JP2003160624A - Graft copolymer and thermoplastic resin composition containing the same - Google Patents
Graft copolymer and thermoplastic resin composition containing the sameInfo
- Publication number
- JP2003160624A JP2003160624A JP2001360071A JP2001360071A JP2003160624A JP 2003160624 A JP2003160624 A JP 2003160624A JP 2001360071 A JP2001360071 A JP 2001360071A JP 2001360071 A JP2001360071 A JP 2001360071A JP 2003160624 A JP2003160624 A JP 2003160624A
- Authority
- JP
- Japan
- Prior art keywords
- graft copolymer
- polymer
- parts
- resin composition
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 72
- 239000011342 resin composition Substances 0.000 title claims abstract description 50
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- 239000002245 particle Substances 0.000 claims abstract description 56
- -1 acrylic ester Chemical class 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 58
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 239000005060 rubber Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 11
- 238000004040 coloring Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 description 45
- 239000004816 latex Substances 0.000 description 37
- 229920000126 latex Polymers 0.000 description 37
- 239000003995 emulsifying agent Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 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 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 9
- 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 8
- 125000000524 functional group Chemical group 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 125000005375 organosiloxane group Chemical group 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229920003244 diene elastomer Polymers 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010559 graft polymerization reaction Methods 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 4
- VLZDYNDUVLBNLD-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C(C)=C VLZDYNDUVLBNLD-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 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 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 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
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 108700004121 sarkosyl Proteins 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-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
- 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
- LVUDMQWOFGGAFN-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione;prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1.O=C1C=CC(=O)N1C1=CC=CC=C1 LVUDMQWOFGGAFN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- IGRYVRNQZARURF-UHFFFAOYSA-N 2-(dimethoxymethylsilyl)ethyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCOC(=O)C(C)=C IGRYVRNQZARURF-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- BQQGVSONEPNPAB-UHFFFAOYSA-N 3-(diethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound CCOC(OCC)[SiH2]CCCOC(=O)C(C)=C BQQGVSONEPNPAB-UHFFFAOYSA-N 0.000 description 1
- WUTSHINWYBIRDG-UHFFFAOYSA-N 3-[ethoxy(diethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](CC)(CC)CCCOC(=O)C(C)=C WUTSHINWYBIRDG-UHFFFAOYSA-N 0.000 description 1
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical group [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- FUINFYCIIMWIDS-UHFFFAOYSA-N dimethoxymethyl(propyl)silane Chemical compound CCC[SiH2]C(OC)OC FUINFYCIIMWIDS-UHFFFAOYSA-N 0.000 description 1
- LIYUFTTVSMBDTB-UHFFFAOYSA-N dimethoxymethyl-(4-ethenylphenyl)silane Chemical compound COC(OC)[SiH2]C1=CC=C(C=C)C=C1 LIYUFTTVSMBDTB-UHFFFAOYSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- UYNIHQFSTRDMAY-UHFFFAOYSA-L dipotassium 4-heptadec-1-enoxy-4-oxobutanoate Chemical compound C(CCC(=O)[O-])(=O)OC=CCCCCCCCCCCCCCCC.[K+].[K+].C(=CCCCCCCCCCCCCCCC)OC(CCC(=O)[O-])=O UYNIHQFSTRDMAY-UHFFFAOYSA-L 0.000 description 1
- DUTQNAMBWKUFQN-UHFFFAOYSA-L dipotassium 4-hexadec-1-enoxy-4-oxobutanoate Chemical compound C(CCC(=O)[O-])(=O)OC=CCCCCCCCCCCCCCC.[K+].[K+].C(=CCCCCCCCCCCCCCC)OC(CCC(=O)[O-])=O DUTQNAMBWKUFQN-UHFFFAOYSA-L 0.000 description 1
- PWZPZEQVSQVWMM-UHFFFAOYSA-L dipotassium 4-octadec-1-enoxy-4-oxobutanoate Chemical compound C(CCC(=O)[O-])(=O)OC=CCCCCCCCCCCCCCCCC.[K+].[K+].C(=CCCCCCCCCCCCCCCCC)OC(CCC(=O)[O-])=O PWZPZEQVSQVWMM-UHFFFAOYSA-L 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- DEAKWVKQKRNPHF-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 DEAKWVKQKRNPHF-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
(57)【要約】
【課題】 耐衝撃性、特に低温での耐衝撃性、鮮鋭的な
着色性、及び耐候性の特性をバランス良く兼備する樹脂
材料を開発する。
【解決手段】 質量平均粒子径が３００ｎｍ〜２０００
ｎｍである架橋アクリル酸エステル系ゴム状重合体
（Ａ）及びポリオルガノシロキサン（Ｓ）の３〜５０重
量部に、（メタ）アクリル酸エステルと架橋剤および／
またはグラフト交叉剤を必須成分とする単量体混合物
（Ｂ）５０〜９７重量部を重合せしめてなる複合ゴム状
重合体（Ｒ）に、さらにビニル系単量体を重合して得ら
れるグラフト共重合体（Ｇ）、かかるグラフト共重合体
と他の熱可塑性樹脂を含有する熱可塑性樹脂組成物及び
その成形品。(57) [PROBLEMS] To develop a resin material having a good balance of impact resistance, particularly impact resistance at low temperatures, sharp coloring, and weather resistance. SOLUTION: Mass average particle diameter is 300 nm to 2000
3 to 50 parts by weight of the cross-linked acrylic ester rubber-like polymer (A) and the polyorganosiloxane (S) which are nm, a (meth) acrylic ester, a cross-linking agent, and / or
Alternatively, a graft copolymer obtained by further polymerizing a vinyl monomer to a composite rubber-like polymer (R) obtained by polymerizing 50 to 97 parts by weight of a monomer mixture (B) containing a graft crossing agent as an essential component. Polymer (G), a thermoplastic resin composition containing such a graft copolymer and another thermoplastic resin, and a molded article thereof.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規なグラフト共
重合体、該グラフト共重合体を含有する衝撃強度、特に
低温環境下での衝撃強度、着色時の発色性、そして耐候
性に優れる熱可塑性樹脂組成物及びその成型品に関す
る。TECHNICAL FIELD The present invention relates to a novel graft copolymer, an impact strength containing the graft copolymer, particularly an impact strength under a low temperature environment, a coloring property at the time of coloring, and a heat resistance excellent in weather resistance. TECHNICAL FIELD The present invention relates to a plastic resin composition and a molded product thereof.
