、ゴム質重合体（Ａ１）のラテックスの質量平均粒子径は、粒度分布測定器を用いて質量基準の粒子径分布を測定し、得られた粒子径分布より算出した。
[Production of rubbery polymer (A)]
<Rubber polymer (A1)>
Ethylene unit / propylene unit / non-conjugated diene (1,4-hexadiene) unit = 51 mass% / 49 mass% / 0 mass%, MFR measured at 230 ° C. and 21.2 N is 0.5 g / 10 min. A certain ethylene / propylene copolymer (a1) 5% by mass, ethylene unit / propylene unit / non-conjugated diene (1,4-hexadiene) unit = 53% by mass / 47% by mass / 0% by mass, 95% by mass of an ethylene / propylene copolymer (b1) having an MFR measured at 21.2 N of 5.2 g / 10 min, an ethylene / propylene copolymer (a1) and an ethylene / propylene copolymer (b1) For 100 parts by mass in total, 12 parts by mass of an acid-modified α-olefin polymer (maleic anhydride-modified polyethylene) as a wax-like polymer and a long-chain alkyl group as an emulsifier. A latex was obtained by adding 2.5 parts by mass of rubonate (potassium oleate) and simultaneously mechanically emulsifying. To the obtained latex, 0.7 parts by mass of t-butylcumyl peroxide and 1.0 part by mass of divinylbenzene (both amounts relative to the solid content in the latex) were added and reacted at 130 ° C. for 5 hours. A latex of coalescence (A1) was obtained. The rubber-like polymer (A1) latex obtained had a mass-average particle diameter of 410 nm.
The mass average particle size of the latex of the rubber polymer (A1) was calculated from the particle size distribution obtained by measuring the mass size particle size distribution using a particle size distribution meter.
＜ゴム質重合体（Ａ２）＞
エチレン・プロピレン共重合体（ａ１）１０質量％、エチレン・プロピレン共重合体（ｂ１）９０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ２）のラテックスを得た。得られたゴム質重合体（Ａ２）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A2)>
Except for the ethylene / propylene copolymer (a1) 10 mass% and the ethylene / propylene copolymer (b1) 90 mass%, the rubber polymer is subjected to mechanical emulsification under the same conditions as the rubber polymer (A1). A latex (A2) was obtained. Table 2 shows the mass average particle diameter of the latex of the obtained rubber polymer (A2).
＜ゴム質重合体（Ａ３）＞
エチレン・プロピレン共重合体（ａ１）３０質量％、エチレン・プロピレン共重合体（ｂ１）７０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ３）のラテックスを得た。得られたゴム質重合体（Ａ３）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A3)>
A rubbery polymer is obtained by mechanical emulsification under the same conditions as the rubbery polymer (A1) except that the ethylene / propylene copolymer (a1) is 30% by mass and the ethylene / propylene copolymer (b1) is 70% by mass. A latex (A3) was obtained. Table 2 shows the mass average particle diameter of the latex of the obtained rubbery polymer (A3).
＜ゴム質重合体（Ａ４）＞
エチレン・プロピレン共重合体（ａ１）５０質量％、エチレン・プロピレン共重合体（ｂ１）５０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ４）のラテックスを得た。得られたゴム質重合体（Ａ４）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A4)>
A rubbery polymer is obtained by mechanical emulsification under the same conditions as the rubbery polymer (A1) except that the ethylene / propylene copolymer (a1) is 50% by mass and the ethylene / propylene copolymer (b1) is 50% by mass. A latex (A4) was obtained. Table 2 shows the mass average particle diameter of the latex of the obtained rubber polymer (A4).
＜ゴム質重合体（Ａ５）＞
エチレン・プロピレン共重合体（ａ１）７０質量％、エチレン・プロピレン共重合体（ｂ１）３０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ５）のラテックスを得た。得られたゴム質重合体（Ａ５）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A5)>
A rubbery polymer is obtained by mechanical emulsification under the same conditions as the rubbery polymer (A1) except that the ethylene / propylene copolymer (a1) is 70% by mass and the ethylene / propylene copolymer (b1) is 30% by mass. A latex (A5) was obtained. Table 2 shows the mass average particle diameter of the latex of the obtained rubbery polymer (A5).
