JP2021024981A - Core shell type particle, graft copolymer, thermoplastic resin composition and molding thereof - Google Patents
Core shell type particle, graft copolymer, thermoplastic resin composition and molding thereof Download PDFInfo
- Publication number
- JP2021024981A JP2021024981A JP2019145540A JP2019145540A JP2021024981A JP 2021024981 A JP2021024981 A JP 2021024981A JP 2019145540 A JP2019145540 A JP 2019145540A JP 2019145540 A JP2019145540 A JP 2019145540A JP 2021024981 A JP2021024981 A JP 2021024981A
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- Prior art keywords
- copolymer
- vinyl
- based monomer
- mass
- graft
- 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.)
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- 239000002245 particle Substances 0.000 title claims abstract description 105
- 239000011258 core-shell material Substances 0.000 title claims abstract description 78
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 73
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 72
- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- 238000000465 moulding Methods 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 146
- 229920001577 copolymer Polymers 0.000 claims abstract description 139
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 110
- 239000000203 mixture Substances 0.000 claims abstract description 90
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 88
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 29
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims description 61
- 239000000047 product Substances 0.000 claims description 43
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 27
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 26
- 230000008961 swelling Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000002954 polymerization reaction product Substances 0.000 claims description 2
- -1 alkyl acrylate ester Chemical class 0.000 abstract description 24
- 230000035939 shock Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 54
- 238000004519 manufacturing process Methods 0.000 description 24
- 239000003995 emulsifying agent Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- 229920001971 elastomer Polymers 0.000 description 19
- 239000003999 initiator Substances 0.000 description 19
- 239000005060 rubber Substances 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 16
- 238000002347 injection Methods 0.000 description 16
- 239000007924 injection Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 150000001451 organic peroxides Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229920001893 acrylonitrile styrene Polymers 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 6
- 229920000800 acrylic rubber Polymers 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 238000010559 graft polymerization reaction Methods 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007869 azo polymerization initiator Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- 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 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
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- 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 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
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-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
- SXTILEHINBCKSS-UHFFFAOYSA-N 1-chloro-3-phenylpyrrole-2,5-dione Chemical class O=C1N(Cl)C(=O)C=C1C1=CC=CC=C1 SXTILEHINBCKSS-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
- 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
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- YEKDUBMGZZTUDY-UHFFFAOYSA-N 1-tert-butylpyrrole-2,5-dione Chemical compound CC(C)(C)N1C(=O)C=CC1=O YEKDUBMGZZTUDY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JZUPFUMEEMVFBV-UHFFFAOYSA-N 2,3-bis(tert-butylperoxy)-1,1,2-trimethylcyclohexane Chemical compound CC(C)(C)OOC1CCCC(C)(C)C1(C)OOC(C)(C)C JZUPFUMEEMVFBV-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、成形外観と耐衝撃性に優れ、流動性にも優れる熱可塑性樹脂組成物を与えるコア−シェル型粒子およびグラフト共重合体と、このグラフト共重合体を含む熱可塑性樹脂組成物とその成形品に関する。 The present invention comprises a core-shell type particle and a graft copolymer that provides a thermoplastic resin composition having excellent molded appearance, impact resistance, and excellent fluidity, and a thermoplastic resin composition containing the graft copolymer. Regarding the molded product.
樹脂材料の耐衝撃性を向上させることは、樹脂材料の用途を拡大させるだけでなく成形品の薄肉化や大型化への対応を可能にするなど、工業的な有用性が非常に高い。樹脂材料の耐衝撃性向上については、これまでに様々な手法が提案されてきた。このうち、ゴム質重合体と硬質樹脂材料とを組み合わせることによって、硬質樹脂材料の特性を保持しつつ耐衝撃性を高める手法は既に工業化されている。このような材料としては、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂が挙げられる。 Improving the impact resistance of a resin material not only expands the use of the resin material, but also makes it possible to cope with thinning and large-sized molded products, and is extremely useful in industry. Various methods have been proposed so far for improving the impact resistance of resin materials. Of these, a method of improving impact resistance while maintaining the characteristics of the hard resin material by combining the rubber polymer and the hard resin material has already been industrialized. Examples of such a material include acrylonitrile-butadiene-styrene (ABS) resin.
しかし、ＡＢＳ樹脂は耐衝撃性と成形外観に優れるものの、ゴム成分であるポリブダジエンの耐候性が低いため、塗装やフィルム等の加飾を施すことなく使用することが困難であった。 However, although ABS resin is excellent in impact resistance and molded appearance, it is difficult to use it without painting or decoration such as a film because the weather resistance of polybudadien, which is a rubber component, is low.
そのようなＡＢＳ樹脂の課題を解決するため、ゴム成分としてアクリルゴムを使用したアクリロニトリル−スチレン−アクリル酸エステル（ＡＳＡ）樹脂が開発され、工業化されている。 In order to solve the problem of such ABS resin, an acrylonitrile-styrene-acrylic acid ester (ASA) resin using acrylic rubber as a rubber component has been developed and industrialized.
例えば、特許文献１には硬質樹脂材料としてアクリロニトリル−スチレン（ＡＳ）樹脂を用い、そこにＡＳＡ樹脂を添加する方法が開示されている。
しかしながら、ＡＳＡ樹脂は、硬質樹脂成分であるアクリロニトリル−スチレン（ＡＳ）樹脂と、アクリルゴム間の屈折率差が大きいため、低射出速度での成形時の成形外観が悪い。また、高射出速度での成形時にはさらに成形外観が悪化するといった問題があった。
For example, Patent Document 1 discloses a method in which an acrylonitrile-styrene (AS) resin is used as a hard resin material and an ASA resin is added thereto.
However, since the ASA resin has a large difference in refractive index between the acrylonitrile-styrene (AS) resin, which is a hard resin component, and the acrylic rubber, the molding appearance at the time of molding at a low injection speed is poor. Further, there is a problem that the molding appearance is further deteriorated at the time of molding at a high injection speed.
特許文献２や特許文献３には、ポリブタジエン粒子の外側をアクリルゴムで覆った構造のポリブタジエン／アクリルゴム複合体をＡＳ樹脂に添加する方法が開示されている。
この方法であれば、ポリブタジエンを複合することでゴム成分とＡＳ樹脂の屈折率差が小さくなり、成形外観が良好となる。しかし、ポリブタジエンを複合するため耐候性が低下するといった問題がある。
Patent Document 2 and Patent Document 3 disclose a method of adding a polybutadiene / acrylic rubber composite having a structure in which the outside of polybutadiene particles is covered with acrylic rubber to an AS resin.
In this method, the difference in refractive index between the rubber component and the AS resin is reduced by combining polybutadiene, and the molded appearance is improved. However, there is a problem that the weather resistance is lowered due to the composite of polybutadiene.
特許文献４には、アクリル酸ブチルとスチレンを共重合することで、アクリルゴムの屈折率を上げる方法が開示されている。
しかし、特許文献４に記載された方法では、耐衝撃性が著しく低下してしまう。また、低射出速度での成形時の成形外観は良好であるが、高射出速度での成形時の成形外観が悪いという問題があった。
Patent Document 4 discloses a method of increasing the refractive index of acrylic rubber by copolymerizing butyl acrylate and styrene.
However, with the method described in Patent Document 4, the impact resistance is significantly lowered. Further, although the molding appearance at the time of molding at a low injection speed is good, there is a problem that the molding appearance at the time of molding at a high injection speed is poor.
本発明は、成形外観と耐衝撃性に優れ、流動性にも優れる熱可塑性樹脂組成物を与えるコア−シェル型粒子およびグラフト共重合体と、このグラフト共重合体を含む熱可塑性樹脂組成物およびその成形品を提供することを課題とする。 The present invention comprises a core-shell type particle and a graft copolymer that provides a thermoplastic resin composition having excellent molded appearance, impact resistance, and excellent fluidity, and a thermoplastic resin composition containing the graft copolymer. An object is to provide the molded product.
本発明者は、上記課題を解決すべく検討を重ねた結果、グラフト共重合体のゴム粒子として、（メタ）アクリル酸アルキルエステル（ａ）を含むビニル系単量体混合物（ｍ１）を重合して得られる共重合体（Ａ）よりなるコア部と、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）を含むビニル系単量体混合物（ｍ２）を重合して得られる共重合体（Ｂ）よりなるシェル部とを有するコア−シェル型粒子（Ｃ）を用いることにより、成形外観と耐衝撃性に優れ、流動性にも優れる熱可塑性樹脂組成物を得ることができることを見出した。 As a result of repeated studies to solve the above problems, the present inventor polymerizes a vinyl-based monomer mixture (m1) containing (meth) acrylic acid alkyl ester (a) as rubber particles of the graft copolymer. A copolymer obtained by polymerizing a core portion made of the copolymer (A) obtained above and a vinyl-based monomer mixture (m2) containing a (meth) acrylic acid ester (b) having an aromatic hydrocarbon group. It has been found that by using the core-shell type particles (C) having the shell portion made of the coalesced (B), it is possible to obtain a thermoplastic resin composition having excellent molded appearance, impact resistance, and excellent fluidity. It was.
即ち、本発明は以下を要旨とする。 That is, the gist of the present invention is as follows.
［１］ （メタ）アクリル酸アルキルエステル（ａ）を含むビニル系単量体混合物（ｍ１）を重合して得られる共重合体（Ａ）よりなるコア部と、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）を含むビニル系単量体混合物（ｍ２）を重合して得られる共重合体（Ｂ）よりなるシェル部とを有するコア−シェル型粒子（Ｃ）。 [1] It has a core portion made of a copolymer (A) obtained by polymerizing a vinyl-based monomer mixture (m1) containing a (meth) acrylic acid alkyl ester (a), and an aromatic hydrocarbon group ( A core-shell type particle (C) having a shell portion made of a copolymer (B) obtained by polymerizing a vinyl-based monomer mixture (m2) containing a meta) acrylic acid ester (b).
［２］ コア−シェル型粒子（Ｃ）１００質量％中の共重合体（Ａ）の含有量が３５〜９７質量％で、共重合体（Ｂ）の含有量が３〜６５質量％である［１］に記載の共重合体（Ａ）。 [2] The content of the copolymer (A) in 100% by mass of the core-shell type particles (C) is 35 to 97% by mass, and the content of the copolymer (B) is 3 to 65% by mass. The copolymer (A) according to [1].
［３］ 共重合体（Ａ）が、（メタ）アクリル酸アルキルエステル（ａ）単位と、架橋剤に由来する単位および／又はグラフト交叉剤に由来する単位を含む、［１］又は［２］に記載のコア−シェル型粒子（Ｃ）。 [3] The copolymer (A) contains a (meth) acrylic acid alkyl ester (a) unit and a unit derived from a cross-linking agent and / or a unit derived from a graft cross-linking agent [1] or [2]. The core-shell type particle (C) according to.
［４］ 共重合体（Ａ）中の架橋剤および／又はグラフト交叉剤に由来する単位の割合が、（メタ）アクリル酸アルキルエステル（ａ）単位と、架橋剤に由来する単位および／又はグラフト交叉剤に由来する単位との合計１００質量％中、０．０１〜３質量％である、［３］に記載のコア−シェル型粒子（Ｃ）。 [4] The proportion of the unit derived from the cross-linking agent and / or the graft cross-linking agent in the copolymer (A) is the (meth) acrylic acid alkyl ester (a) unit and the unit and / or the graft derived from the cross-linking agent. The core-shell type particle (C) according to [3], which is 0.01 to 3% by mass in a total of 100% by mass with the unit derived from the cross-linking agent.
［５］ 共重合体（Ｂ）が、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）単位と、架橋剤に由来する単位および／又はグラフト交叉剤に由来する単位を含む、［１］ないし［４］のいずれかに記載のコア−シェル型粒子（Ｃ）。 [5] The copolymer (B) contains a (meth) acrylic acid ester (b) unit having an aromatic hydrocarbon group and a unit derived from a cross-linking agent and / or a unit derived from a graft cross-linking agent. The core-shell type particle (C) according to any one of 1] to [4].
［６］ 共重合体（Ｂ）中の架橋剤および／又はグラフト交叉剤に由来する単位の割合が、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）単位と、架橋剤に由来する単位との合計１００質量％中、０．０１〜３質量％である、［５］に記載のコア−シェル型粒子（Ｃ）。 [6] The proportion of the unit derived from the cross-linking agent and / or the graft cross-linking agent in the copolymer (B) is derived from the (meth) acrylic acid ester (b) unit having an aromatic hydrocarbon group and the cross-linking agent. The core-shell type particle (C) according to [5], which is 0.01 to 3% by mass in a total of 100% by mass with the unit.
［７］ 共重合体（Ａ）の体積平均粒子径が５０〜８００ｎｍで、膨潤度が２〜１５倍であり、コア−シェル型粒子（Ｃ）の体積平均粒子径が６０〜８２０ｎｍで、膨潤度が２〜１５倍である、［１］ないし［６］のいずれかに記載のコア−シェル型粒子（Ｃ）。 [7] The copolymer (A) has a volume average particle size of 50 to 800 nm and a swelling degree of 2 to 15 times, and the core-shell type particle (C) has a volume average particle size of 60 to 820 nm and swells. The core-shell type particle (C) according to any one of [1] to [6], which has a degree of 2 to 15 times.
［８］ ［１］ないし［７］のいずれかに記載のコア−シェル型粒子（Ｃ）に、ビニル系単量体混合物（ｍ３）をグラフト重合してなるグラフト共重合体（Ｄ）。 [8] A graft copolymer (D) obtained by graft-polymerizing a vinyl-based monomer mixture (m3) onto the core-shell type particles (C) according to any one of [1] to [7].
［９］ ビニル系単量体混合物（ｍ３）が芳香族ビニル系単量体とシアン化ビニル系単量体を含み、ビニル系単量体混合物（ｍ３）に含まれる芳香族ビニル系単量体の含有率が４０〜９０質量％で、シアン化ビニル系単量体の含有率が１０〜６０質量％である、［８］に記載のグラフト共重合体（Ｄ）。 [9] The vinyl-based monomer mixture (m3) contains an aromatic vinyl-based monomer and a vinyl cyanide-based monomer, and the aromatic vinyl-based monomer contained in the vinyl-based monomer mixture (m3). The graft copolymer (D) according to [8], wherein the content of the graft copolymer (D) is 40 to 90% by mass, and the content of the vinyl cyanide-based monomer is 10 to 60% by mass.
［１０］ コア−シェル型粒子（Ｃ）とビニル系単量体混合物（ｍ３）との合計１００質量％に対するコア−シェル型粒子（Ｃ）の割合が５０〜８０質量％で、ビニル系単量体混合物（ｍ３）の割合が２０〜５０質量％で、グラフト率が２５〜１００％である、［８］又は［９］に記載のグラフト共重合体（Ｄ）。 [10] The ratio of the core-shell type particles (C) to 100% by mass of the total of the core-shell type particles (C) and the vinyl-based monomer mixture (m3) is 50 to 80% by mass, and the vinyl-based single amount. The graft copolymer (D) according to [8] or [9], wherein the ratio of the body mixture (m3) is 20 to 50% by mass and the graft ratio is 25 to 100%.