【０００２】[0002]
【従来の技術】樹脂材料の耐衝撃性を向上させること
は、材料の用途の拡大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、工業的な有用性は非常に
大きく、これまでに様々な手法による材料開発がなされ
てきた。これらの中で、ゴム質重合体を硬質樹脂と組み
合わせて材料の耐衝撃性を高めた材料としては、ＡＢＳ
樹脂、ハイインパクトポリスチレン樹脂、変性ＰＰＥ樹
脂およびＭＢＳ樹脂強化ポリ塩化ビニル樹脂等が既に工
業的に使用されている。特にゴム質重合体にアルキル
（メタ）アクリレートゴム等の飽和ゴム成分を用いるこ
とによって、耐候性を高めたＡＢＳ樹脂であるＡＳＡ樹
脂は、様々な目的に用いられているが、耐候性が求めら
れる屋外での使用が増えてきている。2. Description of the Related Art Improving the impact resistance of resin materials not only expands the applications of the materials, but also makes it possible to cope with thinner and larger molded products, which is of great industrial utility. The materials have been developed by various methods so far. Among these, ABS is a material in which a rubbery polymer is combined with a hard resin to improve the impact resistance of the material.
Resins, high-impact polystyrene resins, modified PPE resins, MBS resin-reinforced polyvinyl chloride resins and the like have already been industrially used. Particularly, an ASA resin which is an ABS resin having improved weather resistance by using a saturated rubber component such as an alkyl (meth) acrylate rubber in a rubbery polymer is used for various purposes, but weather resistance is required. The outdoor use is increasing.
【０００３】ＡＳＡ樹脂の欠点である着色成形品の真珠
様光沢（パール光沢不良）の発生等の外観特性と耐衝撃
性のバランスを改良する方法として、特開昭５１−１０
２０９０号公報、同５８−２２２１３９号公報、同６３
−２０２６４４号公報、同６３−２５８９４４号公報、
同６３−２９５６５９号公報あるいは特開平４−２２５
０５１号公報には、異なる粒子径分布を持つ材料を組み
合わせたアクリル酸エステル系ゴム状重合体からなるＡ
ＳＡ樹脂が提案されている。As a method for improving the balance between appearance characteristics such as occurrence of pearly luster (defective pearl luster) and impact resistance of a colored molded product, which is a defect of ASA resin, JP-A-51-10.
2090, 58-222139, 63.
-202644, 63-258944,
63-295659 or JP-A-4-225.
In Japanese Patent No. 051 A, an A-based rubber-like polymer composed of a combination of materials having different particle size distributions is used.
SA resin has been proposed.
【０００４】その他、樹脂特性の改善を目的として、ジ
エン系ゴムを粒子内部に含む多重構造の架橋アクリルゴ
ムに関する方法（特公昭４７−４７８６３号公報、特公
昭５９−４９２４５号公報、特公平３−６６３２９号公
報など）、また、微粒子化されたポリオルガノシロキサ
ンとアクリル酸アルキルエステルとの複合ゴムを用いた
グラフト共重合体（特開平５−２７９４３４号公報及び
同６−２５４９２号公報）などが提案されている。In addition, for the purpose of improving the resin characteristics, a method relating to a cross-linked acrylic rubber having a multi-structure containing a diene rubber inside the particles (Japanese Patent Publication No. 47-47863, Japanese Patent Publication No. 59-49245, and Japanese Patent Publication No. No. 66329) and a graft copolymer using a composite rubber of finely divided polyorganosiloxane and acrylic acid alkyl ester (JP-A-5-279434 and JP-A-6-25492). Has been done.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記従
来の技術による樹脂材料は、耐候性及び着色性のいずれ
かの特性で不十分であったり（上掲特開昭５１−１０２
０９０号公報など）、耐候性に劣るものであったり（上
掲特公昭４７−４７８６３号公報など）、あるいは低温
での耐衝撃性が劣っている（上掲特開平５−２７９４３
４号公報など）など、耐候性、低温での耐衝撃性、そし
て成形外観、特に着色時の発色性（以下、着色性とい
う）などの特性をバランス良く備えた材料は極めて少な
く、近年の厳しいニーズに充分答え得るものとはいえな
かった。However, the resin material according to the above-mentioned conventional technique is insufficient in weather resistance and colorability (see Japanese Patent Laid-Open No. 51-102).
090, etc.), inferior weather resistance (e.g. Japanese Patent Publication No. 47-47863, etc.), or inferior impact resistance at low temperature (e.g. Japanese Patent Application Laid-Open No. 5-27943).
No. 4, etc.) have very good balance of properties such as weather resistance, impact resistance at low temperature, and appearance of molding, especially coloring property at coloring (hereinafter referred to as coloring property). It wasn't enough to answer the needs.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく、グラフト共重合体を構成するゴム状重合
体の構造と該グラフト共重合体を含む樹脂組成物ついて
鋭意検討した結果、架橋アクリル酸エステル系ゴム状重
合体とポリオルガノシロキサンとを含有する複合ゴム状
重合体を構成成分とする新規なグラフト共重合体を開発
し、かかるグラフト共重合体を含む樹脂組成物が、特に
着色性と耐衝撃性において優れた特性を有することを見
出し、本発明をなすに至った。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have diligently studied the structure of a rubber-like polymer constituting a graft copolymer and a resin composition containing the graft copolymer. As a result, a novel graft copolymer having a composite rubber-like polymer containing a crosslinked acrylic ester rubber-like polymer and a polyorganosiloxane as a constituent component was developed, and a resin composition containing the graft copolymer was developed. In particular, they have found that they have excellent properties in terms of colorability and impact resistance, and have completed the present invention.