＜ゴム質重合体（Ａ６）＞
エチレン単位／プロピレン単位／非共役ジエン（１，４−ヘキサジエン）単位＝７０質量％／２８質量％／２質量％であり、２３０℃、２１．２Ｎで測定したＭＦＲが０．３５ｇ/１０分であるエチレン・プロピレン共重合体（ａ２）３０質量％、エチレン・プロピレン共重合体（ｂ１）７０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ６）のラテックスを得た。得られたゴム質重合体（Ａ６）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A6)>
Ethylene unit / propylene unit / non-conjugated diene (1,4-hexadiene) unit = 70% by mass / 28% by mass / 2% by mass, and MFR measured at 230 ° C. and 21.2 N is 0.35 g / 10 min. Except for the ethylene / propylene copolymer (a2) 30% by mass and the ethylene / propylene copolymer (b1) 70% by mass, mechanical emulsification was carried out under the same conditions as the rubbery polymer (A1). A latex of coalescence (A6) was obtained. Table 2 shows the mass average particle diameter of the latex of the obtained rubber polymer (A6).
＜ゴム質重合体（Ａ７）＞
エチレン単位／プロピレン単位／非共役ジエン（１，４−ヘキサジエン）単位＝４４質量％／５６質量％／０質量％であり、２３０℃、２１．２Ｎで測定したＭＦＲが０．９５ｇ/１０分であるエチレン・プロピレン共重合体（ａ３）３０質量％、エチレン・プロピレン共重合体（ｂ１）７０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ７）のラテックスを得た。得られたゴム質重合体（Ａ７）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A7)>
Ethylene unit / propylene unit / non-conjugated diene (1,4-hexadiene) unit = 44% by mass / 56% by mass / 0% by mass, and MFR measured at 230 ° C. and 21.2 N is 0.95 g / 10 min. Except for the ethylene / propylene copolymer (a3) 30% by mass and the ethylene / propylene copolymer (b1) 70% by mass, mechanical emulsification was carried out under the same conditions as the rubbery polymer (A1). A latex of combined (A7) was obtained. Table 2 shows the mass average particle diameter of the latex of the obtained rubber polymer (A7).
＜ゴム質重合体（Ａ８）＞
エチレン・プロピレン共重合体（ａ１）３０質量％、エチレン単位／プロピレン単位／非共役ジエン（１，４−ヘキサジエン）単位＝６３質量％／３７質量％／０質量％であり、２３０℃、２１．２Ｎで測定したＭＦＲが７．３ｇ/１０分であるエチレン・プロピレン共重合体（ｂ３）７０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ８）のラテックスを得た。得られたゴム質重合体（Ａ８）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A8)>
30% by mass of ethylene / propylene copolymer (a1), ethylene unit / propylene unit / non-conjugated diene (1,4-hexadiene) unit = 63% by mass / 37% by mass / 0% by mass, 230 ° C., 21. Rubber emulsification is carried out by mechanical emulsification under the same conditions as the rubbery polymer (A1) except that 70% by mass of the ethylene / propylene copolymer (b3) having an MFR measured at 2N of 7.3 g / 10 min. A latex of coalescence (A8) was obtained. Table 2 shows the mass average particle diameter of the obtained rubber polymer (A8) latex.
＜ゴム質重合体（Ａ９）＞
エチレン・プロピレン共重合体（ａ１）３０質量％、エチレン単位／プロピレン単位／非共役ジエン（１，４−ヘキサジエン）単位＝６１質量％／３９質量％／０質量％であり、２３０℃、２１．２Ｎで測定したＭＦＲが３８ｇ/１０分であるエチレン・プロピレン共重合体（ｂ４）７０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ９）のラテックスを得た。得られたゴム質重合体（Ａ９）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A9)>
30% by mass of ethylene / propylene copolymer (a1), ethylene unit / propylene unit / non-conjugated diene (1,4-hexadiene) unit = 61% by mass / 39% by mass / 0% by mass, 230 ° C., 21. The rubber polymer (M4) was mechanically emulsified under the same conditions as the rubber polymer (A1), except that the ethylene / propylene copolymer (b4) had an MFR measured at 2N of 38 g / 10 min. A latex of A9) was obtained. Table 2 shows the mass average particle diameter of the latex of the obtained rubber polymer (A9).