［１１］ ［８］ないし［１０］のいずれかに記載のグラフト共重合体（Ｄ）を含む熱可塑性樹脂組成物。 [11] A thermoplastic resin composition containing the graft copolymer (D) according to any one of [8] to [10].
［１２］ グラフト共重合体（Ｄ）と、ビニル系単量体混合物（ｍ４）の重合反応物である共重合体（Ｅ）とを含む、［１１］に記載の熱可塑性樹脂組成物。 [12] The thermoplastic resin composition according to [11], which comprises a graft copolymer (D) and a copolymer (E) which is a polymerization reaction product of a vinyl-based monomer mixture (m4).
［１３］ ビニル系単量体混合物（ｍ３）が芳香族ビニル系単量体とシアン化ビニル系単量体を含み、ビニル系単量体混合物（ｍ４）がビニル系単量体混合物（ｍ３）に含まれる芳香族ビニル系単量体と同じ構造の芳香族ビニル系単量体と、ビニル系単量体混合物（ｍ３）に含まれるシアン化ビニル系単量体と同じ構造のシアン化ビニル系単量体を含む、［１２］に記載の熱可塑性樹脂組成物。 [13] The vinyl-based monomer mixture (m3) contains an aromatic vinyl-based monomer and a vinyl cyanide-based monomer, and the vinyl-based monomer mixture (m4) is a vinyl-based monomer mixture (m3). An aromatic vinyl-based monomer having the same structure as the aromatic vinyl-based monomer contained in, and a vinyl cyanide-based monomer having the same structure as the vinyl cyanide-based monomer contained in the vinyl-based monomer mixture (m3). The thermoplastic resin composition according to [12], which comprises a monomer.
［１４］ グラフト共重合体（Ｄ）と共重合体（Ｅ）との合計１００質量％中にグラフト共重合体（Ｄ）を１０〜５０質量％、共重合体（Ｅ）を５０〜９０質量％含む、［１２］又は［１３］に記載の熱可塑性樹脂組成物。 [14] In a total of 100% by mass of the graft copolymer (D) and the copolymer (E), 10 to 50% by mass of the graft copolymer (D) and 50 to 90% by mass of the copolymer (E). %, The thermoplastic resin composition according to [12] or [13].
［１５］ ［１１］ないし［１４］のいずれかに記載の熱可塑性樹脂組成物を成形してなる成形品。 [15] A molded product obtained by molding the thermoplastic resin composition according to any one of [11] to [14].
本発明によれば、成形外観と耐衝撃性に優れ、流動性にも優れる熱可塑性樹脂組成物およびその成形品が提供される。 According to the present invention, there is provided a thermoplastic resin composition having excellent molded appearance, impact resistance, and excellent fluidity, and a molded product thereof.
以下に本発明の実施の形態を詳細に説明する。
なお、本発明において、「（メタ）アクリル酸」とは、「アクリル酸」と「メタクリル酸」の一方又は双方を意味するものであり、「（メタ）アクリレート」についても同様である。
また、「単位」とは、重合体中に含まれる、重合前の化合物（単量体、即ちモノマー）に由来する構造部分を意味し、例えば、「（メタ）アクリル酸アルキルエステル（ａ）単位」とは「（メタ）アクリル酸アルキルエステル（ａ）に由来してコア−シェル型粒子（Ｃ）のコア部である共重合体（Ａ）中に含まれる構造部分」を意味する。重合体の各単量体単位の含有割合は、当該重合体の製造に用いた単量体混合物中の該単量体の含有割合に該当する。
Embodiments of the present invention will be described in detail below.
In the present invention, "(meth) acrylic acid" means one or both of "acrylic acid" and "methacrylic acid", and the same applies to "(meth) acrylate".
Further, the "unit" means a structural portion derived from a compound (monomer, that is, a monomer) before polymerization contained in the polymer, and for example, "(meth) acrylic acid alkyl ester (a) unit". "" Means "a structural portion derived from the (meth) acrylic acid alkyl ester (a) and contained in the copolymer (A) which is the core portion of the core-shell type particles (C)". The content ratio of each monomer unit of the polymer corresponds to the content ratio of the monomer in the monomer mixture used for producing the polymer.
［コア−シェル型粒子（Ｃ）］
本発明のコア−シェル型粒子（Ｃ）は、（メタ）アクリル酸アルキルエステル（ａ）を含むビニル系単量体混合物（ｍ１）を重合して得られる共重合体（Ａ）よりなるコア部と、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）を含むビニル系単量体混合物（ｍ２）を重合して得られる共重合体（Ｂ）よりなるシェル部とを有するものである。
[Core-shell type particles (C)]
The core-shell type particle (C) of the present invention is a core portion made of a copolymer (A) obtained by polymerizing a vinyl-based monomer mixture (m1) containing a (meth) acrylic acid alkyl ester (a). And a shell portion made of a copolymer (B) obtained by polymerizing a vinyl-based monomer mixture (m2) containing a (meth) acrylic acid ester (b) having an aromatic hydrocarbon group. is there.
＜メカニズム＞
芳香族炭化水素基を有する（メタ）アクリル酸エステルがビニル系単量体混合物（ｍ１）に含まれ、共重合体（Ａ）を（メタ）アクリル酸アルキルエステルと芳香族炭化水素基を有する（メタ）アクリル酸エステルの共重合体とした場合、共重合体（Ａ）の屈折率が大きくなる。すなわち、コア−シェル型粒子（Ｃ）の屈折率が上がり、後述のグラフト共重合体（Ｄ）のグラフト層および共重合体（Ｅ）とコア−シェル型粒子（Ｃ）間の屈折率差が小さくなるため、成形外観は向上する。しかし、共重合体（Ａ）のガラス転移温度が高くなるなどの問題が生じ、低温耐衝撃性が低下してしまう。
<Mechanism>
A (meth) acrylic acid ester having an aromatic hydrocarbon group is contained in the vinyl-based monomer mixture (m1), and the copolymer (A) has a (meth) acrylic acid alkyl ester and an aromatic hydrocarbon group (). When a copolymer of a meta) acrylic acid ester is used, the refractive index of the copolymer (A) increases. That is, the refractive index of the core-shell type particles (C) is increased, and the difference in the refractive index between the graft layer of the graft copolymer (D) described later and the copolymer (E) and the core-shell type particles (C) is increased. Since it is smaller, the molded appearance is improved. However, problems such as an increase in the glass transition temperature of the copolymer (A) occur, and the low temperature impact resistance is lowered.
一方で、共重合体（Ａ）を形成するビニル系単量体混合物（ｍ１）が（メタ）アクリル酸アルキルエステルを主成分とし、シェル部を形成するビニル系単量体混合物（ｍ２）の主成分を芳香族炭化水素基を有する（メタ）アクリル酸エステルとした場合、シェル部の屈折率が高く、コア部の屈折率が低いものとなり、コア−シェル型粒子（Ｃ）内部に屈折率の傾斜ができる。すなわち、グラフト共重合体（Ｄ）のグラフト層および共重合体（Ｅ）が最も屈折率が高く、次いでシェル部の屈折率が高く、コア部の屈折率が最も低い、といったように、グラフト共重合体（Ｄ）のグラフト層および共重合体（Ｅ）とコア−シェル型粒子（Ｃ）間、ならびにグラフト共重合体（Ｄ）のグラフト層および共重合体（Ｅ）とコア部の共重合体（Ａ）間で徐々に屈折率が変化する構造となる。そのため、共重合体（Ｅ）に、このような本発明のコア−シェル型粒子（Ｃ）を用いたグラフト共重合体（Ｄ）をブレンドした際、コア−シェル型粒子（Ｃ）による光散乱を抑制することができ、成形外観を向上させることができる。仮に、コア部が芳香族炭化水素基を有する（メタ）アクリル酸エステル単位を主成分とし、シェル部が（メタ）アクリル酸アルキルエステル単位を主成分とした場合、グラフト共重合体（Ｄ）のグラフト層および共重合体（Ｅ）とコア−シェル型粒子（Ｃ）間、ならびにグラフト共重合体（Ｄ）のグラフト層および共重合体（Ｅ）と共重合体（Ａ）のコア部間で徐々に屈折率が変化する構造とはならず、成形外観に劣るものとなる。 On the other hand, the vinyl-based monomer mixture (m1) forming the copolymer (A) is mainly composed of the (meth) acrylic acid alkyl ester as the main component and the vinyl-based monomer mixture (m2) forming the shell portion. When the component is a (meth) acrylic acid ester having an aromatic hydrocarbon group, the refractive index of the shell portion is high and the refractive index of the core portion is low, and the refractive index inside the core-shell type particles (C) is high. Can be tilted. That is, the graft layer of the graft copolymer (D) and the copolymer (E) have the highest refractive index, then the shell portion has the highest refractive index, the core portion has the lowest refractive index, and so on. The weight of the graft layer and copolymer (E) of the polymer (D) and the core-shell type particles (C), and the weight of the graft layer and copolymer (E) of the graft copolymer (D) and the core portion. The structure is such that the refractive index gradually changes between the coalescing (A). Therefore, when the graft copolymer (D) using the core-shell type particles (C) of the present invention is blended with the copolymer (E), light scattering by the core-shell type particles (C) Can be suppressed, and the molding appearance can be improved. If the core portion contains a (meth) acrylic acid ester unit having an aromatic hydrocarbon group as a main component and the shell portion contains a (meth) acrylic acid alkyl ester unit as a main component, the graft copolymer (D) Between the graft layer and copolymer (E) and the core-shell type particles (C), and between the graft layer and copolymer (E) of the graft copolymer (D) and the core portion of the copolymer (A). The structure does not gradually change the refractive index, and the molded appearance is inferior.
本発明のコア−シェル型粒子（Ｃ）では、コア部である（メタ）アクリル酸アルキルエステル（ａ）単位を主成分とする共重合体（Ａ）はガラス転移温度が低いため、コア部である共重合体（Ａ）は低温耐衝撃性に寄与し、一方で、上記の通り、シェル部である共重合体（Ｂ）が成形外観向上に寄与する。
そのため、（メタ）アクリル酸アルキルエステル（ａ）を含むビニル系単量体混合物（ｍ１）を重合して得られる共重合体（Ａ）がコア部で、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）を含むビニル系単量体混合物（ｍ２）を重合して得られる共重合体（Ｂ）をシェル部とすることで、成形外観と耐衝撃性を両立できる。
In the core-shell type particles (C) of the present invention, the copolymer (A) containing the (meth) acrylic acid alkyl ester (a) unit as the main component, which is the core portion, has a low glass transition temperature, so that the core portion has a low glass transition temperature. A certain copolymer (A) contributes to low temperature impact resistance, while the copolymer (B) which is a shell portion contributes to the improvement of the molded appearance as described above.
Therefore, the copolymer (A) obtained by polymerizing the vinyl-based monomer mixture (m1) containing the (meth) acrylic acid alkyl ester (a) has an aromatic hydrocarbon group in the core portion (meth). By using a copolymer (B) obtained by polymerizing a vinyl-based monomer mixture (m2) containing an acrylic acid ester (b) as a shell portion, both a molded appearance and impact resistance can be achieved.
ゴム粒子がコア−シェル型ではなく、ゴム粒子が（メタ）アクリル酸アルキルエステルと芳香族炭化水素基を有する（メタ）アクリル酸エステルの共重合体である場合、成形外観は向上するが、ゴム粒子のガラス転移温度が低いため、低温耐衝撃性が低下する。 When the rubber particles are not a core-shell type and the rubber particles are a copolymer of a (meth) acrylic acid alkyl ester and a (meth) acrylic acid ester having an aromatic hydrocarbon group, the molded appearance is improved, but the rubber. Since the glass transition temperature of the particles is low, the low temperature impact resistance is lowered.
（メタ）アクリル酸アルキルエステル（ａ）を含むビニル系単量体混合物（ｍ１）を重合して得られる共重合体（Ａ）をコア部とし、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）を含むビニル系単量体混合物（ｍ２）を重合して得られる共重合体（Ｂ）をシェル部とするコア−シェル型粒子（Ｃ）を用いたグラフト共重合体（Ｄ）、もしくはこのグラフト共重合体（Ｄ）を含む熱可塑性樹脂組成物においては、０℃〜−１５０℃の低温領域に、ガラス転移温度が２点観測される。
これに対して、ゴム粒子がコア−シェル型ではなく、ゴム粒子が（メタ）アクリル酸アルキルエステルと、芳香族炭化水素基を有する（メタ）アクリル酸エステルの共重合体である場合、０℃〜−１５０℃の低温領域に、ガラス転移温度は１点のみ観測される。
ここで、ガラス転移温度はＤＳＣや動的粘弾性測定（例えば、周波数１Ｈｚでの温度分散測定）により測定できる。
A (meth) acrylic acid having an aromatic hydrocarbon group, with the copolymer (A) obtained by polymerizing a vinyl-based monomer mixture (m1) containing the (meth) acrylic acid alkyl ester (a) as a core portion. A graft copolymer (D) using a core-shell type particle (C) having a copolymer (B) as a shell portion obtained by polymerizing a vinyl-based monomer mixture (m2) containing an ester (b). Or, in the thermoplastic resin composition containing this graft copolymer (D), two glass transition temperatures are observed in the low temperature region of 0 ° C. to −150 ° C.
On the other hand, when the rubber particles are not a core-shell type and the rubber particles are a copolymer of a (meth) acrylic acid alkyl ester and a (meth) acrylic acid ester having an aromatic hydrocarbon group, the temperature is 0 ° C. Only one glass transition temperature is observed in the low temperature region of ~ -150 ° C.
Here, the glass transition temperature can be measured by DSC or dynamic viscoelasticity measurement (for example, temperature dispersion measurement at a frequency of 1 Hz).
＜共重合体（Ａ）＞
共重合体（Ａ）は、（メタ）アクリル酸アルキルエステル（ａ）を含むビニル系単量体混合物（ｍ１）を重合して得られる。
<Copolymer (A)>
The copolymer (A) is obtained by polymerizing a vinyl-based monomer mixture (m1) containing the (meth) acrylic acid alkyl ester (a).
（メタ）アクリル酸アルキルエステル（ａ）としては、アルキル基の炭素数が１〜１２である（メタ）アクリル酸アルキルエステルが好ましい。中でも、得られる熱可塑性樹脂組成物の耐衝撃性が優れることから、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸エチルが特に好ましい。（メタ）アクリル酸アルキルエステルは、１種でまたは２種以上を組み合わせて使用できる。 As the (meth) acrylic acid alkyl ester (a), a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferable. Of these, n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are particularly preferable because the obtained thermoplastic resin composition has excellent impact resistance. The (meth) acrylic acid alkyl ester can be used alone or in combination of two or more.
共重合体（Ａ）は、（メタ）アクリル酸アルキルエステル（ａ）以外に、架橋剤に由来する単位およびグラフト交叉剤に由来する単位のいずれか一方または両方を有する共重合体であることが好ましく、共重合体（Ａ）がグラフト交叉剤および／又は架橋剤に由来する単位を含むことでは、得られる熱可塑性樹脂組成物の成形外観と耐衝撃性をより一層改善する効果が奏される。 The copolymer (A) may be a copolymer having one or both of a unit derived from a cross-linking agent and a unit derived from a graft cross-linking agent, in addition to the (meth) acrylic acid alkyl ester (a). Preferably, when the copolymer (A) contains a unit derived from a graft cross-linking agent and / or a cross-linking agent, the effect of further improving the molded appearance and impact resistance of the obtained thermoplastic resin composition is exhibited. ..