【０００７】すなわち、本発明は、質量平均粒子径が３
００ｎｍ〜２０００ｎｍの架橋アクリル酸エステル系ゴ
ム状重合体（Ａ）及びポリオルガノシロキサン（Ｓ）の
３〜５０重量部に、（メタ）アクリル酸エステルと架橋
剤および／またはグラフト交叉剤を必須成分とする単量
体混合物（Ｂ）５０〜９７重量部を重合せしめてなる複
合ゴム状重合体（Ｒ）に、さらにビニル系単量体を重合
することによって得られる新規な共重合体（Ｇ）を提供
するものであり、また、かかる新規な共重合体（Ｇ）と
他の熱可塑性樹脂とを含有する熱可塑性樹脂組成物およ
びそれを用いて成形した樹脂成形品を提供するものであ
る。以下本発明をその構成に従い順次詳細に説明する。That is, in the present invention, the mass average particle diameter is 3
(Meth) acrylic acid ester and a crosslinking agent and / or a graft crossing agent as essential components in 3 to 50 parts by weight of the crosslinked acrylic acid ester-based rubbery polymer (A) and polyorganosiloxane (S) of 00 nm to 2000 nm. A novel copolymer (G) obtained by further polymerizing a vinyl-based monomer is added to the composite rubber polymer (R) obtained by polymerizing 50 to 97 parts by weight of the monomer mixture (B). The present invention also provides a thermoplastic resin composition containing the novel copolymer (G) and another thermoplastic resin, and a resin molded product molded using the same. Hereinafter, the present invention will be described in detail according to its configuration.
【０００８】[0008]
【発明の実施の形態】本発明のグラフト共重合体を構成
する架橋アクリル酸エステル系ゴム状重合体（Ａ）は、
構成単位として（メタ）アクリル酸エステル単位を必須
成分とする重合体である。この構成単位となっている
（メタ）アクリル酸エステルとしては、アクリル酸メチ
ル、アクリル酸エチル、アクリル酸ｎ−プロピル、アク
リル酸ｎ−ブチル、アクリル酸２−エチルヘキシル等の
アクリル酸アルキルエステルおよびメタクリル酸ヘキシ
ル、メタクリル酸２−エチルヘキシル、メタクリル酸ｎ
−ラウリル等のメタクリル酸アルキルエステルが挙げら
れ、特に、アクリル酸ｎ−ブチルが好ましい。また、架
橋アクリル酸エステル系ゴム状重合体（Ａ）を構成する
単量体混合物中の（メタ）アクリル酸エステルの割合
は、得られる樹脂組成物の耐候性と耐衝撃性とのバラン
スが優れることから、５０〜９９．９質量％が好まし
い。BEST MODE FOR CARRYING OUT THE INVENTION The crosslinked acrylic acid ester rubber-like polymer (A) constituting the graft copolymer of the present invention is
It is a polymer having a (meth) acrylic acid ester unit as an essential component as a constitutional unit. Examples of the (meth) acrylic acid ester serving as the structural unit include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. Hexyl, 2-ethylhexyl methacrylate, n methacrylate
-Methacrylic acid alkyl esters such as lauryl are mentioned, and n-butyl acrylate is particularly preferable. Further, the proportion of the (meth) acrylic acid ester in the monomer mixture constituting the crosslinked acrylic acid ester rubber polymer (A) has an excellent balance between weather resistance and impact resistance of the obtained resin composition. Therefore, 50 to 99.9 mass% is preferable.
【０００９】また、本発明の樹脂組成物の着色性を改善
する目的から、架橋アクリル酸エステル系ゴム状重合体
（Ａ）には架橋剤および／またはグラフト交叉剤を使用
する必要がある。このグラフト交叉剤としては、メタク
リル酸アリル、シアヌル酸トリアリルおよびイソシアヌ
ル酸トリアリル等が挙げられる。そして、架橋剤として
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および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。架橋剤および／また
はグラフト交叉剤の使用量の下限は、特に樹脂組成物の
着色性に影響がでてくることから、架橋アクリル酸エス
テル系ゴム状重合体（Ａ）を形成する単量体混合物に対
し、０．１質量％程度であり、好ましくは０．２％、よ
り好ましくは０．５％である。他方上限は、複合ゴム状
重合体（Ｒ）およびグラフト共重合体（Ｇ）製造時の凝
塊物（カレット）がみられるようになることから５質量
％程度であり、好ましくは３質量％、より好ましくは２
質量％である。Further, for the purpose of improving the colorability of the resin composition of the present invention, it is necessary to use a crosslinking agent and / or a graft crossing agent in the crosslinked acrylic ester type rubbery polymer (A). Examples of the graft crossing agent include allyl methacrylate, triallyl cyanurate and triallyl isocyanurate. Examples of the cross-linking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate. The lower limit of the amount of the cross-linking agent and / or the graft crossing agent used particularly affects the colorability of the resin composition. Therefore, a monomer mixture for forming the cross-linked acrylic acid ester rubber-like polymer (A) is used. On the other hand, it is about 0.1% by mass, preferably 0.2%, and more preferably 0.5%. On the other hand, the upper limit is about 5% by mass, preferably 3% by mass, since agglomerates (cullet) during the production of the composite rubber-like polymer (R) and the graft copolymer (G) can be seen. More preferably 2
It is% by mass.
【００１０】また、本発明の目的である良好な着色性と
光沢度、耐衝撃性に優れた樹脂組成物を得るうえで、架
橋アクリル酸エステル系ゴム状重合体（Ａ）の質量平均
粒子径が重要な要素となる。その下限は、耐衝撃性に影
響がでることから３００ｎｍであり、好ましくは４００
ｎｍ、より好ましくは５００ｎｍである。他方、上限は
特に着色性と光沢度の観点から２０００ｎｍであり、好
ましくは１５００ｎｍ、より好ましくは１０００ｎｍで
ある。Further, in order to obtain a resin composition excellent in coloring property, glossiness and impact resistance, which is the object of the present invention, the mass average particle diameter of the crosslinked acrylic ester type rubbery polymer (A) is obtained. Is an important factor. The lower limit is 300 nm because impact resistance is affected, and preferably 400 nm.
nm, more preferably 500 nm. On the other hand, the upper limit is 2000 nm, preferably 1500 nm, and more preferably 1000 nm, particularly from the viewpoint of colorability and glossiness.