＜ゴム質重合体（Ａ１０）＞
エチレン・プロピレン共重合体（ａ１）３０質量％、エチレン単位／プロピレン単位／非共役ジエン（１，４−ヘキサジエン）単位＝７２質量％／２７質量％／１質量％であり、２３０℃、２１．２Ｎで測定したＭＦＲが６．２ｇ/１０分であるエチレン・プロピレン共重合体（ｂ２）７０質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ１０）のラテックスを得た。得られたゴム質重合体（Ａ１０）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A10)>
30% by mass of ethylene / propylene copolymer (a1), ethylene unit / propylene unit / non-conjugated diene (1,4-hexadiene) unit = 72% by mass / 27% by mass / 1% by mass, 230 ° C., 21. Rubber emulsification is carried out by mechanical emulsification under the same conditions as the rubber polymer (A1) except that the ethylene / propylene copolymer (b2) having an MFR measured at 2N of 6.2 g / 10 min is 70% by mass. A latex of coalescence (A10) was obtained. Table 2 shows the mass average particle diameter of the latex of the resulting rubbery polymer (A10).
＜ゴム質重合体（Ａ１１）＞
エチレン・プロピレン共重合体（ａ１）１００質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ１１）のラテックスを得た。得られたゴム質重合体（Ａ１１）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A11)>
Except for the ethylene / propylene copolymer (a1) of 100% by mass, mechanical emulsification was performed under the same conditions as the rubber polymer (A1) to obtain a latex of the rubber polymer (A11). Table 2 shows the mass average particle diameter of the latex of the obtained rubbery polymer (A11).
＜ゴム質重合体（Ａ１２）＞
エチレン・プロピレン共重合体（ｂ１）１００質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ１２）のラテックスを得た。得られたゴム質重合体（Ａ１２）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A12)>
Except for the ethylene / propylene copolymer (b1) of 100% by mass, mechanical emulsification was performed under the same conditions as the rubber polymer (A1) to obtain a latex of the rubber polymer (A12). Table 2 shows the mass average particle diameter of the latex of the obtained rubber polymer (A12).
＜ゴム質重合体（Ａ１３）＞
エチレン・プロピレン共重合体（ｂ２）１００質量％とした以外は、ゴム質重合体（Ａ１）と同様の条件で機械乳化を行いゴム質重合体（Ａ１３）のラテックスを得た。得られたゴム質重合体（Ａ１３）のラテックスの質量平均粒子径を表２に示す。
<Rubber polymer (A13)>
Except for the ethylene / propylene copolymer (b2) being 100% by mass, mechanical emulsification was performed under the same conditions as the rubber polymer (A1) to obtain a latex of the rubber polymer (A13). Table 2 shows the mass average particle diameter of the latex of the obtained rubber polymer (A13).