グラフト交叉剤としては、アリル化合物、具体的には、メタクリル酸アリル、シアヌル酸トリアリル、イソシアヌル酸トリアリル等が挙げられる。これらは１種のみを用いてもよく、２種以上を混合して用いてもよい。 Examples of the graft crossover include allyl compounds, specifically, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like. Only one of these may be used, or two or more thereof may be mixed and used.
架橋剤としては、ジメタクリレート系化合物、具体例には、エチレングリコールジメタクリレート、プロピレングリコールジメタクリレート、１，３−ブチレングリコールジメタクリレート、１，４−ブチレングリコールジメタクリレート等が挙げられる。これらは１種のみを用いてもよく、２種以上を混合して用いてもよい。 Examples of the cross-linking agent include dimethacrylate compounds, and specific examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. Only one of these may be used, or two or more thereof may be mixed and used.
架橋剤および／又はグラフト交叉剤を用いる場合、共重合体（Ａ）中の架橋剤および／又はグラフト交叉剤に由来する単位の割合は、得られる熱可塑性樹脂組成物の成形外観と耐衝撃性が優れることから、（メタ）アクリル酸アルキルエステル（ａ）単位と、架橋剤に由来する単位および／又はグラフト交叉剤に由来する単位との合計１００質量％中、０．０１〜３質量％が好ましく、０．０５〜２質量％がより好ましい。 When a cross-linking agent and / or a graft cross-linking agent is used, the proportion of units derived from the cross-linking agent and / or the graft cross-linking agent in the copolymer (A) determines the molded appearance and impact resistance of the obtained thermoplastic resin composition. 0.01 to 3% by mass out of a total of 100% by mass of the (meth) acrylic acid alkyl ester (a) unit and the unit derived from the cross-linking agent and / or the unit derived from the graft copolymer. Preferably, 0.05 to 2% by mass is more preferable.
なお、共重合体（Ａ）は、本発明の目的を損なわない範囲で、（メタ）アクリル酸アルキルエステル（ａ）単位、必要に応じて用いられる架橋剤および／又はグラフト交叉剤に由来する単位以外のその他の単量体単位を含んでいてもよい。共重合体（Ａ）に含まれていてもよいその他の単量体単位としては、後述のビニル系単量体混合物（ｍ３）に含まれる（メタ）アクリル酸アルキルエステル（ａ）以外のビニル系単量体単位の１種又は２種以上が挙げられるが、本発明の効果を有効に得る上で、これらのその他のビニル系単量体単位の含有量は、共重合体（Ａ）１００質量％中２０質量％以下、特に１０質量％以下であることが好ましく、前述の理由から、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）単位は含まれていないことが好ましい。 The copolymer (A) is a unit of (meth) acrylic acid alkyl ester (a), a unit derived from a cross-linking agent and / or a graft cross-linking agent used as necessary, as long as the object of the present invention is not impaired. Other monomer units other than the above may be contained. Other monomer units that may be contained in the copolymer (A) include vinyl-based products other than the (meth) acrylic acid alkyl ester (a) contained in the vinyl-based monomer mixture (m3) described later. One type or two or more types of monomer units can be mentioned, but in order to effectively obtain the effects of the present invention, the content of these other vinyl-based monomer units is 100 mass by mass of the copolymer (A). It is preferably 20% by mass or less, particularly 10% by mass or less, and for the above-mentioned reason, it is preferable that the (meth) acrylic acid ester (b) unit having an aromatic hydrocarbon group is not contained.
共重合体（Ａ）の製造方法としては特に制限されないが、（メタ）アクリル酸アルキルエステル（ａ）と、架橋剤および／又はグラフト交叉剤とを含む混合物を乳化重合、またはミニエマルション重合させる方法が好ましく、得られる熱可塑性樹脂組成物の物性が優れることからミニエマルション重合させる方法が特に好ましい。 The method for producing the copolymer (A) is not particularly limited, but a method of emulsion polymerization or miniemulsion polymerization of a mixture containing (meth) acrylic acid alkyl ester (a) and a cross-linking agent and / or a graft cross-linking agent. Is preferable, and the method of miniemulsion polymerization is particularly preferable because the physical properties of the obtained thermoplastic resin composition are excellent.
共重合体（Ａ）の乳化重合法による製造方法としては、水系溶媒にラジカル開始剤と、（メタ）アクリル酸アルキルエステル（ａ）と、架橋剤および／又はグラフト交叉剤とを加えて、乳化剤の存在下で共重合させる方法が挙げられる。
ラジカル開始剤と、（メタ）アクリル酸アルキルエステル（ａ）と、架橋剤および／又はグラフト交叉剤の添加方法は、一括、分割、連続のいずれでもよい。
As a method for producing the copolymer (A) by the emulsification polymerization method, a radical initiator, a (meth) acrylic acid alkyl ester (a), a cross-linking agent and / or a graft cross-linking agent are added to an aqueous solvent, and an emulsifier is used. There is a method of copolymerizing in the presence of.
The method of adding the radical initiator, the (meth) acrylic acid alkyl ester (a), the cross-linking agent and / or the graft cross-linking agent may be batch, split or continuous.
共重合体（Ａ）を製造するミニエマルション重合は、これに限定されるものではないが、例えば、（メタ）アクリル酸アルキルエステル（ａ）と、架橋剤および／又はグラフト交叉剤と、疎水性物質と、開始剤とを混合し、得られた混合物に水と、乳化剤とを加え、せん断力を付与してプレエマルション（ミニエマルション）を作製する工程、並びにこの混合物を重合開始温度まで加熱して重合させる工程を含むことができる。 The miniemulsion polymerization for producing the copolymer (A) is, but is not limited to, hydrophobicity with, for example, the (meth) acrylic acid alkyl ester (a), the cross-linking agent and / or the graft crossover. The process of mixing the substance and the initiator, adding water and an emulsifier to the obtained mixture and applying shearing force to prepare a pre-emulsion (miniemulsion), and heating this mixture to the polymerization initiation temperature. It can include a step of polymerizing.
ミニエマルション化の工程では、例えば、超音波照射による剪断工程を実施することにより、前記剪断力によりモノマーが引きちぎられ、乳化剤に覆われたモノマー微小油滴が形成される。その後、開始剤の重合開始温度まで加熱することにより、モノマー微小油滴をそのまま重合し、高分子微粒子が得られる。ミニエマルションを形成させるための剪断力を加える方法は公知の任意の方法を用いることができ、ミニエマルションを形成できる高剪断装置としては、これらに限定されるものではないが、例えば、高圧ポンプおよび相互作用チャンバーからなる乳化装置、超音波エネルギーや高周波によりミニエマルションを形成させる装置等がある。高圧ポンプおよび相互作用チャンバーからなる乳化装置としては、例えば、ＳＰＸ Ｃｏｒｐｏｒａｔｉｏｎ ＡＰＶ社製「圧力式ホモジナイザー」、（株）パウレック製「マイクロフルイダイザー」等が挙げられ、超音波エネルギーや高周波によりミニエマルションを形成させる装置としては、例えば、Ｆｉｓｈｅｒ Ｓｃｉｅｎｔ製「ソニックディスメンブレーター」や（株）日本精機製作所製「ＵＬＴＲＡＳＯＮＩＣ ＨＯＭＯＧＥＮＩＺＥＲ」等が挙げられるがこれらに限定されるものではない。 In the miniemulsion step, for example, by carrying out a shearing step by ultrasonic irradiation, the monomer is torn off by the shearing force, and monomer fine oil droplets covered with an emulsifier are formed. Then, by heating to the polymerization initiation temperature of the initiator, the monomer fine oil droplets are polymerized as they are, and polymer fine particles are obtained. Any known method can be used as the method of applying the shearing force for forming the miniemulsion, and the high shearing device capable of forming the miniemulsion is not limited to these, but for example, a high pressure pump and There is an emulsification device consisting of an interaction chamber, a device for forming a miniemulsion by ultrasonic energy or high frequency, and the like. Examples of the emulsifying device including a high-pressure pump and an interaction chamber include a "pressure homogenizer" manufactured by SPX Corporation APV and a "microfluidizer" manufactured by Paulec Co., Ltd., and a miniemulsion is formed by ultrasonic energy or high frequency. Examples of the device for forming include, but are not limited to, "Sonic Dismulsioner" manufactured by Fisher Scientific and "ULTRASONIC HOMOGENIZER" manufactured by Nippon Seiki Seisakusho Co., Ltd.
なお、ミニエマルション化の際の水溶媒の使用量は、作業性、安定性、製造性等の観点から、重合後の反応系の固形分濃度が５〜５０質量％程度となるように、水以外の混合物１００質量部に対して１００〜５００質量部程度とすることが好ましい。 The amount of water solvent used in the miniemulsion is such that the solid content concentration of the reaction system after polymerization is about 5 to 50% by mass from the viewpoint of workability, stability, manufacturability, and the like. It is preferably about 100 to 500 parts by mass with respect to 100 parts by mass of the mixture other than the above.
ミニエマルション重合で共重合体（Ａ）を製造する場合、疎水性物質を所定の割合で用いることが好ましい。プレエマルションを形成させる際に、疎水性物質を添加するとミニエマルション重合の製造安定性がより向上する傾向にあり、本発明に好適な共重合体（Ａ）を製造することができる。 When the copolymer (A) is produced by miniemulsion polymerization, it is preferable to use a hydrophobic substance in a predetermined ratio. When a hydrophobic substance is added when forming the pre-emulsion, the production stability of the miniemulsion polymerization tends to be further improved, and the copolymer (A) suitable for the present invention can be produced.
疎水性物質としては、例えば炭素数１０以上の炭化水素類、炭素数１０以上のアルコール、質量平均分子量（Ｍｗ）１００００未満の疎水性ポリマー、疎水性モノマー、例えば、炭素数１０〜３０のアルコールのビニルエステル、炭素数１２〜３０のアルコールのビニルエーテル、炭素数１２〜３０の（メタ）アクリル酸アルキル、炭素数１０〜３０（好ましくは炭素数１０〜２２）のカルボン酸ビニルエステル、ｐ−アルキルスチレン、疎水性の連鎖移動剤、疎水性の過酸化物等が挙げられる。これらは、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 Examples of the hydrophobic substance include hydrocarbons having 10 or more carbon atoms, alcohols having 10 or more carbon atoms, hydrophobic polymers having a mass average molecular weight (Mw) of less than 10000, and hydrophobic monomers, for example, alcohols having 10 to 30 carbon atoms. Vinyl ester, vinyl ether of alcohol having 12 to 30 carbon atoms, alkyl (meth) acrylate having 12 to 30 carbon atoms, vinyl acid vinyl ester having 10 to 30 carbon atoms (preferably 10 to 22 carbon atoms), p-alkylstyrene. , Hydrophobic chain transfer agents, hydrophobic peroxides and the like. One of these may be used alone, or two or more thereof may be mixed and used.
疎水性物質としては、より具体的には、ヘキサデカン、オクタデカン、イコサン、流動パラフィン、流動イソパラフィン、パラフィンワックス、ポリエチレンワックス、オリーブ油、セチルアルコール、アクリル酸ステアリル、アクリル酸ラウリル、アクリル酸ステアリル、メタクリル酸ラウリル、メタクリル酸ステアリル、５００〜１００００の数平均分子量（Ｍｎ）を有するポリスチレン、ポリ（メタ）アクリル酸エステル等が挙げられる。 More specifically, the hydrophobic substance includes hexadecane, octadecane, icosan, liquid paraffin, liquid isoparaffin, paraffin wax, polyethylene wax, olive oil, cetyl alcohol, stearyl acrylate, lauryl acrylate, stearyl acrylate, and lauryl methacrylate. , Stearyl methacrylate, polystyrene having a number average molecular weight (Mn) of 500 to 10000, poly (meth) acrylic acid ester and the like.
疎水性物質は、（メタ）アクリル酸アルキルエステル（ａ）と、架橋剤および／又はグラフト交叉剤の合計１００質量部に対し、好ましくは０．１〜１０質量部、より好ましくは１〜３質量部用いることが、共重合体（Ａ）の粒子径制御の点で好ましい。 The hydrophobic substance is preferably 0.1 to 10 parts by mass, more preferably 1 to 3 parts by mass, based on 100 parts by mass of the total of the (meth) acrylic acid alkyl ester (a) and the cross-linking agent and / or the graft cross-linking agent. It is preferable to use the part from the viewpoint of controlling the particle size of the copolymer (A).
共重合体（Ａ）を製造する際に用いる乳化剤としては、オレイン酸、パルミチン酸、ステアリン酸、ロジン酸のアルカリ金属塩、アルケニルコハク酸のアルカリ金属塩等で例示されるカルボン酸系の乳化剤、アルキル硫酸エステル、アルキルベンゼンスルホン酸ナトリウム、アルキルスルホコハク酸ナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸エステルナトリウムなどの中から選ばれるアニオン系乳化剤等、公知の乳化剤を単独または２種以上を組み合わせて使用することができる。 Examples of the emulsifier used in producing the copolymer (A) include carboxylic acid-based emulsifiers such as oleic acid, palmitic acid, stearic acid, alkali metal salts of logonic acid, and alkali metal salts of alkenyl succinic acid. Known emulsifiers such as anionic emulsifiers selected from alkyl sulfate ester, sodium alkylbenzene sulfonate, sodium alkylsulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfate, etc. can be used alone or in combination of two or more. it can.
乳化剤の添加量としては、（メタ）アクリル酸アルキルエステル（ａ）と、架橋剤および／又はグラフト交叉剤の合計１００質量部に対し、０．０１〜３．０質量部が好ましく、さらに好ましくは０．０５〜１．５質量部であることが、共重合体（Ａ）の粒子径制御の点で好ましい。 The amount of the emulsifier added is preferably 0.01 to 3.0 parts by mass, more preferably 0.01 to 3.0 parts by mass, based on 100 parts by mass of the total of the (meth) acrylic acid alkyl ester (a) and the cross-linking agent and / or the graft copolymer. The amount is preferably 0.05 to 1.5 parts by mass from the viewpoint of controlling the particle size of the copolymer (A).
共重合体（Ａ）の製造に用いられる開始剤はラジカル重合するためのラジカル重合開始剤であり、その種類に特に制限はないが、例えば、アゾ重合開始剤、光重合開始剤、無機過酸化物、有機過酸化物、有機過酸化物と遷移金属と還元剤とを組み合わせたレドックス系開始剤等が挙げられる。これらのうち、加熱により重合を開始できるアゾ重合開始剤、無機過酸化物、有機過酸化物、レドックス系開始剤が好ましい。これらは１種のみを用いてもよく、２種以上を組み合わせて用いてもよい。 The initiator used in the production of the copolymer (A) is a radical polymerization initiator for radical polymerization, and the type thereof is not particularly limited. For example, an azo polymerization initiator, a photopolymerization initiator, and an inorganic peroxide are used. Examples thereof include organic peroxides, redox-based initiators in which organic peroxides, transition metals, and reducing agents are combined. Of these, azo polymerization initiators, inorganic peroxides, organic peroxides, and redox-based initiators that can initiate polymerization by heating are preferable. Only one type of these may be used, or two or more types may be used in combination.