【００１１】架橋アクリル酸エステル系ゴム状重合体
（Ａ）の製造方法については、特に制限されないが、架
橋アクリル酸エステル系ゴム状重合体（Ａ）や複合ゴム
状重合体（Ｒ）、グラフト共重合体（Ｇ）製造時の凝塊
物の発生が少ないことから、ソープフリー重合によって
製造されたものが好ましい。ここでのソープフリー重合
は、乳化剤を全く使用しないで行なう重合を意味するも
のではなく、新たな小粒子の発生を抑制できる範囲（重
合中であれば臨界ミセル濃度以上、もしくは重合完了後
の添加）において、架橋アクリル酸エステル系ゴム状重
合体（Ａ）のラテックス粒子を安定化させるために少量
の乳化剤を補助的に使用することは差し支えない。The method for producing the crosslinked acrylic acid ester-based rubbery polymer (A) is not particularly limited, but the crosslinked acrylic acid ester-based rubbery polymer (A), the composite rubbery polymer (R) and the graft copolymer may be used. The polymer (G) is preferably produced by soap-free polymerization because it produces less agglomerates during production. Soap-free polymerization here does not mean polymerization carried out without using an emulsifier, but within a range in which generation of new small particles can be suppressed (at least the critical micelle concentration during polymerization, or addition after completion of polymerization). In (), a small amount of an emulsifier may be supplementarily used for stabilizing the latex particles of the crosslinked acrylic acid ester rubber-like polymer (A).
【００１２】ソープフリー重合においてカレット生成が
少ない理由は、粒子径分布の比較的狭い架橋アクリル酸
エステル系ゴム状重合体（Ａ）が得られることによると
の推定がなされているが、本発明によれば、それのみで
なく、目的の樹脂組成物の着色性、光沢度、及び耐衝撃
性などにおいても特性を向上する効果がみられた。この
ことから、架橋アクリル酸エステル系ゴム状重合体
（Ａ）中に存在する粒子径が２００ｎｍ以下の粒子は１
０質量％以下であることが好ましく、さらに５質量％以
下がより好ましい。It is presumed that the reason why the cullet formation is small in the soap-free polymerization is that the crosslinked acrylate rubber polymer (A) having a relatively narrow particle size distribution is obtained. According to the above, not only that, but the effect of improving the properties was observed in the coloring property, glossiness, impact resistance and the like of the intended resin composition. From this, the number of particles having a particle diameter of 200 nm or less present in the crosslinked acrylic acid ester-based rubbery polymer (A) is 1
It is preferably 0% by mass or less, and more preferably 5% by mass or less.
【００１３】ポリオルガノシロキサン（Ｓ）としては、
特に制限はないが、ビニル重合性官能基をもつポリオル
ガノシロキサンが好ましい。さらに好ましくは、ビニル
重合性官能基を含有するシロキサン単位０．３〜３モル
％と、ジメチルシロキサン単位９７〜９９．７モル％か
らなり、さらに３個以上のシロキサン結合を有するケイ
素原子がポリジメチルシロキサン中の全ケイ素原子に対
し１モル％以下のポリオルガノシロキサンである。ポリ
オルガノシロキサン（Ｓ）の製造に用いるジメチルシロ
キサンとしては、３員環以上のジメチルシロキサン系環
状体が挙げられ、３〜７員環のものが好ましい。具体的
にはヘキサメチルシクロトリシロキサン、オクタメチル
シクロテトラシロキサン、デカメチルシクロペンタシロ
キサン、ドデカメチルシクロヘキサシロキサン等が挙げ
られ、これらを単独でまたは二種以上混合して用いられ
る。As the polyorganosiloxane (S),
Although not particularly limited, a polyorganosiloxane having a vinyl polymerizable functional group is preferable. More preferably, it is composed of 0.3 to 3 mol% of a siloxane unit containing a vinyl-polymerizable functional group and 97 to 99.7 mol% of a dimethylsiloxane unit, and the silicon atom having three or more siloxane bonds is polydimethyl. It is 1 mol% or less of polyorganosiloxane with respect to all silicon atoms in siloxane. Examples of the dimethylsiloxane used for producing the polyorganosiloxane (S) include 3-membered or higher-membered dimethylsiloxane cyclic compounds, and those having a 3- to 7-membered ring are preferable. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc. These may be used alone or in combination of two or more.
【００１４】また、ビニル重合性官能基含有シロキサン
としては、ビニル重合性官能基を含有し、かつ、ジメチ
ルシロキサンとシロキサン結合を介して結合しうるもの
であり、ジメチルシロキサンとの反応性を考慮するとビ
ニル重合性官能基を含有する各種アルコキシシラン化合
物が好ましい。具体的には、β−メタクリロイルオキシ
エチルジメトキシメチルシラン、γ−メタクリロイルオ
キシプロピルジメトキシメチルシラン、γ−メタクリロ
イルオキシプロピルメトキシジメチルシラン、γ−メタ
クリロイルオキシプロピルトリメトキシシラン、γ−メ
タクリロイルオキシプロピルエトキシジエチルシラン、
γ−メタクリロイルオキシプロピルジエトキシメチルシ
ランおよび∂−メタクリロイルオキシブチルジエトキシ
メチルシラン等のメタクリロイルオキシシロキサン、テ
トラメチルテトラビニルシクロテトラシロキサン等のビ
ニルシロキサン、ｐ−ビニルフエニルジメトキシメチル
シランさらにγ−メルカブトプロピルジメトキシメチル
シラン、γ−メルカプトプロピルトリメトキシシラン等
のメルカプトシロキサンが挙げられる。これらビニル重
合性官能基含有シロキサンは、単独で、または二種以上
の混合物として用いることができる。The vinyl-polymerizable functional group-containing siloxane has a vinyl-polymerizable functional group and can be bonded to dimethylsiloxane through a siloxane bond. Considering the reactivity with dimethylsiloxane. Various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane,
γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane and other methacryloyloxysiloxanes, tetramethyltetravinylcyclotetrasiloxane and other vinylsiloxanes, p-vinylphenyldimethoxymethylsilane and γ-mercapto Examples include mercaptosiloxanes such as propyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These vinyl-polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more kinds.