［グラフト重合体（Ｂ）の製造］
＜グラフト重合体（Ｂ１）＞
撹拌装置を備えた２０Ｌの重合反応器に、ゴム質重合体（Ａ１）のラテックス７０質量部（固形分換算）と、蒸留水１５５質量部（ゴム質重合体（Ａ１）のラテックス中の水も含む）と、ピロリン酸ナトリウム０．１５質量部と、硫酸第一鉄七水塩０．００６質量部と、フラクトース０．３５質量部とを仕込み、内温を８０℃に保った。これに、スチレン（Ｓｔ）２１質量部およびアクリロニトリル（ＡＮ）９質量部からなる単量体混合物と、クメンハイドロパーオキサイド０．６質量部とを、各々別の供給口から１４０分かけて同時に滴下して重合を行った。この間、内温は８０℃で一定に制御した。滴下終了後、さらに１００分間８０℃のまま保持した後に冷却して乳化グラフト重合を完結させ、反応生成物のラテックスを得た。得られた生成物のラテックスを硫酸水溶液で凝固、水洗した後、乾燥してグラフト重合体（Ｂ１）を得た。
[Production of Graft Polymer (B)]
<Graft polymer (B1)>
In a 20 L polymerization reactor equipped with a stirrer, 70 parts by mass of rubber polymer (A1) latex (in terms of solid content) and 155 parts by mass of distilled water (rubber polymer (A1) in water) And 0.15 parts by mass of sodium pyrophosphate, 0.006 parts by mass of ferrous sulfate heptahydrate, and 0.35 parts by mass of fructose, and the internal temperature was kept at 80 ° C. To this, a monomer mixture composed of 21 parts by mass of styrene (St) and 9 parts by mass of acrylonitrile (AN) and 0.6 parts by mass of cumene hydroperoxide were simultaneously added dropwise from another supply port over 140 minutes. Then, polymerization was performed. During this time, the internal temperature was controlled to be constant at 80 ° C. After completion of dropping, the mixture was further kept at 80 ° C. for 100 minutes and then cooled to complete the emulsion graft polymerization to obtain a reaction product latex. The obtained latex product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft polymer (B1).
＜グラフト重合体（Ｂ２）〜（Ｂ１３）＞
表３に示す種類のゴム質重合体（Ａ）のラテックスを、グラフト重合体（Ｂ１）と同様の条件で乳化グラフト重合し、得られた生成物のラテックスを硫酸水溶液で凝固、水洗した後、乾燥してグラフト重合体（Ｂ２）〜（Ｂ１３）を得た。
<Graft polymer (B2) to (B13)>
The latex of the type of rubbery polymer (A) shown in Table 3 was subjected to emulsion graft polymerization under the same conditions as the graft polymer (B1), and the resulting latex was coagulated with an aqueous sulfuric acid solution and washed with water. Drying gave graft polymers (B2) to (B13).
［共重合体（Ｃ）の製造］
蒸留水１２０質量部に、アルキルベンゼンスルホン酸ナトリウム０．００３質量部と、スチレン６８質量％およびアクリロニトリル３２質量％を含む単量体混合物１００質量部と、ｔ−ドデシルメルカプタン０．３５質量部と、過酸化ベンゾイル０．１５質量部と、リン酸カルシウム０．５質量部とを添加して、１１０℃で１０時間懸濁重合し、共重合体（Ｃ）を得た。
[Production of Copolymer (C)]
To 120 parts by mass of distilled water, 0.003 part by mass of sodium alkylbenzenesulfonate, 100 parts by mass of a monomer mixture containing 68% by mass of styrene and 32% by mass of acrylonitrile, 0.35 parts by mass of t-dodecyl mercaptan, 0.15 parts by mass of benzoyl oxide and 0.5 parts by mass of calcium phosphate were added, and suspension polymerization was performed at 110 ° C. for 10 hours to obtain a copolymer (C).
［実施例１〜８、比較例１〜８］
グラフト重合体（Ｂ）と共重合体（Ｃ）とを表４、５に示す組成（質量部）で混合し、３０ｍｍ二軸押出機（株式会社日本製鋼所製、「ＴＥＸ−３０α」）を用いて２３０℃で溶融混練し、ペレット状の熱可塑性樹脂組成物を得た。得られた熱可塑性樹脂組成物の成形加工性を、以下の方法により評価した。評価結果を表４、５に示す。
また、得られた熱可塑性樹脂組成物を射出成形して１００×１００ｍｍ（厚み２ｍｍ、または４ｍｍ）の成形品（試験片）を作製し、成形外観、耐衝撃性および低温耐衝撃性、低温環境下における破壊形態を、以下の方法により評価した。評価結果を表４、５に示す。
[Examples 1-8, Comparative Examples 1-8]
The graft polymer (B) and the copolymer (C) were mixed in the compositions (parts by mass) shown in Tables 4 and 5, and a 30 mm twin screw extruder (manufactured by Nippon Steel Works, Ltd., “TEX-30α”) was used. The mixture was melt kneaded at 230 ° C. to obtain a pellet-shaped thermoplastic resin composition. The molding processability of the obtained thermoplastic resin composition was evaluated by the following method. The evaluation results are shown in Tables 4 and 5.