アゾ重合開始剤としては、例えば、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、１−［（１−シアノ−１−メチルエチル）アゾ］フォルムアミド、４，４’−アゾビス（４−シアノバレリックアシッド）、ジメチル２，２’−アゾビス（２−メチルプロピオネート）、ジメチル１，１’−アゾビス（１−シクヘキサンカルボキシレート）、２，２’−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］、２，２’−アゾビス（Ｎ−ブチル−２−メチルプロピオンアミド）、２，２’−アゾビス（Ｎ−シクロヘキシル−２−メチルプロピオンアミド）、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］、２，２’−アゾビス（２，４，４−トリメチルペンタン）等が挙げられる。 Examples of the azo polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-. Azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) Azo] formamide, 4,4'-azobis (4-cyanovaleric acid), dimethyl 2,2'-azobis (2-methylpropionate), dimethyl 1,1'-azobis (1-sixhexanecarboxylate) ), 2,2'-Azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis ( N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (2,4,4-trimethylpentane), etc. Can be mentioned.
無機過酸化物としては、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素等が挙げられる。 Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide and the like.
有機過酸化物としては、例えばペルオキシエステル化合物が挙げられ、その具体例としては、α，α’−ビス（ネオデカノイルペルオキシ）ジイソプロピルベンゼン、クミルペルオキシネオデカノエート、１，１，３，３−テトラメチルブチルペルオキシネオデカノエート、１−シクロヘキシル−１−メチルエチルペルオキシネオデカノエート、ｔ−ヘキシルペルオキシネオデカノエート、ｔ−ブチルペルオキシネオデカノエート、ｔ−ヘキシルペルオキシピバレート、ｔ−ブチルペルオキシピバレート、１，１，３，３−テトラメチルブチルペルオキシ−２−エチルヘキサノエート、２，５−ジメチル−２，５−ビス（２−エチルヘキサノイルペルオキシ）ヘキサン、１−シクロヘキシル−１−メチルエチルペルオキシ−２−エチルヘキサノエート、ｔ−ヘキシルペルオキシ２−ヘキシルヘキサノエート、ｔ−ブチルペルオキシ２−ヘキシルヘキサノエート、ｔ−ブチルペルオキシイソブチレート、ｔ−ヘキシルペルオキシイソプロピルモノカーボネート、ｔ−ブチルペルオキシマレイックアシッド、ｔ−ブチルペルオキシ３，５，５−トリメチルヘキサノエート、ｔ−ブチルペルオキシラウレート、２，５−ジメチル−２，５−ビス（ｍ−トルオイルペルオキシ）ヘキサン、ｔ−ブチルペルオキシイソプロピルモノカーボネート、ｔ−ブチルペルオキシ２−エチルヘキシルモノカーボネート、ｔ−ヘキシルペルオキシベンゾエート、２，５−ジメチル−２，５−ビス（ベンゾイルペルオキシ）ヘキサン、ｔ−ブチルペルオキシアセテート、ｔ−ブチルペルオキシ−ｍ−トルオイルベンゾエート、ｔ−ブチルペルオキシベンゾエート、ビス（ｔ−ブチルペルオキシ）イソフタレート、１，１−ビス（ｔ−ヘキシルペルオキシ）３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ヘキシルペルオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルペルオキシ）３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルペルオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルペルオキシ）シクロドデカン、２，２−ビス（ｔ−ブチルペルオキシ）ブタン、ｎ−ブチル４，４−ビス（ｔ−ブチルペルオキシ）バレレート、２，２−ビス（４，４−ジ−ｔ−ブチルペルオキシシクロヘキシル）プロパン、α，α’−ビス（ｔ−ブチルペルオキシド）ジイソプロピルベンゼン、ジクミルペルオキシド、２，５−ジメチル−２，５−ビス（ｔ−ブチルペルオキシ）ヘキサン、ｔ−ブチルクミルペルオキシド、ジ−ｔ−ブチルペルオキシド、クメンヒドロペルオキシド、ジイソプロピルベンゼンヒドロペルオキシド、ジラウロイルペルオキシド、ジイソノナノイルペルオキシド、ｔ−ブチルヒドロペルオキシド、ベンゾイルペルオキシド、ラウロイルペルオキシド、ジメチルビス（ｔ−ブチルペルオキシ）−３−ヘキシン、ビス（ｔ−ブチルペルオキシイソプロピル）ベンゼン、ビス（ｔ−ブチルペルオキシ）トリメチルシクロヘキサン、ブチル−ビス（ｔ−ブチルペルオキシ）バレラート、２−エチルヘキサンペルオキシ酸ｔ−ブチル、ジベンゾイルペルオキシド、パラメンタンハイドロペルオキシドおよびｔ−ブチルペルオキシベンゾエート等が挙げられる。 Examples of the organic peroxide include a peroxy ester compound, and specific examples thereof include α, α'-bis (neodecanoyl peroxy) diisopropylbenzene, cumylperoxy neodecanoate, 1,1,3. 3-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1- Cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy2-hexylhexanoate, t-butylperoxy2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl Monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoleperoxy) ) Hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-Butylperoxy-m-toluoleoxide benzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1 -Bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t) -Butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,5-di-t-) Butylperoxycyclohexyl) propane, α, α'-bis (t-butyl peroxide) diisopropylbenzene, dicumyl peroxide, 2,5 -Dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, dilauroyl peroxide, diisononanoyl peroxide, t -Butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, dimethylbis (t-butylperoxy) -3-hexine, bis (t-butylperoxyisopropyl) benzene, bis (t-butylperoxy) trimethylcyclohexane, butyl-bis (t-) Butylperoxy) valerate, t-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramentan hydroperoxide, t-butylperoxybenzoate and the like.
レドックス系開始剤としては、有機過酸化物と硫酸第一鉄、キレート剤および還元剤を組み合わせたものが好ましい。例えば、クメンヒドロペルオキシド、硫酸第一鉄、ピロリン酸ナトリウム、およびデキストロースからなるものや、ｔ−ブチルヒドロペルオキシド、ナトリウムホルムアルデヒトスルホキシレート（ロンガリット）、硫酸第一鉄、およびエチレンジアミン四酢酸二ナトリウムを組み合わせたもの等が挙げられる。 As the redox-based initiator, a combination of an organic peroxide, ferrous sulfate, a chelating agent and a reducing agent is preferable. For example, cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose, or a combination of t-butyl hydroperoxide, sodium formaldehyde sulfoxylate (longalit), ferrous sulfate, and disodium ethylenediaminetetraacetate. And so on.
開始剤としては、これらのうち、特に有機過酸化物が好ましい。 Of these, organic peroxides are particularly preferable as the initiator.
開始剤の添加量としては、（メタ）アクリル酸アルキルエステル（ａ）と、架橋剤および／又はグラフト交叉剤の合計１００質量部に対して通常５質量部以下、好ましくは３質量部以下、例えば０．００１〜３質量部である。 The amount of the initiator added is usually 5 parts by mass or less, preferably 3 parts by mass or less, for example, with respect to 100 parts by mass of the total of the (meth) acrylic acid alkyl ester (a) and the cross-linking agent and / or the graft cross-linking agent. It is 0.001 to 3 parts by mass.
上記のプレエマルションを調製する工程は通常常温（１０〜５０℃程度）で行われ、ミニエマルション重合の工程は４０〜１００℃で３０〜６００分程度行われる。 The step of preparing the above pre-emulsion is usually carried out at room temperature (about 10 to 50 ° C.), and the step of miniemulsion polymerization is carried out at 40 to 100 ° C. for about 30 to 600 minutes.
水性分散体に分散している共重合体（Ａ）の平均粒子径は、得られる成形品の物性が優れることから、５０〜８００ｎｍが好ましく、１００〜６００ｎｍがより好ましく、２５０〜４５０ｎｍがさらに好ましい。
共重合体（Ａ）の平均粒子径を制御する方法として、特に制限されないが、乳化剤の種類または使用量を調整する方法が挙げられる。
なお、ここで共重合体（Ａ）の平均粒子径及び後述のコア−シェル型粒子（Ｃ）の平均粒子径とは、後述の実施例の項に記載される方法で測定される体積平均粒子径である。
The average particle size of the copolymer (A) dispersed in the aqueous dispersion is preferably 50 to 800 nm, more preferably 100 to 600 nm, and even more preferably 250 to 450 nm because the obtained molded product has excellent physical properties. ..
The method for controlling the average particle size of the copolymer (A) is not particularly limited, and examples thereof include a method for adjusting the type or amount of the emulsifier used.
Here, the average particle size of the copolymer (A) and the average particle size of the core-shell type particles (C) described later are the volume average particles measured by the method described in the section of Examples described later. The diameter.
また、共重合体（Ａ）の膨潤度は、得られる熱可塑性樹脂組成物の耐衝撃性、成形外観が優れることから、２〜１５倍が好ましく、４〜１２倍であることがさらに好ましい。
なお、共重合体（Ａ）の膨潤度は、後述の実施例の項に記載される方法で測定される。
The degree of swelling of the copolymer (A) is preferably 2 to 15 times, more preferably 4 to 12 times, because the obtained thermoplastic resin composition is excellent in impact resistance and molded appearance.
The degree of swelling of the copolymer (A) is measured by the method described in the section of Examples described later.
＜共重合体（Ｂ）＞
共重合体（Ｂ）は芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）を含むビニル系単量体混合物（ｍ２）を重合して得られる共重合体である。共重合体（Ｂ）は、（メタ）アクリル酸アルキルエステル（ａ）を含むビニル系単量体混合物（ｍ１）を重合して得られる共重合体（Ａ）よりなるコア部を被包する外殻としてのシェル部を構成するものである。従って、例えば共重合体（Ａ）の存在下にビニル系単量体混合物（ｍ２）を重合することで、コア部が共重合体（Ａ）で、シェル部が共重合体（Ｂ）であるコア−シェル型粒子（Ｃ）を得ることができる。
<Copolymer (B)>
The copolymer (B) is a copolymer obtained by polymerizing a vinyl-based monomer mixture (m2) containing a (meth) acrylic acid ester (b) having an aromatic hydrocarbon group. The copolymer (B) covers the core portion made of the copolymer (A) obtained by polymerizing a vinyl-based monomer mixture (m1) containing the (meth) acrylic acid alkyl ester (a). It constitutes a shell portion as a shell. Therefore, for example, by polymerizing the vinyl-based monomer mixture (m2) in the presence of the copolymer (A), the core portion is the copolymer (A) and the shell portion is the copolymer (B). Core-shell type particles (C) can be obtained.
ビニル系単量体混合物（ｍ２）に含まれる、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）としては、芳香族炭化水素基を有する（メタ）アクリル酸エステルであればよく、例えば（メタ）アクリル酸アリールエステルや（メタ）アクリル酸アリーロキシエステル、アルキルエステル部分の置換基としてフェニル基等のアリール基やフェノキシ基等のアリーロキシ基、或いはベンジル基等のアリールアルキル基を有する（メタ）アクリル酸アルキルエステルが挙げられるが、何らこれらに限定されるものではない。芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）としては、得られる熱可塑性樹脂組成物の耐衝撃性が優れることから、アクリル酸２−フェノキシエチルが特に好ましい。芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）は、１種を単独でまたは２種以上を組み合わせて使用することができる。 The (meth) acrylic acid ester having an aromatic hydrocarbon group (b) contained in the vinyl-based monomer mixture (m2) may be any (meth) acrylic acid ester having an aromatic hydrocarbon group. For example, it has an aryl group such as a (meth) acrylic acid aryl ester, a (meth) acrylic acid aryloxy ester, an aryl group such as a phenyl group or an aryloxy group such as a phenoxy group as a substituent of an alkyl ester moiety, or an arylalkyl group such as a benzyl group ( Meta) Arylic acid alkyl esters include, but are not limited to. As the (meth) acrylic acid ester (b) having an aromatic hydrocarbon group, 2-phenoxyethyl acrylate is particularly preferable because the obtained thermoplastic resin composition has excellent impact resistance. The (meth) acrylic acid ester (b) having an aromatic hydrocarbon group can be used alone or in combination of two or more.
共重合体（Ｂ）は、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）以外に、架橋剤に由来する単位およびグラフト交叉剤に由来する単位のいずれか一方または両方を有する共重合体であることが好ましく、共重合体（Ｂ）がグラフト交叉剤および／又は架橋剤に由来する単位を含むことでは、得られる熱可塑性樹脂組成物の成形外観と耐衝撃性をより一層改善する効果が奏される。 The copolymer (B) has one or both of a unit derived from a cross-linking agent and a unit derived from a graft cross-linking agent, in addition to the (meth) acrylic acid ester (b) having an aromatic hydrocarbon group. It is preferably a polymer, and when the copolymer (B) contains a unit derived from a graft cross-linking agent and / or a cross-linking agent, the molded appearance and impact resistance of the obtained thermoplastic resin composition are further improved. The effect of
グラフト交叉剤、架橋剤としては、共重合体（Ａ）に用いるグラフト交叉剤、架橋剤として例示したものを用いることができる。 As the graft cross-linking agent and the cross-linking agent, those exemplified as the graft cross-linking agent and the cross-linking agent used for the copolymer (A) can be used.
架橋剤および／又はグラフト交叉剤を用いる場合、共重合体（Ｂ）中の架橋剤および／又はグラフト交叉剤に由来する単位の割合は、得られる熱可塑性樹脂組成物の成形外観と耐衝撃性が優れることから、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）単位と、架橋剤に由来する単位および／又はグラフト交叉剤に由来する単位との合計１００質量％中、０．０１〜３質量％が好ましく、０．０５〜２質量％がより好ましい。 When a cross-linking agent and / or a graft cross-linking agent is used, the proportion of units derived from the cross-linking agent and / or the graft cross-linking agent in the copolymer (B) determines the molded appearance and impact resistance of the obtained thermoplastic resin composition. In 100% by mass of the total of the (meth) acrylic acid ester (b) unit having an aromatic hydrocarbon group and the unit derived from the cross-linking agent and / or the unit derived from the graft cross-linking agent, 0. It is preferably 0 to 1% by mass, more preferably 0.05 to 2% by mass.