【００１５】ポリオルガノシロキサン（Ｓ）を製造する
ためには、まず、ジメチルシロキサンとビニル重合性官
能基を含有するシロキサンからなる混合物に、必要に応
じてシロキサン系架橋剤を添加して、乳化剤と水によっ
て乳化させてラテックスを得る。ついで、このラテック
スを高速回転による剪断力で微粒子化するホモミキサー
や、高圧発生機による噴出力で微粒子化するホモジナイ
ザー等を使用して微粒子化させる。ホモジナイザー等の
高圧乳化装置を使用すると、ポリオルガノシロキサン
（Ｓ）ラテックスの粒子径の分布が小さくなるので好ま
しい。そして、この微粒子化後のラテックスを酸触媒が
含まれる酸水溶液中に添加して高温下で重合させる。重
合の停止は、反応液を冷却し、さらに苛性ソーダ、苛性
カリ、炭酸ナトリウムなどのアルカリ性物質で中和する
ことにより行う。In order to produce the polyorganosiloxane (S), first, if necessary, a siloxane-based crosslinking agent is added to a mixture of dimethylsiloxane and a siloxane having a vinyl polymerizable functional group to form an emulsifier. Emulsify with water to obtain a latex. Next, this latex is made into fine particles by using a homomixer for making it into fine particles by shearing force by high-speed rotation, a homogenizer for making fine particles by jetting output from a high-pressure generator, or the like. It is preferable to use a high-pressure emulsifying device such as a homogenizer because the polyorganosiloxane (S) latex has a small particle size distribution. Then, the finely divided latex is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. The termination of the polymerization is carried out by cooling the reaction solution and further neutralizing it with an alkaline substance such as caustic soda, potassium hydroxide and sodium carbonate.
【００１６】上記シロキサン系架橋剤としては、３官能
性または４官能性のシラン系架橋剤、例えばトリメトキ
シメチルシラン、トリエトキシフェニルシラン、テトラ
メトキシシラン、テトラエトキシシラン、テトラブトキ
シシラン等が用いられる。また、乳化剤としては、アニ
オン系乳化剤が好ましく、アルキルベンゼンスルホン酸
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た乳化剤
が使用される。これらの中では、特にアルキルベンゼン
スルホン酸ナトリウム、ラウリルスルホン酸ナトリウム
などのスルホン酸系の乳化剤が好ましい。これらの乳化
剤は、シロキサン混合物１００質量部に対して、０．０
５〜５質量部程度の範囲で使用される。As the siloxane-based crosslinking agent, a trifunctional or tetrafunctional silane-based crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, etc. is used. . As the emulsifier, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, and the like is used. Of these, sulfonic acid emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are particularly preferable. These emulsifiers are used in an amount of 0.0 to 100 parts by mass of the siloxane mixture.
It is used in the range of about 5 to 5 parts by mass.
【００１７】ポリオルガノシロキサン（Ｓ）の重合に用
いる酸触媒としては、脂肪族スルホン酸、脂肪族置換ベ
ンゼンスルホン酸、脂肪族置換ナフタレンスルホン酸な
どのスルホン酸類および硫酸、塩酸、硝酸などの鉱酸類
が挙げられる。これらの酸触媒は一種でまたは二種以上
を組み合わせて用いられる。また、これらの中では、ポ
リオルガノシロキサンラテックスの安定化作用にも優れ
ているため、脂肪族置換ベンゼンスルホン酸が好まし
く、ｎ−ドデシルベンゼンスルホン酸が特に好ましい。
また、ｎ−ドデシルベンゼンスルホン酸と硫酸などの鉱
酸とを併用すると、ポリオルガノシロキサンラテックス
に使用した乳化剤の色が樹脂組成物成形品の色に与える
影響を小さく抑えることができる。ポリオルガノシロキ
サン（Ｓ）粒子の大きさには特に制限はないが、得られ
る樹脂組成物の光沢度および着色性が優れることから、
質量平均粒子径の下限３０ｎｍ、好ましくは４０ｎｍ、
より好ましくは５０ｎｍである。また同じくその上限は
５００ｎｍ、より好ましくは４００ｎｍ、さらに好まし
くは３００ｎｍ以下である。Examples of the acid catalyst used for the polymerization of polyorganosiloxane (S) include sulfonic acids such as aliphatic sulfonic acid, aliphatic-substituted benzenesulfonic acid and aliphatic-substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid. Is mentioned. These acid catalysts may be used alone or in combination of two or more. Among these, aliphatic-substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable, because it has an excellent stabilizing effect on the polyorganosiloxane latex.
When n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the effect of the color of the emulsifier used in the polyorganosiloxane latex on the color of the resin composition molded article can be suppressed to a small level. The size of the polyorganosiloxane (S) particles is not particularly limited, but since the obtained resin composition has excellent gloss and colorability,
The lower limit of the mass average particle diameter is 30 nm, preferably 40 nm,
More preferably, it is 50 nm. Similarly, the upper limit is 500 nm, more preferably 400 nm, and further preferably 300 nm or less.
【００１８】次に、複合ゴム状重合体（Ｒ）は、架橋ア
クリル酸エステル系ゴム状重合体（Ａ）およびポリオル
ガノシロキサン（Ｓ）存在下で、（メタ）アクリル酸エ
ステルとグラフト交叉剤および／または架橋剤とからな
る（メタ）アクリル酸エステル単量体混合物（Ｂ）を乳
化重合することによって調製することができる。ここで
の乳化重合は、架橋剤および／またはグラフト交叉剤を
含む（メタ）アクリル酸エステル単量体混合物を一括重
合させることの望ましい。なお、グラフト交叉剤、架橋
剤は前述のものと同種のものが利用できる。Next, the composite rubber-like polymer (R) is mixed with the (meth) acrylic acid ester and the graft crossing agent in the presence of the cross-linked acrylic acid ester rubber-like polymer (A) and the polyorganosiloxane (S). It can be prepared by emulsion-polymerizing a (meth) acrylic acid ester monomer mixture (B) composed of / or a crosslinking agent. In the emulsion polymerization here, it is desirable to collectively polymerize a (meth) acrylic acid ester monomer mixture containing a crosslinking agent and / or a graft crossing agent. The graft crossing agent and the cross-linking agent may be the same as those mentioned above.