Further, the obtained thermoplastic resin composition is injection molded to produce a molded product (test piece) of 100 × 100 mm (thickness 2 mm or 4 mm), and the molded appearance, impact resistance and low temperature impact resistance, low temperature environment The fracture mode below was evaluated by the following method. The evaluation results are shown in Tables 4 and 5.
＜評価方法＞
（成形加工性の評価）
熱可塑性樹脂組成物について、ＩＳＯ １１３３に準拠し、２２０℃でのメルトボリュームレート（ＭＶＲ（ｃｍ３／１０分））を測定した。
<Evaluation method>
(Evaluation of moldability)
The thermoplastic resin composition, conforming to ISO 1133, were measured melt volume rate at 220 ℃ (MVR (cm 3/ 10 min)).
（成形外観の評価）
１００×１００ｍｍ（厚み２ｍｍ）の成形品について、表面に観測されたブツの数を目視で確認し、以下に示す評価基準にて成形外観を評価した。なお、ブツが成形品表面にあると不良成形品となることから、「○」の場合を表面平滑性に優れると判断し、合格とした。
○：ブツが観測されない。
△：ブツの数が１〜４個
×：ブツの数が５個以上
(Evaluation of molding appearance)
About the molded product of 100x100mm (thickness 2mm), the number of the spots observed on the surface was confirmed visually, and the shaping | molding external appearance was evaluated on the evaluation criteria shown below. In addition, since it will become a defective molded product if there are bumps on the surface of the molded product, the case of “◯” was judged to be excellent in surface smoothness, and was accepted.
○: No irregularities are observed.
Δ: 1 to 4 pieces ×: 5 or more pieces
（耐衝撃性および低温耐衝撃性の評価）
成形品について、ＩＳＯ １７９に準拠し、測定温度２３℃または−３０℃、成形品の厚さ４ｍｍの条件で、Ｖノッチ付きシャルピー衝撃強度（ＫＪ／ｍ２）を測定した。
(Evaluation of impact resistance and low temperature impact resistance)
The molded product was measured for Charpy impact strength (KJ / m 2 ) with V notch in accordance with ISO 179 under the conditions of a measurement temperature of 23 ° C. or −30 ° C. and a thickness of the molded product of 4 mm.
（破壊形態の評価）
高速衝撃試験機（株式会社島津製作所製、「ＨＴＭ−１型」）を用い、−３０℃において、１００ｍｍ×１００ｍｍ（厚み２ｍｍ）の成形品の中央に、先端径１／２インチラウンドミサイルを２ｍ／秒の速度で落下させ、破壊試験を行った。１０枚の成形品について破壊試験を行い、試験後の成形品の破壊形態を目視にて観測し、延性破壊しているか、脆性破壊しているかを確認し、以下の評価基準にて破壊形態を評価した。なお、「○」または「◎」の場合を延性破壊すると判断し、合格とした。
◎：９〜１０枚が延性破壊
○：６〜８枚が延性破壊
△：３〜５枚が延性破壊
×：０〜２枚が延性破壊
(Evaluation of destruction mode)
Using a high-speed impact tester (manufactured by Shimadzu Corporation, “HTM-1 type”), at −30 ° C., 2 m of a round missile with a tip diameter of 1/2 inch is formed in the center of a molded product of 100 mm × 100 mm (thickness 2 mm). The sample was dropped at a speed of / sec and subjected to a destructive test. A destructive test is performed on 10 molded products, and the fracture form of the molded product after the test is visually observed to confirm whether it is ductile fracture or brittle fracture. evaluated. In addition, the case of “◯” or “◎” was judged to be ductile fracture, and was accepted.