なお、共重合体（Ｂ）は、本発明の目的を損なわない範囲で、芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）単位、必要に応じて用いられる架橋剤および／又はグラフト交叉剤に由来する単位以外のその他の単量体単位を含んでいてもよい。共重合体（Ｂ）に含まれていてもよいその他の単量体単位としては、後述のビニル系単量体混合物（ｍ３）に含まれる芳香族炭化水素基を有する（メタ）アクリル酸エステル（ｂ）以外のビニル系単量体単位の１種又は２種以上が挙げられるが、本発明の効果を有効に得る上で、これらのその他のビニル系単量体単位の含有量は、共重合体（Ｂ）１００質量％中２０質量％以下、特に１０質量％以下であることが好ましく、前述の理由から、（メタ）アクリル酸アルキルエステル（ａ）単位は含まれていないことが好ましい。 The copolymer (B) is a (meth) acrylic acid ester (b) unit having an aromatic hydrocarbon group, a cross-linking agent and / or a graft used as necessary, as long as the object of the present invention is not impaired. It may contain other monomeric units other than the units derived from the crosslinker. As another monomer unit that may be contained in the copolymer (B), a (meth) acrylic acid ester having an aromatic hydrocarbon group contained in the vinyl-based monomer mixture (m3) described later (meth). One or more vinyl-based monomer units other than b) can be mentioned, but in order to effectively obtain the effects of the present invention, the content of these other vinyl-based monomer units is copolymerized. It is preferably 20% by mass or less, particularly 10% by mass or less in 100% by mass of the coalesced (B), and for the above-mentioned reason, it is preferable that the (meth) acrylic acid alkyl ester (a) unit is not contained.
＜コア−シェル型粒子（Ｃ）＞
コア−シェル型粒子（Ｃ）の製造方法としては特に制限されないが、共重合体（Ａ）を乳化重合もしくはミニエマルション重合で製造した場合、ビニル系単量体混合物（ｍ２）を用いて乳化重合で製造することが好ましい。
<Core-shell type particles (C)>
The method for producing the core-shell type particles (C) is not particularly limited, but when the copolymer (A) is produced by emulsion polymerization or miniemulsion polymerization, emulsion polymerization is carried out using a vinyl-based monomer mixture (m2). It is preferable to manufacture in.
乳化重合の方法としては、共重合体（Ａ）のエマルションの存在下に、ビニル系単量体混合物（ｍ２）を一括で、または連続的、または断続的に添加してラジカル重合する方法が挙げられる。また、共重合体（Ｂ）の重合の際には、共重合体（Ｂ）の分子量調節やグラフト率を制御する目的で連鎖移動剤を使用したり、ラテックスの粘度やｐＨを調節する目的で公知の無機電解質等を使用したりしてもよい。また、乳化重合においては、各種の乳化剤やラジカル開始剤を必要に応じて使用することができる。 Examples of the method of emulsion polymerization include a method of radical polymerization in which a vinyl-based monomer mixture (m2) is added all at once, continuously or intermittently in the presence of an emulsion of the copolymer (A). Be done. Further, in the polymerization of the copolymer (B), a chain transfer agent is used for the purpose of adjusting the molecular weight and the graft ratio of the copolymer (B), and for the purpose of adjusting the viscosity and pH of the latex. A known inorganic electrolyte or the like may be used. Further, in emulsion polymerization, various emulsifiers and radical initiators can be used as needed.
乳化剤、ラジカル開始剤の種類や添加量については特に制限されない。また、乳化剤、ラジカル開始剤としては、共重合体（Ａ）の説明において先に例示した乳化剤、ラジカル開始剤が挙げられる。 The type and amount of emulsifier and radical initiator added are not particularly limited. Further, examples of the emulsifier and the radical initiator include the emulsifier and the radical initiator exemplified above in the description of the copolymer (A).
得られる熱可塑性樹脂組成物の耐衝撃性や成形外観が優れることから、コア−シェル型粒子（Ｃ）１００質量％中の共重合体（Ｂ）の割合は３〜６５質量％が好ましく、５〜５０質量％がより好ましく、１０〜３０質量％がさらに好ましい。
また、得られる熱可塑性樹脂組成物の耐衝撃性や成形外観が優れることから、コア−シェル型粒子（Ｃ）１００質量％中の共重合体（Ａ）は３５〜９７質量％が好ましく、５０〜９５質量％がより好ましく、７０〜９０質量％がさらに好ましい。
The proportion of the copolymer (B) in 100% by mass of the core-shell type particles (C) is preferably 3 to 65% by mass because the obtained thermoplastic resin composition is excellent in impact resistance and molded appearance. ~ 50% by mass is more preferable, and 10 to 30% by mass is further preferable.
Further, since the obtained thermoplastic resin composition is excellent in impact resistance and molded appearance, the copolymer (A) in 100% by mass of the core-shell type particles (C) is preferably 35 to 97% by mass, preferably 50. It is more preferably ~ 95% by mass, further preferably 70 to 90% by mass.
水性分散体に分散しているコア−シェル型粒子（Ｃ）の平均粒子径は、得られる成形品の物性が優れることから、６０〜８２０ｎｍが好ましく、１１０〜６２０ｎｍがより好ましく、２６０〜４７０ｎｍがさらに好ましい。
コア−シェル型粒子（Ｃ）の平均粒子径を制御する方法として、特に制限されないが、主として共重合体（Ａ）製造時の乳化剤の種類または使用量を調整する方法が挙げられる。
The average particle size of the core-shell type particles (C) dispersed in the aqueous dispersion is preferably 60 to 820 nm, more preferably 110 to 620 nm, and preferably 260 to 470 nm because the obtained molded product has excellent physical properties. More preferred.
The method for controlling the average particle size of the core-shell type particles (C) is not particularly limited, and mainly includes a method for adjusting the type or amount of the emulsifier used during the production of the copolymer (A).
コア−シェル型粒子（Ｃ）の膨潤度は、得られる熱可塑性樹脂組成物の耐衝撃性、成形外観が優れることから、２〜１５倍が好ましく、４〜１２倍であることがさらに好ましい。
なお、コア−シェル型粒子（Ｃ）の膨潤度は、後述の実施例の項に記載される方法で測定される。
The degree of swelling of the core-shell type particles (C) is preferably 2 to 15 times, more preferably 4 to 12 times, because the obtained thermoplastic resin composition is excellent in impact resistance and molded appearance.
The degree of swelling of the core-shell type particles (C) is measured by the method described in the section of Examples described later.
［グラフト共重合体（Ｄ）］
グラフト共重合体（Ｄ）は、コア−シェル型粒子（Ｃ）の存在下に、ビニル系単量体混合物（ｍ３）をグラフト重合して得られる。
[Graft copolymer (D)]
The graft copolymer (D) is obtained by graft-polymerizing a vinyl-based monomer mixture (m3) in the presence of core-shell type particles (C).
ビニル系単量体混合物（ｍ３）は、得られるグラフト共重合体（Ｄ）を配合してなる熱可塑性樹脂組成物の物性が優れることから、芳香族ビニル系単量体とシアン化ビニル系単量体を含むことが好ましい。 Since the vinyl-based monomer mixture (m3) has excellent physical properties of the thermoplastic resin composition obtained by blending the obtained graft copolymer (D), the aromatic vinyl-based monomer and the vinyl cyanide-based simple substance are used. It is preferable to include a monomer.
ビニル系単量体混合物（ｍ３）に含まれる芳香族ビニル系単量体としては、例えば、スチレン、α−メチルスチレン、ｏ−，ｍ−もしくはｐ−メチルスチレン、ビニルキシレン、ｐ−ｔ−ブチルスチレン、エチルスチレンなどが挙げられ、これらは１種を単独でまたは２種以上を組み合わせて使用することができる。芳香族ビニル系単量体の構造に特に制限は無いが、後述のビニル系単量体混合物（ｍ４）に含まれる芳香族ビニル系単量体と同じ構造であることが、熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観の点で好ましい。 Examples of the aromatic vinyl-based monomer contained in the vinyl-based monomer mixture (m3) include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, and pt-butyl. Examples thereof include styrene and ethylstyrene, and these can be used alone or in combination of two or more. The structure of the aromatic vinyl-based monomer is not particularly limited, but the thermoplastic resin composition must have the same structure as the aromatic vinyl-based monomer contained in the vinyl-based monomer mixture (m4) described later. It is preferable in terms of impact resistance and molded appearance of the molded product.
ビニル系単量体混合物（ｍ３）に含まれる芳香族ビニル系単量体の含有率は４０〜９０質量％であることが、得られるグラフト共重合体（Ｄ）を配合してなる熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観の点で好ましく、６０〜８０質量％であることがより好ましい。 The content of the aromatic vinyl-based monomer contained in the vinyl-based monomer mixture (m3) is 40 to 90% by mass, which is a thermoplastic resin obtained by blending the obtained graft copolymer (D). It is preferable in terms of impact resistance and molded appearance of the composition and its molded product, and more preferably 60 to 80% by mass.
ビニル系単量体混合物（ｍ３）に含まれるシアン化ビニル系単量体としては、例えば、アクリロニトリル、メタクリロニトリルなどが挙げられ、これらのうちの１種以上を使用できる。シアン化ビニル系単量体の構造に特に制限は無いが、後述のビニル系単量体混合物（ｍ４）に含まれるシアン化ビニル系単量体と同じ構造であることが、得られる熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観の点で好ましい。 Examples of the vinyl cyanide-based monomer contained in the vinyl-based monomer mixture (m3) include acrylonitrile and methacrylonitrile, and one or more of these can be used. The structure of the vinyl cyanide-based monomer is not particularly limited, but the thermoplastic resin obtained can have the same structure as the vinyl cyanide-based monomer contained in the vinyl-based monomer mixture (m4) described later. It is preferable in terms of impact resistance and molded appearance of the composition and its molded product.
ビニル系単量体混合物（ｍ３）に含まれるシアン化ビニル系単量体の含有率は１０〜６０質量％であることが、得られるグラフト共重合体（Ｄ）を配合してなる熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観の点で好ましく、２０〜４０質量％であることがより好ましい。 The content of the vinyl cyanide-based monomer contained in the vinyl-based monomer mixture (m3) is 10 to 60% by mass, which is a thermoplastic resin prepared by blending the obtained graft copolymer (D). It is preferable in terms of impact resistance and molded appearance of the composition and its molded product, and more preferably 20 to 40% by mass.
ビニル系単量体混合物（ｍ３）は、上記の芳香族ビニル系単量体およびシアン化ビニル系単量体と、これらと共重合可能な他のビニル系単量体を含んでいてもよい。
ビニル系単量体混合物（ｍ３）中の共重合可能な他のビニル系単量体の含有量としては２０質量％以下、特に１０質量％以下が好ましい。
他のビニル系単量体としては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｉ−プロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸アミル、メタクリル酸イソアミル、メタクリル酸オクチル、メタクリル酸−２−エチルヘキシル、メタクリル酸デシル、メタクリル酸ラウリル、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、メタクリル酸フェニル等のメタクリル酸エステルや、Ｎ−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−ｎ−プロピルマレイミド、Ｎ−ｉ−プロピルマレイミド、Ｎ−ｎ−ブチルマレイミド、Ｎ−ｉ−ブチルマレイミド、Ｎ−ｔｅｒｔ−ブチルマレイミド、Ｎ−シクロヘキシルマレイミド等のＮ−シクロアルキルマレイミド、Ｎ−フェニルマレイミド、Ｎ−アルキル置換フェニルマレイミド、Ｎ−クロロフェニルマレイミド等のＮ−アリールマレイミド、Ｎ−アラルキルマレイミド等のマレイミド系化合物や、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エステル等が挙げられる。これらは１種のみを用いてもよく、２種以上を混合して用いてもよい。
The vinyl-based monomer mixture (m3) may contain the above-mentioned aromatic vinyl-based monomer and vinyl cyanide-based monomer, and other vinyl-based monomers copolymerizable with these.
The content of the other copolymerizable vinyl-based monomer in the vinyl-based monomer mixture (m3) is preferably 20% by mass or less, particularly preferably 10% by mass or less.
Examples of other vinyl-based monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, and t-butyl methacrylate. Methacrylic acid esters such as amyl methacrylate, isoamyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, N-methylmaleimide, N-Cycloalkyl such as N-ethylmaleimide, Nn-propylmaleimide, N-i-propylmaleimide, Nn-butylmaleimide, N-i-butylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, etc. N-arylmaleimide such as maleimide, N-phenylmaleimide, N-alkyl substituted phenylmaleimide, N-chlorophenylmaleimide, maleimide compound such as N-aralkylmaleimide, methylacrylic acid, ethylacrylic acid, propylacrylic acid, acrylic acid. Examples thereof include acrylic acid esters such as butyl. Only one of these may be used, or two or more thereof may be mixed and used.
グラフト共重合体（Ｄ）は、コア−シェル型粒子（Ｃ）にビニル系単量体混合物（ｍ３）がグラフト重合している。
得られるグラフト共重合体（Ｄ）を配合してなる熱可塑性樹脂組成物の耐衝撃性や成形外観が優れ、特に成形外観の射出速度依存性を小さくできることから、グラフト共重合体（Ｄ）の製造に用いるコア−シェル型粒子（Ｃ）及びビニル系単量体混合物（ｍ３）は、グラフト共重合体（Ｄ）１００質量％中、コア−シェル型粒子（Ｃ）が５０〜８０質量％、ビニル系単量体混合物（ｍ３）が２０〜５０質量％であることが好ましい。
In the graft copolymer (D), a vinyl-based monomer mixture (m3) is graft-polymerized on the core-shell type particles (C).
The thermoplastic resin composition obtained by blending the obtained graft copolymer (D) is excellent in impact resistance and molded appearance, and in particular, the injection rate dependence of the molded appearance can be reduced. Therefore, the graft copolymer (D) can be used. The core-shell type particles (C) and the vinyl-based monomer mixture (m3) used in the production contained 50 to 80% by mass of the core-shell type particles (C) in 100% by mass of the graft copolymer (D). The vinyl-based monomer mixture (m3) is preferably 20 to 50% by mass.
また、グラフト共重合体（Ｄ）は、得られるグラフト共重合体（Ｄ）を配合してなる熱可塑性樹脂組成物の耐衝撃性、成形外観が優れることから、グラフト率が２５〜１００％であることが好ましい。グラフト共重合体（Ｄ）のグラフト率は、後述の実施例の項に記載の方法で測定される。 Further, since the graft copolymer (D) is excellent in impact resistance and molded appearance of the thermoplastic resin composition containing the obtained graft copolymer (D), the graft ratio is 25 to 100%. It is preferable to have. The graft ratio of the graft copolymer (D) is measured by the method described in the section of Examples described later.
グラフト共重合体（Ｄ）は、塊状重合法、溶液重合法、塊状懸濁重合法、懸濁重合法、乳化重合法、ミニエマルション重合法等の公知の方法により製造されるが、得られるグラフト共重合体（Ｄ）を配合してなる熱可塑性樹脂組成物の耐衝撃性が良好なことから乳化重合法が好ましい。 The graft copolymer (D) is produced by a known method such as a massive polymerization method, a solution polymerization method, a massive suspension polymerization method, a suspension polymerization method, an emulsion polymerization method, or a miniemulsion polymerization method, and the obtained graft is obtained. The emulsion polymerization method is preferable because the thermoplastic resin composition containing the copolymer (D) has good impact resistance.