【００１９】上記一括重合とは、（メタ）アクリル酸エ
ステル単量体混合物（Ｂ）の全量または５０％を越える
量を架橋アクリル酸エステル系ゴム状重合体（Ａ）およ
びポリオルガノシロキサン（Ｓ）の混合ラテックスに添
加し、これに適正な重合開始剤を添加して行なう方法を
指す。架橋アクリル酸エステル系ゴム状重合体（Ａ）お
よびポリオルガノシロキサン（Ｓ）混合ラテックスおよ
び重合開始剤存在下で、（メタ）アクリル酸エステル単
量体混合物（Ｂ）の全量または５０％を越える量を連続
的に供給して重合せしめた場合には、本発明の目的であ
る優れた発色性と耐衝撃性は発現し得ない。The above-mentioned batch polymerization means that the total amount or more than 50% of the (meth) acrylic acid ester monomer mixture (B) is cross-linked acrylic acid ester type rubbery polymer (A) and polyorganosiloxane (S). The method is carried out by adding a suitable polymerization initiator to this mixed latex. The total amount of the (meth) acrylic acid ester monomer mixture (B) or the amount exceeding 50% in the presence of the mixed latex of the crosslinked acrylic acid ester-based rubbery polymer (A) and the polyorganosiloxane (S) and the polymerization initiator. When the above is continuously fed and polymerized, the excellent color developability and impact resistance, which are the objects of the present invention, cannot be exhibited.
【００２０】複合ゴム状重合体（Ｒ）中の架橋アクリル
酸エステル系ゴム状重合体（Ａ）およびポリオルガノシ
ロキサン（Ｓ）の使用量は、得られる樹脂組成物の低温
での耐衝撃性と光沢度、着色性が良好となることから、
その合計量として、２質量％〜５０質量％であり、好ま
しくは５質量％〜４０質量％、さらに好ましくは１０質
量％〜３０質量％である。また、各々の量として、目的
の樹脂組成物の耐衝撃性が良好となることから、複合ゴ
ム状重合体（Ｒ）％中。架橋アクリル酸エステル系ゴム
状重合体（Ａ）の下限は１質量％で、好ましくは３質量
％、さらに好ましくは５質量％である。また、得られる
樹脂組成物の着色性および光沢度が良好となることか
ら、上限は４０質量％で、好ましくは３０質量％、さら
に好ましくは２０質量％である。The amounts of the crosslinked acrylic acid ester type rubbery polymer (A) and polyorganosiloxane (S) used in the composite rubbery polymer (R) depend on the impact resistance of the resulting resin composition at low temperature. Since the glossiness and colorability are good,
The total amount thereof is 2% by mass to 50% by mass, preferably 5% by mass to 40% by mass, and more preferably 10% by mass to 30% by mass. Moreover, since the impact resistance of the intended resin composition is good as the respective amounts, it is in the composite rubber-like polymer (R)%. The lower limit of the crosslinked acrylic acid ester rubber polymer (A) is 1% by mass, preferably 3% by mass, more preferably 5% by mass. Further, the upper limit is 40% by mass, preferably 30% by mass, and more preferably 20% by mass, since the obtained resin composition has good colorability and glossiness.
【００２１】さらに、目的とする樹脂組成物の低温での
耐衝撃性が良好となることから、複合ゴム状重合体
（Ｒ）中、ポリオルガノシロキサン（Ｓ）の下限は１質
量％、好ましくは３質量％、さらに好ましくは５質量％
である。他方、樹脂組成物の着色性および光沢度が良好
となることから、上限は４０質量％、好ましくは３０質
量％、さらに好ましくは２０質量％である。このように
して得られた複合ゴム状重合体（Ｒ）の質量平均粒子径
は、１００ｎｍ〜４００ｎｍであり、好ましくは１３０
ｎｍ〜３００ｎｍ、より好ましくは１６０ｎｍ〜２５０
ｎｍの範囲のものである。複合ゴム状重合体（Ｒ）の質
量平均粒子径がこのような範囲にあると、耐衝撃性や着
色性、光沢度が優れた熱可塑性樹脂組成物を得ることが
できる。Further, since the desired resin composition has good impact resistance at low temperature, the lower limit of the polyorganosiloxane (S) in the composite rubber polymer (R) is 1% by mass, preferably 3% by mass, more preferably 5% by mass
Is. On the other hand, the upper limit is 40% by mass, preferably 30% by mass, and more preferably 20% by mass, because the colorability and gloss of the resin composition are good. The composite rubber-like polymer (R) thus obtained has a mass average particle diameter of 100 nm to 400 nm, preferably 130 nm.
nm-300 nm, more preferably 160 nm-250
in the nm range. When the mass average particle diameter of the composite rubber-like polymer (R) is in such a range, a thermoplastic resin composition having excellent impact resistance, coloring property and glossiness can be obtained.
【００２２】また、複合ゴム状重合体（Ｒ）の粒子径分
布は、グラフト共重合体（Ｇ）を含む熱可塑性樹脂組成
物の高温成形時の光沢や耐衝撃性が優れることから、複
合ゴム状重合体（Ｒ）中に占める２００ｎｍ未満の粒子
の質量割合は、１０質量％〜９０質量％、好ましくは２
０質量％〜８０質量％、より好ましくは３０質量％〜７
０質量％である。複合ゴム状重合体（Ｒ）の粒子径分布
をこのように制御する方法には制限はないが、例えば、
前述のごとく架橋アクリル酸エステル系ゴム状重合体
（Ａ）に（メタ）アクリル酸エステル単量体混合物
（Ｂ）の全量または５０％を越える量を一括重合させる
方法や、予め製造しておいた２００ｎｍを超える複合ゴ
ム状重合体と２００ｎｍ未満のゴム質重合体とを混合す
る方法、あるいは適正な乳化剤を用いて重合する方法等
が挙げられる。これらの中では、適性な乳化剤を使用す
る方法が、製造プロセスが簡単であるため好ましい。The particle size distribution of the composite rubber-like polymer (R) is excellent in gloss and impact resistance at the time of high temperature molding of the thermoplastic resin composition containing the graft copolymer (G). The mass ratio of particles of less than 200 nm in the polymer (R) is 10% by mass to 90% by mass, preferably 2% by mass.