◎: 9-10 sheets are ductile fracture ○: 6-8 sheets are ductile fracture △: 3-5 sheets are ductile fracture ×: 0-2 sheets are ductile fracture
表４から明らかなように、実施例１〜８の熱可塑性樹脂組成物は成形加工性に優れていた。また、実施例１〜８の熱可塑性樹脂組成物より得られた成形品は、成形外観（表面平滑性）および低温耐衝撃性に優れていた。しかも、低温環境下における破壊形態が延性破壊であった。また、実施例１〜６を比較すると、エチレン・プロピレン共重合体（ａ）の含有量が５０質量％、エチレン・プロピレン共重合体（ｂ）の含有量が５０質量％である実施例３の成形品は、耐衝撃性が特に優れていた。
従って、本発明の熱可塑性樹脂組成物を成形してなる成形品は、バンパー、ドアミラー、リアスポイラーなどの自動車外装部品等に好適であることが示された。
As is clear from Table 4, the thermoplastic resin compositions of Examples 1 to 8 were excellent in moldability. In addition, the molded articles obtained from the thermoplastic resin compositions of Examples 1 to 8 were excellent in molding appearance (surface smoothness) and low temperature impact resistance. In addition, the fracture mode in a low temperature environment was ductile fracture. Further, when Examples 1 to 6 are compared, the content of the ethylene / propylene copolymer (a) is 50% by mass, and the content of the ethylene / propylene copolymer (b) is 50% by mass. The molded article was particularly excellent in impact resistance.
Therefore, it has been shown that a molded product obtained by molding the thermoplastic resin composition of the present invention is suitable for automobile exterior parts such as bumpers, door mirrors, rear spoilers, and the like.
一方、表５から明らかなように、比較例１は、エチレン・プロピレン共重合体（ａ１）の含有量が５質量％と少なく、エチレン・プロピレン共重合体（ｂ１）の含有量が９５質量％と多いゴム質重合体（Ａ１）を用いたため、破壊形態の評価において延性破壊を示した成形品は３〜５枚と少なかった。
比較例２は、エチレン・プロピレン共重合体（ａ１）の含有量が７０質量％と多く、エチレン・プロピレン共重合体（ｂ１）の含有量が３０質量％と少ないゴム質重合体（Ａ５）を用いたため、成形品は成形外観に劣っていた。
比較例３は、ＭＦＲが３８ｇ／１０分であるエチレン・プロピレン共重合体（ｂ４）を含むゴム質重合体（Ａ９）を用いたため、成形品の低温耐衝撃性が低かった。また、破壊形態の評価において延性破壊を示した成形品は０〜２枚と著しく少なかった。
比較例４は、エチレン単位が７２質量％と多く、プロピレン単位が２７質量％と少ないエチレン・プロピレン共重合体（ｂ２）を含むゴム質重合体（Ａ１０）を用いたため、成形品の低温耐衝撃性が低かった。また、破壊形態の評価において延性破壊を示した成形品は０〜２枚と著しく少なかった。
比較例５は、エチレン・プロピレン共重合体（ｂ）を含まないゴム質重合体（Ａ１１）を用いたため、成形品は成形外観に劣っていた。
比較例６は、エチレン・プロピレン共重合体（ａ）を含まないゴム質重合体（Ａ１２）を用いたため、成形品の低温耐衝撃性が低かった。また、破壊形態の評価において延性破壊を示した成形品は３〜５枚と少なかった。
比較例７は、エチレン・プロピレン共重合体（ａ）を含まず、かつエチレン単位が７２質量％と多く、プロピレン単位が２７質量％と少ないエチレン・プロピレン共重合体（ｂ２）を含むゴム質重合体（Ａ１３）を用いたため、成形品の低温耐衝撃性が低かった。また、破壊形態の評価において延性破壊を示した成形品は０〜２枚と著しく少なかった。
比較例８は、エチレン・プロピレン共重合体（ａ）とエチレン・プロピレン共重合体（ｂ）が均一に混合されていないため、成形品は成形外観に劣っていた。また、破壊形態の評価において延性破壊を示した成形品は０〜２枚と著しく少なかった。
On the other hand, as is clear from Table 5, Comparative Example 1 has a low content of ethylene / propylene copolymer (a1) of 5% by mass and a content of ethylene / propylene copolymer (b1) of 95% by mass. Since a large amount of rubbery polymer (A1) was used, the number of molded products that exhibited ductile fracture in the evaluation of the fracture mode was small, 3-5.