乳化グラフト重合の方法としては、コア−シェル型粒子（Ｃ）のエマルションの存在下に、ビニル系単量体混合物（ｍ３）を一括で、または連続的、または断続的に添加してラジカル重合する方法が挙げられる。また、グラフト重合の際には、グラフト共重合体（Ｄ）の分子量の調節やグラフト率を制御する目的で連鎖移動剤を使用したり、ラテックスの粘度やｐＨを調節する目的で公知の無機電解質等を使用したりしてもよい。また、乳化グラフト重合においては、各種の乳化剤やラジカル開始剤を必要に応じて使用することができる。
乳化剤、ラジカル開始剤の種類や添加量については特に制限されない。また、乳化剤、ラジカル開始剤としては、共重合体（Ａ）の説明において先に例示した乳化剤、ラジカル開始剤が挙げられる。
As a method of emulsification graft polymerization, a vinyl-based monomer mixture (m3) is added in a batch, continuously or intermittently in the presence of an emulsion of core-shell type particles (C) to carry out radical polymerization. The method can be mentioned. Further, in the case of graft polymerization, a chain transfer agent is used for the purpose of adjusting the molecular weight of the graft copolymer (D) and the graft ratio, and an inorganic electrolyte known for the purpose of adjusting the viscosity and pH of latex. Etc. may be used. Further, in the emulsified graft polymerization, various emulsifiers and radical initiators can be used as needed.
The type and amount of emulsifier and radical initiator added are not particularly limited. Further, examples of the emulsifier and the radical initiator include the emulsifier and the radical initiator exemplified above in the description of the copolymer (A).
グラフト共重合体（Ｄ）の水性分散体から、グラフト共重合体（Ｄ）を回収する方法としては、（i）凝固剤を溶解させた熱水中にグラフト共重合体（Ｄ）の水性分散体を投入して、スラリー状態に凝析することによって回収する方法（湿式法）、（ii）加熱雰囲気中にグラフト共重合体（Ｄ）の水性分散体を噴霧することにより、半直接的にグラフト共重合体（Ｄ）を回収する方法（スプレードライ法）等が挙げられる。 As a method for recovering the graft copolymer (D) from the aqueous dispersion of the graft copolymer (D), (i) the aqueous dispersion of the graft copolymer (D) in hot water in which a coagulant is dissolved. A method of collecting the body by charging it into a slurry state (wet method), (ii) semi-directly by spraying an aqueous dispersion of the graft copolymer (D) in a heated atmosphere. Examples thereof include a method of recovering the graft copolymer (D) (spray dry method).
凝固剤としては、硫酸、塩酸、リン酸、硝酸等の無機酸、塩化カルシウム、酢酸カルシウム、硫酸アルミニウム等の金属塩等が挙げられる。凝固剤は、重合で用いた乳化剤に対応させて選定される。すなわち、脂肪酸石鹸、ロジン酸石鹸等のカルボン酸石鹸のみを用いた場合、どのような凝固剤を用いてもよい。ドデシルベンゼンスルホン酸ナトリウム等の酸性領域でも安定な乳化力を示す乳化剤が含まれている場合、金属塩を用いる必要がある。 Examples of the coagulant include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and metal salts such as calcium chloride, calcium acetate and aluminum sulfate. The coagulant is selected according to the emulsifier used in the polymerization. That is, when only carboxylic acid soap such as fatty acid soap and rosin acid soap is used, any coagulant may be used. When an emulsifier that exhibits stable emulsifying power even in an acidic region such as sodium dodecylbenzenesulfonate is contained, it is necessary to use a metal salt.
スラリー状態のグラフト共重合体（Ｄ）から乾燥状態のグラフト共重合体（Ｄ）を得る方法としては、（i）洗浄によって、スラリーに残存する乳化剤残渣を水中に溶出させた後に、該スラリーを遠心脱水機またはプレス脱水機で脱水し、さらに気流乾燥機等で乾燥する方法、（ii）圧搾脱水機、押出機等で脱水と乾燥とを同時に実施する方法等が挙げられる。乾燥後により、グラフト共重合体（Ｄ）は、粉体または粒子状で得られる。また、圧搾脱水機または押出機から排出されたグラフト共重合体（Ｄ）を直接、熱可塑性樹脂組成物を製造する押出機または成形機に送ることもできる。 As a method for obtaining the graft copolymer (D) in a dry state from the graft copolymer (D) in a slurry state, (i) washing is performed to elute the emulsifier residue remaining in the slurry into water, and then the slurry is used. Examples thereof include a method of dehydrating with a centrifugal dehydrator or a press dehydrator and further drying with an air flow dryer or the like, (ii) a method of simultaneously performing dehydration and drying with a pressing dehydrator, an extruder or the like. After drying, the graft copolymer (D) is obtained in powder or particulate form. Further, the graft copolymer (D) discharged from the squeezing dehydrator or extruder can be directly sent to the extruder or molding machine for producing the thermoplastic resin composition.
［共重合体（Ｅ）］
共重合体（Ｅ）は、ビニル系単量体混合物（ｍ４）を重合して得られる。
[Copolymer (E)]
The copolymer (E) is obtained by polymerizing a vinyl-based monomer mixture (m4).
ビニル系単量体混合物（ｍ４）は、共重合体（Ｅ）を配合して得られる熱可塑性樹脂組成物の物性が優れることから、前述のビニル系単量体混合物（ｍ３）と同様の組成であることが好ましく、芳香族ビニル系単量体とシアン化ビニル系単量体を含むことが好ましい。 Since the vinyl-based monomer mixture (m4) has excellent physical properties of the thermoplastic resin composition obtained by blending the copolymer (E), it has the same composition as the vinyl-based monomer mixture (m3) described above. It is preferable that the aromatic vinyl-based monomer and the vinyl cyanide-based monomer are contained.
ビニル系単量体混合物（ｍ４）に含まれる芳香族ビニル系単量体としては、例えば、スチレン、α−メチルスチレン、ｏ−，ｍ−もしくはｐ−メチルスチレン、ビニルキシレン、ｐ−ｔ−ブチルスチレン、エチルスチレンなどが挙げられ、これらは１種を単独でまたは２種以上を組み合わせて使用することができる。芳香族ビニル系単量体の構造に特に制限は無いが、前述のビニル系単量体混合物（ｍ３）に含まれる芳香族ビニル系単量体と同じ構造であることが、得られる熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観の点で好ましい。 Examples of the aromatic vinyl-based monomer contained in the vinyl-based monomer mixture (m4) include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, and pt-butyl. Examples thereof include styrene and ethylstyrene, and these can be used alone or in combination of two or more. The structure of the aromatic vinyl-based monomer is not particularly limited, but the obtained thermoplastic resin has the same structure as the aromatic vinyl-based monomer contained in the above-mentioned vinyl-based monomer mixture (m3). It is preferable in terms of impact resistance and molded appearance of the composition and its molded product.
ビニル系単量体混合物（ｍ４）に含まれる芳香族ビニル系単量体の含有率は４０〜９０質量％であることが、得られる熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観の点で好ましく、６０〜８０質量％であることがより好ましい。 The content of the aromatic vinyl-based monomer contained in the vinyl-based monomer mixture (m4) is 40 to 90% by mass, so that the obtained thermoplastic resin composition and its molded product have impact resistance and molding. It is preferable in terms of appearance, and more preferably 60 to 80% by mass.
ビニル系単量体混合物（ｍ４）に含まれるシアン化ビニル系単量体としては、例えば、アクリロニトリル、メタクリロニトリルなどが挙げられ、これらのうちの１種以上を使用できる。シアン化ビニル系単量体の構造に特に制限は無いが、前述のビニル系単量体混合物（ｍ３）に含まれるシアン化ビニル系単量体と同じ構造であることが、得られる熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観の点で好ましい。 Examples of the vinyl cyanide-based monomer contained in the vinyl-based monomer mixture (m4) include acrylonitrile and methacrylonitrile, and one or more of these can be used. The structure of the vinyl cyanide-based monomer is not particularly limited, but the thermoplastic resin obtained can have the same structure as the vinyl cyanide-based monomer contained in the vinyl-based monomer mixture (m3) described above. It is preferable in terms of impact resistance and molded appearance of the composition and its molded product.
ビニル系単量体混合物（ｍ４）に含まれるシアン化ビニル系単量体の含有率は１０〜６０質量％であることが、得られる熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観の点で好ましく、２０〜４０質量％であることがより好ましい。 The content of the vinyl cyanide-based monomer contained in the vinyl-based monomer mixture (m4) is 10 to 60% by mass, so that the obtained thermoplastic resin composition and its molded product have impact resistance and molding. It is preferable in terms of appearance, and more preferably 20 to 40% by mass.
ビニル系単量体混合物（ｍ４）は、上記の芳香族ビニル系単量体およびシアン化ビニル系単量体と、これらと共重合可能な他のビニル系単量体を含んでいてもよい。
ビニル系単量体混合物（ｍ４）中の共重合可能な他のビニル系単量体の含有量としては２０質量％以下、特に１０質量％以下が好ましい。
他のビニル系単量体としては、ビニル系単量体混合物（ｍ３）が含んでいてもよい他のビニル系単量体として例示したものが挙げられ、これらの他のビニル系単量体は、１種を単独でまたは２種以上を組み合わせて使用することができる。
The vinyl-based monomer mixture (m4) may contain the above-mentioned aromatic vinyl-based monomer and vinyl cyanide-based monomer, and other vinyl-based monomers copolymerizable with these.
The content of the other copolymerizable vinyl-based monomer in the vinyl-based monomer mixture (m4) is preferably 20% by mass or less, particularly preferably 10% by mass or less.
Examples of other vinyl-based monomers include those exemplified as other vinyl-based monomers that may be contained in the vinyl-based monomer mixture (m3), and these other vinyl-based monomers are One type can be used alone or two or more types can be used in combination.
共重合体（Ｅ）の質量平均分子量に特に制限は無いが、１０，０００から３００，０００の範囲であることが好ましく、特に５０，０００から２００，０００の範囲であることが好ましい。共重合体（Ｅ）の質量平均分子量が上記範囲内であれば、得られる熱可塑性樹脂組成物の流動性、耐衝撃性が優れるものとなる。
なお、共重合体（Ｅ）の質量平均分子量は、後述の実施例の項に記載の方法で測定される。
The mass average molecular weight of the copolymer (E) is not particularly limited, but is preferably in the range of 10,000 to 300,000, particularly preferably in the range of 50,000 to 200,000. When the mass average molecular weight of the copolymer (E) is within the above range, the obtained thermoplastic resin composition has excellent fluidity and impact resistance.
The mass average molecular weight of the copolymer (E) is measured by the method described in the section of Examples described later.
共重合体（Ｅ）の製造方法としては特に制限されず、乳化重合、懸濁重合、塊状重合、溶液重合などの公知の方法が挙げられる。得られる熱可塑性樹脂組成物の耐熱性の点からは、懸濁重合、塊状重合が好ましい The method for producing the copolymer (E) is not particularly limited, and examples thereof include known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Suspension polymerization and bulk polymerization are preferable from the viewpoint of heat resistance of the obtained thermoplastic resin composition.
共重合体（Ｅ）の製造時に用いる重合開始剤に特に制限はないが、例えば有機過酸化物類が挙げられる。 The polymerization initiator used in the production of the copolymer (E) is not particularly limited, and examples thereof include organic peroxides.
共重合体（Ｅ）の製造時に、共重合体（Ｅ）の分子量を調整するため、連鎖移動剤を用いることができる。連鎖移動剤に特に制限はないが、メルカプタン類、α−メチルスチレンダイマー、テルペン類等が挙げられる。 A chain transfer agent can be used to adjust the molecular weight of the copolymer (E) during the production of the copolymer (E). The chain transfer agent is not particularly limited, and examples thereof include mercaptans, α-methylstyrene dimers, and terpenes.
［熱可塑性樹脂組成物］
本発明の熱可塑性樹脂組成物は、前述の本発明のグラフト共重合体（Ｄ）を含むものであり、好ましくは、本発明のグラフト共重合体（Ｄ）と上述の共重合体（Ｅ）とを含む。
[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains the above-mentioned graft copolymer (D) of the present invention, and preferably the above-mentioned graft copolymer (D) of the present invention and the above-mentioned copolymer (E). Including and.
本発明の熱可塑性樹脂組成物における本発明のグラフト共重合体（Ｄ）の含有率は、グラフト共重合体（Ｄ）と共重合体（Ｅ）の合計を１００質量％とした場合に、１０〜５０質量％であることが好ましく、共重合体（Ｅ）の含有率は５０〜９０質量％であることが好ましい。グラフト共重合体（Ｄ）および共重合体（Ｅ）の含有率が上記範囲であると、熱可塑性樹脂組成物及びその成形品の耐衝撃性、成形外観が優れたものとなる。 The content of the graft copolymer (D) of the present invention in the thermoplastic resin composition of the present invention is 10 when the total of the graft copolymer (D) and the copolymer (E) is 100% by mass. The content of the copolymer (E) is preferably 50 to 90% by mass, and the content of the copolymer (E) is preferably 50 to 90% by mass. When the contents of the graft copolymer (D) and the copolymer (E) are in the above range, the thermoplastic resin composition and its molded product have excellent impact resistance and molded appearance.
本発明の熱可塑性樹脂組成物は、必要に応じて、他の熱可塑性樹脂を含有してもよい。他の熱可塑性樹脂としては特に制限はなく、例えば、ポリカーボネート樹脂、ポリブチレンテレフタレート（ＰＢＴ樹脂）、ポリエチレンテレフタレート（ＰＥＴ樹脂）、ポリ塩化ビニル、ポリスチレン、ポリアセタール樹脂、変性ポリフェニレンエーテル（変性ＰＰＥ樹脂）、エチレン−酢酸ビニル共重合体、ポリアリレート、液晶ポリエステル樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、フッ素樹脂およびポリアミド樹脂（ナイロン）等が挙げられる。これらは１種のみを用いてもよく、２種以上を混合して用いてもよい。 The thermoplastic resin composition of the present invention may contain other thermoplastic resins, if necessary. The other thermoplastic resin is not particularly limited, and for example, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, polyacetal resin, modified polyphenylene ether (modified PPE resin), Examples thereof include ethylene-vinyl acetate copolymer, polyarylate, liquid crystal polyester resin, polyethylene resin, polypropylene resin, fluororesin and polyamide resin (nylon). Only one of these may be used, or two or more thereof may be mixed and used.
本発明の熱可塑性樹脂組成物には、熱可塑性樹脂組成物及びその成形品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）、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、帯電防止剤等を配合することができる。 The thermoplastic resin composition of the present invention includes other conventional additives during the production (mixing) and molding of the thermoplastic resin composition as long as the physical properties of the thermoplastic resin composition and the molded product thereof are not impaired. For example, lubricants, pigments, dyes, fillers (carbon black, silica, titanium oxide, etc.), heat resistant agents, antioxidants, weather resistant agents, mold release agents, plastics, antioxidants, etc. can be blended. ..
本発明の熱可塑性樹脂組成物は、公知の装置を使用した公知の方法で製造できる。例えば、一般的な方法として溶融混合法があり、この方法で使用する装置としては、押出機、バンバリーミキサー、ローラー、ニーダー等が挙げられる。混合には回分式、連続式のいずれを採用してもよい。また、各成分の混合順序などにも特に制限はなく、全ての成分が均一に混合されればよい。 The thermoplastic resin composition of the present invention can be produced by a known method using a known device. For example, there is a melt mixing method as a general method, and examples of the apparatus used in this method include an extruder, a Banbury mixer, a roller, a kneader, and the like. Either a batch type or a continuous type may be adopted for mixing. Further, the mixing order of each component is not particularly limited, and all the components may be uniformly mixed.