0 mass% to 80 mass%, more preferably 30 mass% to 7
It is 0 mass%. The method for controlling the particle size distribution of the composite rubber-like polymer (R) in this way is not limited, but, for example,
As described above, the cross-linked acrylic acid ester-based rubber-like polymer (A) is batch polymerized with the total amount of the (meth) acrylic acid ester monomer mixture (B) or an amount exceeding 50%, or prepared in advance. Examples thereof include a method of mixing a composite rubber-like polymer having a particle size of more than 200 nm and a rubbery polymer having a particle size of less than 200 nm, or a method of polymerizing using a proper emulsifier. Among these, the method of using a suitable emulsifier is preferable because the manufacturing process is simple.
【００２３】上記乳化重合では、乳化剤が１０〜５０Å
２、好ましくは１０〜４０Å２の分子占有面積を持つも
のが適している。このような分子占有面積の乳化剤を用
いると、ゴム質重合体の重合中に２００ｎｍ未満の粒子
が生成し、一度で望ましい粒子径分布のものが得られ
る。上記分子占有面積を有する乳化剤の例としては、オ
レイン酸、ステアリン酸、ミリスチン酸、ステアリン
酸、パルミチン酸等の脂肪酸のナトリウムまたはカリウ
ム塩、ラウリル硫酸ナトリウム、Ｎ−ラウロイルサルコ
シン酸ナトリウム、アルケニルコハク酸ジカリウム、ア
ルキルジフェニルエーテルジスルホン酸ナトリウム等を
例示できる。これらのなかでは、一分子中に官能基を二
つ以上有する酸型乳化剤またはその塩を用いると、熱可
塑性樹脂組成物の成形時のガス発生をより抑制でき好ま
しい。具体的には、アルケニルコハク酸ジカリウムまた
はアルキルジフェニルエーテルジスルホン酸ナトリウム
である。さらに、硫酸を使用して、ラテックスからゴム
質重合体を凝固させ回収することが容易であるため、ア
ルケニルコハク酸ジカリウムがより好ましい。アルケニ
ルコハク酸ジカリウムとしては、オクタデセニルコハク
酸ジカリウム、ヘプタデセニルコハク酸ジカリウム、ヘ
キサデセニルコハク酸ジカリウムなどがある。この場
合、全乳化剤量の５０質量％未満の範囲で他の乳化剤を
併用してもよい。In the above emulsion polymerization, the emulsifier is 10 to 50Å
Those having a molecular occupation area of 2 , preferably 10 to 40Å 2 are suitable. When an emulsifier having such a molecular occupied area is used, particles having a particle size of less than 200 nm are generated during the polymerization of the rubbery polymer, and a desired particle size distribution can be obtained at one time. Examples of the emulsifier having the above-mentioned molecular occupied area are sodium or potassium salts of fatty acids such as oleic acid, stearic acid, myristic acid, stearic acid and palmitic acid, sodium lauryl sulfate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate. , Sodium alkyl diphenyl ether disulfonate, and the like. Among these, it is preferable to use an acid-type emulsifier having two or more functional groups in one molecule or a salt thereof because gas generation during molding of the thermoplastic resin composition can be further suppressed. Specifically, it is dipotassium alkenyl succinate or sodium alkyl diphenyl ether disulfonate. Further, dipotassium alkenyl succinate is more preferred because it is easy to coagulate and recover the rubbery polymer from the latex using sulfuric acid. Examples of the dipotassium alkenyl succinate include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, and dipotassium hexadecenyl succinate. In this case, other emulsifiers may be used together within the range of less than 50% by mass of the total amount of emulsifiers.
【００２４】本発明のグラフト共重合体（Ｇ）は、上記
複合ゴム状重合体（Ｒ）に常温下で硬質な重合体を形成
するビニル系単量休または単量体混合物を重合してなる
グラフト重合体であり、この重合に用いることができる
単量体の種類としては特に制限されない。好ましくは、
芳香族アルケニル化合物、メタクリル酸エステル、アク
リル酸エステルおよびシアン化ビニル化合物から選ばれ
る少なくとも一種の単量体が、乳化剤の存在下で乳化グ
ラフト重合に供される。単量体のうち芳香族アルケニル
化合物としては、スチレン、α−メチルスチレン、ビニ
ルトルエン等である。メタクリル酸エステルとしては、
メタクリル酸メチル、メタクリル酸エチル、メタクリル
酸２−エチルヘキシル等である。またアクリル酸エステ
ルとしては、アクリル酸メチル、アクリル酸エチル、ア
クリル酸ｎ−ブチル等である。そして、シアン化ビニル
化合物としては、アクリロニトリル、メタクリロニトリ
ル等である。これらのうち、グラフト共重合体（Ｇ）の
熱安定性が優れることから、単量体としては、スチレン
とアクリロニトリルとの混合物が好ましい。The graft copolymer (G) of the present invention is obtained by polymerizing the above-mentioned composite rubber-like polymer (R) with a vinyl monomer or a monomer mixture which forms a hard polymer at room temperature. It is a graft polymer, and the type of monomer that can be used for this polymerization is not particularly limited. Preferably,
At least one monomer selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters and vinyl cyanide compounds is subjected to emulsion graft polymerization in the presence of an emulsifier. Among the monomers, examples of the aromatic alkenyl compound include styrene, α-methylstyrene, vinyltoluene and the like. As methacrylic acid ester,
Examples thereof include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and the like. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, and n-butyl acrylate. The vinyl cyanide compound is acrylonitrile, methacrylonitrile, or the like. Among these, a mixture of styrene and acrylonitrile is preferable as the monomer because the graft copolymer (G) has excellent thermal stability.