Comparative Example 2 is a rubber polymer (A5) having a high ethylene / propylene copolymer (a1) content of 70% by mass and a low ethylene / propylene copolymer (b1) content of 30% by mass. Since it was used, the molded product was inferior in molded appearance.
Since the rubbery polymer (A9) containing the ethylene propylene copolymer (b4) whose MFR is 38 g / 10min was used for the comparative example 3, the low temperature impact resistance of the molded article was low. Moreover, the molded product which showed the ductile fracture in evaluation of the fracture | rupture form was remarkably few with 0-2 sheets.
Comparative Example 4 uses a rubbery polymer (A10) containing an ethylene / propylene copolymer (b2) having a high ethylene unit of 72% by mass and a small amount of propylene unit of 27% by mass. The sex was low. Moreover, the molded product which showed the ductile fracture in evaluation of a fracture form was remarkably few with 0-2 sheets.
Since the comparative example 5 used the rubber-like polymer (A11) which does not contain an ethylene propylene copolymer (b), the molded article was inferior to the shaping | molding external appearance.
In Comparative Example 6, since the rubber polymer (A12) not containing the ethylene / propylene copolymer (a) was used, the low-temperature impact resistance of the molded product was low. Moreover, there were few molded articles which showed the ductile fracture in evaluation of the fracture | rupture form with 3-5 sheets.
Comparative Example 7 does not contain an ethylene / propylene copolymer (a), has a large ethylene unit of 72% by mass, and contains an ethylene / propylene copolymer (b2) with a small amount of propylene units of 27% by mass. Since coalescence (A13) was used, the low-temperature impact resistance of the molded product was low. Moreover, the molded product which showed the ductile fracture in evaluation of the fracture | rupture form was remarkably few with 0-2 sheets.
In Comparative Example 8, since the ethylene / propylene copolymer (a) and the ethylene / propylene copolymer (b) were not uniformly mixed, the molded product was inferior in molding appearance. Moreover, the molded product which showed the ductile fracture in evaluation of the fracture | rupture form was remarkably few with 0-2 sheets.
Claims (1)
芳香族ビニル系単量体とシアン化ビニル系単量体とを含む単量体混合物を重合した共重合体（Ｃ）とを含有することを特徴とする熱可塑性樹脂組成物。 10 to 60% by mass of an ethylene / propylene copolymer (a) having a melt flow rate measured at 230 ° C. and 21.2 N of 0.1 g / 10 min or more and less than 1 g / 10 min, and 230 ° C. and 21.2 N An ethylene / propylene copolymer (b) having a melt flow rate of 1 to 35 g / 10 min, 40 to 65% by mass of ethylene units and 35 to 60% by mass of propylene units, and 40 to 90% by mass. A graft polymer (B) obtained by emulsion graft polymerization of a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer to the rubber polymer (A).
A thermoplastic resin composition comprising a copolymer (C) obtained by polymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer.
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| JPH05222138A (en) * | 1992-02-10 | 1993-08-31 | Mitsui Petrochem Ind Ltd | Propylene polymer composition and its production |
| JPH0848731A (en) * | 1994-08-03 | 1996-02-20 | Sanyo Chem Ind Ltd | Composite resin composition and hot-melt adhesive |
| JP2004231969A (en) * | 2004-03-29 | 2004-08-19 | Mitsui Chemicals Inc | Crosslinked amorphous copolymer latex composition and its application |
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| JPH05222138A (en) * | 1992-02-10 | 1993-08-31 | Mitsui Petrochem Ind Ltd | Propylene polymer composition and its production |
| JPH0848731A (en) * | 1994-08-03 | 1996-02-20 | Sanyo Chem Ind Ltd | Composite resin composition and hot-melt adhesive |
| JP2004231969A (en) * | 2004-03-29 | 2004-08-19 | Mitsui Chemicals Inc | Crosslinked amorphous copolymer latex composition and its application |
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