［成形品］
本発明の成形品は、本発明の熱可塑性樹脂組成物が成形されたものである。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、カレンダー成形法およびインフレーション成形法等が挙げられる。これらのなかでも、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。
[Molding]
The molded product of the present invention is a molded product of the thermoplastic resin composition of the present invention. Examples of the molding method include an injection molding method, an injection compression molding machine 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, an injection molding method and an injection compression molding method are preferable because they are excellent in mass productivity and can obtain a molded product with high dimensional accuracy.
［用途］
本発明の熱可塑性樹脂組成物及びその成形品の用途については特に制限はないが、本発明の熱可塑性樹脂組成物及びその成形品は、耐衝撃性に優れ、成形外観、流動性にも優れることから、ＯＡ・家電分野、車両・船舶分野、家具・建材などの住宅関連分野、サニタリー分野、雑貨、文具・玩具・スポーツ用品分野などの幅広い分野に有用である。
[Use]
The use of the thermoplastic resin composition of the present invention and its molded product is not particularly limited, but the thermoplastic resin composition of the present invention and its molded product are excellent in impact resistance, molded appearance, and fluidity. Therefore, it is useful in a wide range of fields such as OA / home appliances, vehicles / ships, housing-related fields such as furniture / building materials, sanitary fields, miscellaneous goods, stationery / toys / sporting goods.
以下に、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明は、その要旨を超えない限り、以下の実施例に何ら制限されるものではない。
なお、以下において、「部」は「質量部」、「％」は「質量％」を意味する。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
In the following, "part" means "part by mass" and "%" means "% by mass".
以下の実施例および比較例における各種測定および評価方法は以下の通りである。 Various measurement and evaluation methods in the following examples and comparative examples are as follows.
＜共重合体（Ａ）およびコア−シェル型粒子（Ｃ）の体積平均粒子径＞
マイクロトラック（日機装社製「ナノトラック１５０」）を用い、測定溶媒としてイオン交換水を用いて、水性分散体に分散している共重合体（Ａ）又はコア−シェル型粒子（Ｃ）の体積平均粒子径を測定した。
<Volume average particle size of copolymer (A) and core-shell type particles (C)>
Volume of copolymer (A) or core-shell type particles (C) dispersed in an aqueous dispersion using Microtrac (“Nanotrack 150” manufactured by Nikkiso Co., Ltd.) and ion-exchanged water as a measurement solvent. The average particle size was measured.
＜共重合体（Ａ）およびコア−シェル型粒子（Ｃ）の膨潤度＞
共重合体（Ａ）又はコア−シェル型粒子（Ｃ）の水性分散体を８０℃で２４時間乾燥させ、その後８０℃で２４時間真空乾燥させることで、フィルム状の共重合体（Ａ）又はコア−シェル型粒子（Ｃ）の乾燥物を作成した。得られた乾燥物の重量をＷ１とする。この乾燥物１ｇを８０ｍＬのアセトンに浸漬後、そのアセトンを６５〜７０℃で３時間還流した。次いで、得られた懸濁アセトン溶液を遠心分離機（日立工機社製「ＣＲ２１Ｅ」）にて１４，０００ｒｐｍで３０分間遠心分離して、沈殿成分（アセトン不溶成分）を分取した。アセトン不溶成分の重量をＷ２とする。その後、アセトン不溶成分を常温で２４時間真空乾燥した。真空乾燥後のアセトン不溶成分の重量をＷ３とする。共重合体（Ａ）、コア−シェル型粒子（Ｃ）の膨潤度は、下記式（１）で算出される。
膨潤度（％）＝（Ｗ２／Ｗ３）×１００ …（１）
<Swelling degree of copolymer (A) and core-shell type particles (C)>
The aqueous dispersion of the copolymer (A) or the core-shell type particles (C) is dried at 80 ° C. for 24 hours and then vacuum dried at 80 ° C. for 24 hours to form a film-like copolymer (A) or A dried product of core-shell type particles (C) was prepared. Let the weight of the obtained dried product be W1. After immersing 1 g of this dried product in 80 mL of acetone, the acetone was refluxed at 65 to 70 ° C. for 3 hours. Next, the obtained suspended acetone solution was centrifuged at 14,000 rpm for 30 minutes with a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.) to separate a precipitate component (acetone insoluble component). The weight of the acetone-insoluble component is W2. Then, the acetone-insoluble component was vacuum dried at room temperature for 24 hours. The weight of the acetone-insoluble component after vacuum drying is W3. The degree of swelling of the copolymer (A) and the core-shell type particles (C) is calculated by the following formula (1).
Swelling degree (%) = (W2 / W3) × 100… (1)
＜グラフト共重合体（Ｄ）のグラフト率＞
グラフト共重合体（Ｄ）１ｇを８０ｍＬのアセトンに添加し、６５〜７０℃にて３時間加熱還流し、得られた懸濁アセトン溶液を遠心分離機（日立工機社製「ＣＲ２１Ｅ」）にて１４，０００ｒｐｍ、３０分間遠心分離して、沈殿成分（アセトン不溶成分）とアセトン溶液（アセトン可溶成分）を分取した。そして、沈殿成分（アセトン不溶成分）を乾燥させてその質量（Ｙ（ｇ））を測定し、下記式（２）によりグラフト率を算出した。なお、式（２）におけるＹは、グラフト共重合体（Ｄ）のアセトン不溶成分の質量（ｇ）、ＸはＹを求める際に使用したグラフト共重合体（Ｄ）の全質量（ｇ）、ゴム分率はグラフト共重合体（Ｄ）の製造に用いたコア−シェル型粒子（Ｃ）の水性分散体における固形分濃度である。
グラフト率（質量％）＝｛（Ｙ−Ｘ×ゴム分率）／Ｘ×ゴム分率｝
×１００ …（２）
<Graft ratio of graft copolymer (D)>
1 g of the graft copolymer (D) was added to 80 mL of acetone, heated and refluxed at 65 to 70 ° C. for 3 hours, and the obtained suspended acetone solution was placed in a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.). Then, the mixture was centrifuged at 14,000 rpm for 30 minutes to separate a precipitate component (acetone insoluble component) and an acetone solution (acetone soluble component). Then, the precipitated component (acetone insoluble component) was dried, its mass (Y (g)) was measured, and the graft ratio was calculated by the following formula (2). In the formula (2), Y is the mass (g) of the acetone-insoluble component of the graft copolymer (D), and X is the total mass (g) of the graft copolymer (D) used in determining Y. The rubber fraction is the solid content concentration of the core-shell type particles (C) used in the production of the graft copolymer (D) in the aqueous dispersion.
Graft ratio (mass%) = {(YX x rubber fraction) / X x rubber fraction}
× 100… (2)
＜共重合体（Ｅ）の質量平均分子量＞
共重合体（Ｅ）の質量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）を用い、テトラヒドロフラン（ＴＨＦ）に溶解して測定したものを標準ポリスチレン（ＰＳ）換算で求めた。
<Mass average molecular weight of copolymer (E)>
The mass average molecular weight of the copolymer (E) was determined by dissolving it in tetrahydrofuran (THF) using gel permeation chromatography (GPC) in terms of standard polystyrene (PS).
［実施例Ｉ−１：コア−シェル型粒子（Ｃ−１）の製造］
＜共重合体（Ａ−１）の製造＞
まず、以下の配合で共重合体（Ａ−１）を製造した。
[Example I-1: Production of core-shell type particles (C-1)]
<Manufacturing of copolymer (A-1)>
First, a copolymer (A-1) was produced with the following composition.
〔配合〕
アクリル酸ｎ−ブチル（ＢＡ） ４８部
メタクリル酸アリル ０．１９部
流動パラフィン（ＬＰ） ０．５部
アルケニルコハク酸ジカリウム（ＡＳＫ） ０．２９部
ジラウロイルペルオキシド ０．２９部
イオン交換水 １４０部
[Mixing]
N-Butyl acrylate (BA) 48 parts Allyl methacrylate 0.19 parts Liquid paraffin (LP) 0.5 parts Dipotassium alkenyl succinate (ASK) 0.29 parts Dilauroyl peroxide 0.29 parts Ion-exchanged water 140 parts
試薬注入容器、冷却管、ジャケット加熱機および攪拌装置を備えた反応器に、アクリル酸ｎ−ブチル、流動パラフィン、メタクリル酸アリル、ジラウロイルペルオキシド、イオン交換水、アルケニルコハク酸ジカリウムを仕込み、常温下で（株）日本精機製作所製ＵＬＴＲＡＳＯＮＩＣ ＨＯＭＯＧＥＮＩＺＥＲ ＵＳ−６００を用いて振幅３５μｍで２０分間超音波処理を行うことでプレエマルションを得た。得られたラテックスの体積平均粒子径は２７０ｎｍであった。
プレエマルションを６０℃に加熱し、ラジカル重合を開始した。重合により、液温は７８℃まで上昇した。３０分間７５℃で維持し、重合を完結させ、水性分散体に分散している共重合体（Ａ−１）を得た。
A reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer is charged with n-butyl acrylate, liquid paraffin, allyl methacrylate, dilauroyl peroxide, ion-exchanged water, and dipotassium alkenyl succinate at room temperature. A pre-emulsion was obtained by performing ultrasonic treatment for 20 minutes at an amplitude of 35 μm using ULTRASONIC HOMOGENIZER US-600 manufactured by Nippon Seiki Seisakusho Co., Ltd. The volume average particle size of the obtained latex was 270 nm.
The preemulsion was heated to 60 ° C. to initiate radical polymerization. Due to the polymerization, the liquid temperature rose to 78 ° C. The temperature was maintained at 75 ° C. for 30 minutes to complete the polymerization, and a copolymer (A-1) dispersed in an aqueous dispersion was obtained.
＜コア−シェル型粒子（Ｃ−１）の製造＞
共重合体（Ａ−１）を製造後、反応器の内温を７５℃に保ったまま、硫酸第一鉄０．０００１部、エチレンジアミン四酢酸二ナトリウム塩０．０００３部、ロンガリット０．２部、およびイオン交換水５部からなる水溶液を添加し、次いで、アルケニルコハク酸ジカリウム０．０１部を添加した。その後、アクリル酸２−フェノキシエチル２部、メタクリル酸アリル０．０１部、およびｔ−ブチルヒドロペルオキシド０．００４部からなる混合液を０．２６部／分のレートで滴下し、共重合体（Ｂ−１）の重合を行って、コア−シェル型粒子（Ｃ−１）の水性分散体を得た。
<Manufacturing of core-shell type particles (C-1)>
After producing the copolymer (A-1), while maintaining the internal temperature of the reactor at 75 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetate, 0.2 part of longalit. , And an aqueous solution consisting of 5 parts of ion-exchanged water was added, and then 0.01 part of dipotassium alkenyl succinate was added. Then, a mixed solution consisting of 2 parts of 2-phenoxyethyl acrylate, 0.01 part of allyl methacrylate, and 0.004 part of t-butyl hydroperoxide was added dropwise at a rate of 0.26 part / min, and the copolymer ( Polymerization of B-1) was carried out to obtain an aqueous dispersion of core-shell type particles (C-1).
［実施例Ｉ−２〜８、比較例Ｉ−４，５，７：コア−シェル型粒子（Ｃ−２）〜（Ｃ−８），（Ｃ−１２），（Ｃ−１３），（Ｃ−１５）の製造］
共重合体（Ａ−１）を製造する際の（メタ）アクリル酸アルキルｎ−ブチル、メタクリル酸アリル等の単量体や、アルケニルコハク酸ジカリウム、ジラウロイルペルオキシドの種類や量と、共重合体（Ｂ）を共重合する際のアクリル酸２−フェノキシエチル等の単量体や、アルケニルコハク酸ジカリウム、メタクリル酸アリル、ｔ−ブチルヒドロペルオキシドの種類や量を表１（表１Ａ，１Ｂ）に示す通り変更したこと以外は、コア−シェル型粒子（Ｃ−１）と同様にして、水性分散体に分散しているコア−シェル型粒子（Ｃ−２）〜（Ｃ−８），（Ｃ−１２），（Ｃ−１３），（Ｃ−１５）を得た。
[Examples I-2 to 8, Comparative Examples I-4, 5, 7: Core-shell type particles (C-2) to (C-8), (C-12), (C-13), (C) -15) Manufacture]
The type and amount of monomers such as alkyl n-butyl (meth) acrylate and allyl methacrylate when producing the copolymer (A-1), dipotassium alkenyl succinate, and dilauroyl peroxide, and the copolymer. Table 1 (Tables 1A and 1B) shows the types and amounts of monomers such as 2-phenoxyethyl acrylate and dipotassium alkenyl succinate, allyl methacrylate, and t-butyl hydroperoxide when copolymerizing (B). Core-shell type particles (C-2) to (C-8), (C-8) dispersed in the aqueous dispersion in the same manner as the core-shell type particles (C-1) except for the changes as shown. -12), (C-13), and (C-15) were obtained.
［比較例Ｉ−１〜３，６：ゴム粒子（Ｃ−９）〜（Ｃ−１１），（Ｃ−１４）の製造］
共重合体（Ａ−１）を製造する際の（メタ）アクリル酸アルキルｎ−ブチル、メタクリル酸アリル等の単量体や、アルケニルコハク酸ジカリウム、ジラウロイルペルオキシドの種類や量を表１Ｂに示す通り変更し、共重合体（Ａ−１）の製造と同様にして、共重合体（Ａ−９）〜（Ａ−１１），（Ａ−１４）のみからなる非コア−シェル型のゴム粒子（Ｃ−９）〜（Ｃ−１１），（Ｃ−１４）の水性分散体を得た。
[Comparative Examples I-1 to 3, 6: Production of Rubber Particles (C-9) to (C-11), (C-14)]
Table 1B shows the types and amounts of monomers such as alkyl n-butyl (meth) acrylate and allyl methacrylate in the production of the copolymer (A-1), dipotassium alkenyl succinate, and dilauroyl peroxide. Non-core-shell type rubber particles consisting only of the copolymers (A-9) to (A-11) and (A-14) in the same manner as in the production of the copolymer (A-1). Aqueous dispersions of (C-9) to (C-11) and (C-14) were obtained.
実施例Ｉ−１〜８および比較例Ｉ−１〜７で得られた水性分散体に分散している共重合体（Ａ−１）〜（Ａ−１５）の体積平均粒子径及び膨潤度と、水性分散体に分散しているコア−シェル型粒子又はゴム粒子（Ｃ−１）〜（Ｃ−１５）の体積平均粒子径及び膨潤度を、表１（表１Ａ，１Ｂ）に示す。 The volume average particle size and swelling degree of the copolymers (A-1) to (A-15) dispersed in the aqueous dispersions obtained in Examples I-1 to 8 and Comparative Examples I-1 to 7. The volume average particle diameters and swelling degrees of the core-shell type particles or rubber particles (C-1) to (C-15) dispersed in the aqueous dispersion are shown in Table 1 (Tables 1A and 1B).
［実施例II−１：グラフト共重合体（Ｄ−１）の製造］
コア−シェル型粒子（Ｃ−１）を製造後、反応器の内温を７５℃に保ったまま、コア−シェル型粒子（Ｃ−１）５０部（固形分として）に対して、硫酸第一鉄０．００１部、エチレンジアミン四酢酸二ナトリウム塩０．００３部、ロンガリット０．３部、およびイオン交換水５部からなる水溶液を添加し、次いで、アルケニルコハク酸ジカリウム０．１部を添加した。その後、アクリロニトリル１４部、スチレン３６部、およびｔ−ブチルヒドロペルオキシド０．１７部からなる混合液を１時間４０分にわたって滴下し、グラフト重合させた。
[Example II-1: Production of graft copolymer (D-1)]
After producing the core-shell type particles (C-1), the sulfuric acid is added to 50 parts (as solid content) of the core-shell type particles (C-1) while maintaining the internal temperature of the reactor at 75 ° C. An aqueous solution consisting of 0.001 part of ferrous iron, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.3 part of longalit, and 5 parts of ion-exchanged water was added, and then 0.1 part of dipotassium alkenyl succinate was added. .. Then, a mixed solution consisting of 14 parts of acrylonitrile, 36 parts of styrene, and 0.17 parts of t-butyl hydroperoxide was added dropwise over 1 hour and 40 minutes for graft polymerization.
滴下終了後、内温を７５℃に１０分間保持した後、冷却し、内温が６０℃となった時点で、アルケニルコハク酸ジカリウム０．２部をイオン交換水５部に溶解した水溶液を添加した。次いで、反応生成物の水性分散体を硫酸水溶液で凝固、水洗した後、乾燥してグラフト共重合体（Ｄ−１）を得た。 After completion of the dropping, the internal temperature was maintained at 75 ° C. for 10 minutes, then cooled, and when the internal temperature reached 60 ° C., an aqueous solution prepared by dissolving 0.2 parts of dipotassium alkenyl succinate in 5 parts of ion-exchanged water was added. did. Next, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a graft copolymer (D-1).
［実施例II−２〜８、比較例II−１〜７：グラフト共重合体（Ｄ−２）〜（Ｄ−１５）の製造］
用いたコア−シェル型粒子又はゴム粒子（Ｃ）の種類を表２に示す通り変更したこと以外は、グラフト共重合体（Ｄ−１）と同様にして、グラフト共重合体（Ｄ−２）〜（Ｄ−１５）を得た。
[Examples II-2 to 8, Comparative Examples II-1 to 7: Production of Graft Copolymers (D-2) to (D-15)]
The graft copolymer (D-2) was the same as the graft copolymer (D-1) except that the types of core-shell type particles or rubber particles (C) used were changed as shown in Table 2. ~ (D-15) was obtained.
実施例II−１〜８および比較例II−１〜７で得られたグラフト共重合体（Ｄ−１）〜（Ｄ−１５）のグラフト率を表２に示す。 Table 2 shows the graft ratios of the graft copolymers (D-1) to (D-15) obtained in Examples II-1 to 8 and Comparative Examples II-1 to 7.
［共重合体（Ｅ−１）の製造］
耐圧反応容器にイオン交換水１５０部と、ビニル系単量体混合物（ｍ４）としてアクリロニトリル３４部、スチレン６６部の混合物と、２，２’−アゾビス（イソブチロニトリル）０．２部、ｎ−オクチルメルカプタン０．４５部、カルシウムハイドロオキシアパタイト０．４７部、アルケニルコハク酸カリウム０．００３部を仕込み、内温を７５℃まで昇温し、３時間反応を行った。その後、９０℃まで昇温し、６０分間保持することで反応を完結させた。内容物を遠心脱水機で洗浄、脱水を繰り返し、乾燥させて質量平均分子量９５，０００の共重合体（Ｅ−１）を得た。
[Production of copolymer (E-1)]
In a pressure-resistant reaction vessel, 150 parts of ion-exchanged water, 34 parts of acrylonitrile and 66 parts of styrene as a vinyl-based monomer mixture (m4), 0.2 parts of 2,2'-azobis (isobutyronitrile), n -0.45 parts of octyl mercaptan, 0.47 parts of calcium hydroxyapatite, and 0.003 parts of potassium alkenyl succinate were charged, the internal temperature was raised to 75 ° C., and the reaction was carried out for 3 hours. Then, the temperature was raised to 90 ° C. and held for 60 minutes to complete the reaction. The contents were washed with a centrifugal dehydrator and dehydrated repeatedly, and dried to obtain a copolymer (E-1) having a mass average molecular weight of 95,000.
［実施例III−１〜８、比較例III−１〜７：熱可塑性樹脂組成物の製造と評価］
表３に示す組成（質量部）で各成分を混合し、さらにそこにカーボンブラック０．８部を混合し、３０ｍｍφの真空ベント付き２軸押し出し機（池貝社製「ＰＣＭ３０」）を用いて２４０℃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についてメルトボリュームレートを以下の方法により評価した。また、得られた熱可塑性樹脂組成物を射出成形した成形品について、成形外観、耐衝撃性を以下の方法により評価した。
評価結果を表３に示す。
[Examples III-1 to 8, Comparative Examples III-1 to 7: Production and evaluation of thermoplastic resin composition]
Each component is mixed according to the composition (mass part) shown in Table 3, and 0.8 part of carbon black is further mixed therein, and 240 using a twin-screw extruder with a vacuum vent of 30 mmφ (“PCM30” manufactured by Ikegai Corp.). The mixture was melt-kneaded at ° C to obtain a pellet-shaped thermoplastic resin composition. The melt volume rate of the obtained thermoplastic resin composition was evaluated by the following method. Further, the molded product obtained by injection molding the obtained thermoplastic resin composition was evaluated for its molding appearance and impact resistance by the following methods.
The evaluation results are shown in Table 3.
［各評価方法］
＜メルトボリュームレート（ＭＶＲ）の測定＞
ＩＳＯ １１３３：１９９７に準拠し、２２０℃における熱可塑性樹脂組成物のＭＶＲを、９８Ｎ（１０ｋｇ）の荷重で測定した。なお、ＭＶＲは熱可塑性樹脂組成物の流動性の目安となり、数値が高いほど流動性に優れることを意味する。
[Each evaluation method]
<Measurement of melt volume rate (MVR)>
The MVR of the thermoplastic resin composition at 220 ° C. was measured under a load of 98N (10kg) according to ISO 1133: 1997. In addition, MVR is a measure of the fluidity of the thermoplastic resin composition, and the higher the value, the better the fluidity.
＜射出成形１＞
溶融混練して得られた熱可塑性樹脂組成物のペレットを射出成型機（東芝機械社製、「ＩＳ５５ＦＰ−１．５Ａ」）によりシリンダー温度２００〜２７０℃、金型温度６０℃の条件で、縦８０ｍｍ、横１０ｍｍ、厚さ４ｍｍの成形品を成形し、シャルピー衝撃試験用成形品（成形品（Ｍａ１））として用いた。
<Injection molding 1>
Pellets of a thermoplastic resin composition obtained by melt-kneading are vertically formed by an injection molding machine (manufactured by Toshiba Machine Co., Ltd., "IS55FP-1.5A") under the conditions of a cylinder temperature of 200 to 270 ° C and a mold temperature of 60 ° C. A molded product having a thickness of 80 mm, a width of 10 mm, and a thickness of 4 mm was molded and used as a molded product for a Charpy impact test (molded product (Ma1)).
＜射出成形２＞
溶融混練して得られた熱可塑性樹脂組成物のペレットを射出成型機（東芝機械社製、「ＩＳ５５ＦＰ−１．５Ａ」）によりシリンダー温度２００〜２７０℃、金型温度６０℃、射出率７ｇ／秒の条件で、縦１００ｍｍ、横１００ｍｍ、厚さ３ｍｍの成形品を成形し、外観評価用成形品（成形品（Ｍａ２））として用いた。
<Injection molding 2>
Pellets of thermoplastic resin composition obtained by melt-kneading are injected by an injection molding machine (manufactured by Toshiba Machine Co., Ltd., "IS55FP-1.5A"), cylinder temperature 200 to 270 ° C, mold temperature 60 ° C, injection rate 7 g / A molded product having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm was molded under the condition of seconds, and used as a molded product for appearance evaluation (molded product (Ma2)).
＜射出成形３＞
溶融混練して得られた熱可塑性樹脂組成物のペレットを射出成型機（東芝機械社製、「ＩＳ５５ＦＰ−１．５Ａ」）によりシリンダー温度２００〜２７０℃、金型温度６０℃、射出率１２８ｇ／秒の条件で、縦１００ｍｍ、横１００ｍｍ、厚さ３ｍｍの成形品を成形し、外観評価用成形品（成形品（Ｍａ３））として用いた。
<Injection molding 3>
Pellets of thermoplastic resin composition obtained by melt-kneading are injected by an injection molding machine (manufactured by Toshiba Machine Co., Ltd., "IS55FP-1.5A"), cylinder temperature 200 to 270 ° C, mold temperature 60 ° C, injection rate 128 g / A molded product having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm was molded under the condition of seconds, and used as a molded product for appearance evaluation (molded product (Ma3)).
＜外観評価（１）＞
成形品（Ｍａ２）について、分光測色計（コニカミノルタオプティプス社製「ＣＭ−３５００ｄ」）を用いて明度Ｌ＊を、ＳＣＥ方式にて測定した。こうして測定されたＬ＊を「Ｌ＊（ｍａ）」とする。Ｌ＊が低いほど黒色となり、外観が良好である。
<Appearance evaluation (1)>
With respect to the molded product (Ma2), the brightness L * was measured by the SCE method using a spectrocolorimeter (“CM-3500d” manufactured by Konica Minolta Optips). Let L * measured in this way be "L * (ma)". The lower the L * , the blacker the color and the better the appearance.
＜外観評価（２）＞
成形品（Ｍａ３）について、分光測色計（コニカミノルタオプティプス社製「ＣＭ−３５００ｄ」）を用いて明度Ｌ＊を、ＳＣＥ方式にて測定した。こうして測定されたＬ＊を「Ｌ＊（ｍｂ）」とする。Ｌ＊が低いほど黒色となり、外観が良好である。
射出速度が速い条件で成形した際に、樹脂中のゴム成分が配向することで、白化やブロンズ現象が生じ、Ｌ＊が大きくなる。そのため、射出速度が速い条件での成形外観が重要となる。
<Appearance evaluation (2)>
For the molded product (Ma3), the brightness L * was measured by the SCE method using a spectrocolorimeter (“CM-3500d” manufactured by Konica Minolta Optips). Let L * measured in this way be "L * (mb)". The lower the L * , the blacker the color and the better the appearance.
When molding is performed under conditions of high injection speed, the rubber components in the resin are oriented, causing whitening and bronze phenomena, resulting in an increase in L *. Therefore, the molding appearance under the condition that the injection speed is high is important.
＜外観評価（３）（外観の射出速度依存性評価）＞
ΔＬ＊＝（Ｌ＊（ｍｂ）−Ｌ＊（ｍａ））２の式よりΔＬ＊を算出した。ΔＬ＊が小さいほど、外観の射出速度依存性が小さい。一般に、車輛部品等の成形品においては、部品箇所により射出速度が異なる。そのため、射出速度依存性の大きい樹脂では、成形時に部品表面に色むらが生じる、といった外観不良が起こる。
<Appearance evaluation (3) (Appearance injection speed dependence evaluation)>
ΔL * = (L * (mb) -L * (ma)) ΔL * was calculated from the equation of 2. The smaller ΔL * , the smaller the dependence of the appearance on the injection speed. Generally, in a molded product such as a vehicle part, the injection speed differs depending on the part location. Therefore, with a resin having a large dependence on the injection speed, an appearance defect such as color unevenness on the surface of the component during molding occurs.
＜耐衝撃性の評価：シャルピー衝撃試験＞
成形品（Ｍａ１）について、ＩＳＯ １７９−１：２０１３年度版に準拠し、試験温度２３℃もしくは−２０℃の条件で成形品（タイプＢ１、ノッチ有：形状Ａ シングルノッチ）のシャルピー衝撃強度（打撃方向：エッジワイズ）を測定した。シャルピー衝撃強度が高いほど、耐衝撃性に優れることを意味する。
<Evaluation of impact resistance: Charpy impact test>
Regarding the molded product (Ma1), in accordance with ISO 179-1: 2013 edition, the Charpy impact strength (impact) of the molded product (type B1, with notch: shape A single notch) under the condition of test temperature 23 ° C or -20 ° C. Direction: edgewise) was measured. The higher the Charpy impact strength, the better the impact resistance.
表３の実施例III−１〜８に示すように、各実施例によれば、耐衝撃性や流動性、外観に優れる熱可塑性樹脂組成物および成形品が得られた。 As shown in Examples III-1 to 8 of Table 3, according to each Example, a thermoplastic resin composition and a molded product having excellent impact resistance, fluidity, and appearance were obtained.
一方、比較例III−１は、ゴム粒子がコア−シェル型ではなく、（メタ）アクリル酸アルキルエステル単位が主成分であるため、成形外観に劣った。
比較例III−２、比較例III−３は、粒子がコア−シェル型ではなく、芳香族炭化水素基を有する（メタ）アクリル酸エステル単位を含むため、成形外観は良好であるが、低温耐衝撃性に劣った。
比較例III−４、比較例III−５は、シェル部が芳香族炭化水素基を有する（メタ）アクリル酸エステル単位ではないため、耐衝撃性と成形外観に劣った。
比較例III−６は、粒子がコア−シェル型ではなく、（メタ）アクリル酸アルキルエステルとスチレンの共重合体であるため、耐衝撃性と成形外観に劣った。
比較例III−７は、シェル部が（メタ）アクリル酸アルキルエステル単位よりなるため、成形外観に劣った。
On the other hand, Comparative Example III-1 was inferior in molded appearance because the rubber particles were not core-shell type and mainly contained (meth) acrylic acid alkyl ester units.
Comparative Example III-2 and Comparative Example III-3 have a good molded appearance because the particles are not core-shell type and contain (meth) acrylic acid ester units having aromatic hydrocarbon groups, but are resistant to low temperatures. It was inferior in impact resistance.
In Comparative Example III-4 and Comparative Example III-5, since the shell portion was not a (meth) acrylic acid ester unit having an aromatic hydrocarbon group, the impact resistance and the molded appearance were inferior.
Comparative Example III-6 was inferior in impact resistance and molded appearance because the particles were not a core-shell type but a copolymer of (meth) acrylic acid alkyl ester and styrene.
In Comparative Example III-7, the shell portion was composed of (meth) acrylic acid alkyl ester units, so that the molded appearance was inferior.
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| WO2014162369A1 (en) * | 2013-04-05 | 2014-10-09 | 株式会社カネカ | Resin composition and film thereof |
| JP2014211513A (en) * | 2013-04-18 | 2014-11-13 | 日油株式会社 | Optical laminate |
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