【００２５】また、単量体の量には、特に制限はない
が、グラフト共重合体（Ｇ）を含む熱可塑性樹脂組成物
の耐衝撃性と着色性が優れることから、ゴム質重合体に
対し、好ましくは４０質量部〜２００質量部であり、よ
り好ましくは５０質量部〜１８０質量部、さらに好まし
くは６０質量部〜１５０質量部である。The amount of the monomer is not particularly limited, however, since the thermoplastic resin composition containing the graft copolymer (G) is excellent in impact resistance and colorability, it can be used as a rubbery polymer. On the other hand, it is preferably 40 parts by mass to 200 parts by mass, more preferably 50 parts by mass to 180 parts by mass, further preferably 60 parts by mass to 150 parts by mass.
【００２６】グラフト共重合体（Ｇ）を製造する乳化グ
ラフト重合は、複合ゴム状重合体（Ｒ）ラテックスに、
芳香族アルケニル化合物、メタクリル酸エステル、アク
リル酸エステルおよびシアン化ビニル化合物から選ばれ
る少なくとも一種の単量体を加え、乳化剤の存在下、公
知のラジカル重合技術により行うことができる。また、
単量体中には、グラフト率およびグラフト成分の分子量
の制御のための各種公知の連鎖移動剤を添加することが
できる。上記ラジカル重合開始剤としては、過酸化物、
アゾ系開始剤または酸化剤・還元剤を組み合わせたレド
ックス系開始剤が用いられる。この中でレドックス系開
始剤が好ましく、特に硫酸第一鉄・エチレンジアミン四
酢酸二ナトリウム塩・ロンガリット・ヒドロパーオキサ
イドを組み合わせたスルホキシレート系開始剤が好まし
い。The emulsion graft polymerization for producing the graft copolymer (G) is carried out on the composite rubber-like polymer (R) latex.
It can be carried out by a known radical polymerization technique in the presence of an emulsifier by adding at least one monomer selected from an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester and a vinyl cyanide compound. Also,
Various known chain transfer agents for controlling the graft ratio and the molecular weight of the graft component can be added to the monomer. As the radical polymerization initiator, a peroxide,
An azo initiator or a redox initiator in which an oxidizing agent and a reducing agent are combined is used. Among these, a redox type initiator is preferable, and a sulfoxylate type initiator in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide are combined is particularly preferable.
【００２７】また、上記乳化剤としては、前述のゴム質
重合体の製造に用いた乳化剤と同種の乳化剤が用いられ
る。乳化剤としては特に制限はなく、乳化重合時のラテ
ックスの安定性が優れ、グラフト重合率が高くなり易い
ことから、アルケニルコハク酸ジカリウム、アルキルジ
フェニルエーテルジスルホン酸ナトリウム、Ｎ−ラウロ
イルサルコシン酸ソーダ、脂肪酸カリウム、脂肪酸ナト
リウム、ロジン酸石鹸等の各種カルボン酸塩が挙げられ
る。As the emulsifier, the same type of emulsifier as used in the production of the rubbery polymer described above is used. The emulsifier is not particularly limited, since the stability of the latex during emulsion polymerization is excellent and the graft polymerization rate tends to be high, dipotassium alkenyl succinate, sodium alkyldiphenyl ether disulfonate, sodium N-lauroyl sarcosinate, potassium fatty acid, Examples include various carboxylic acid salts such as sodium fatty acid and rosin acid soap.
【００２８】本発明の目的である良好な耐衝撃性と光沢
度を有する樹脂組成物を得る目的から、グラフト共重合
体（Ｇ）中のアセトン可溶分０．２ｇをＮ，Ｎ−ジメチ
ルホルムアミド溶媒１００ｃｃに溶解した溶液（２５
℃）の還元粘度が０．３〜０．９ｄｌ／ｇであることが
好ましい。この還元粘度が０．３ｄｌ／ｇ未満の場合
は、グラフト共重合体を含む樹脂組成物の耐衝撃性が低
下し、一方、０．９ｄｌ／ｇを超えるとグラフト共重合
体を含む樹脂組成物の低温度成形時の光沢が低下する傾
向にある。より好ましくは０．３５〜０．８ｄｌ／ｇ、
さらに好ましくは０．４〜０．７ｄｌ／ｇである。For the purpose of obtaining a resin composition having good impact resistance and glossiness, which is an object of the present invention, 0.2 g of acetone-soluble matter in the graft copolymer (G) is added to N, N-dimethylformamide. Solution dissolved in 100 cc of solvent (25
The reduced viscosity (° C.) Is preferably 0.3 to 0.9 dl / g. If the reduced viscosity is less than 0.3 dl / g, the impact resistance of the resin composition containing the graft copolymer will decrease, while if it exceeds 0.9 dl / g, the resin composition containing the graft copolymer will be reduced. The luster during low temperature molding tends to decrease. More preferably 0.35 to 0.8 dl / g,
More preferably, it is 0.4 to 0.7 dl / g.
【００２９】グラフト共重合体（Ｇ）は、乳化グラフト
重合で得られたグラフト共重合体（Ｇ）ラテックスか
ら、例えば、擬固剤を溶解させた熱水中に投入すること
によってスラリー状態に凝析する湿式法によって回収し
たり、加熱雰囲気の中にグラフト共重合体（Ｇ）ラテッ
クスを噴霧することにより、半直接的にグラフト共重合
体（Ｇ）を回収するスプレードライ法などの方法によっ
て回収される。上記湿式回収法に用いる凝固剤として
は、硫酸、塩酸、リン酸、硝酸等の無機酸や、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
等を用いることができる。凝固剤の選定は重合で用いた
乳化剤と対にして選定される。すなわち、脂肪酸石鹸や
ロジン酸石鹸等のカルボン酸石鹸のみが使用されていた
場合にはどの様な凝固剤を用いても回収可能であるが、
アルキルベンゼンスルホン酸ナトリウムの様な酸性領域
でも安定な乳化力を示す乳化剤が含まれている場合には
上記無機酸では不十分であり、金属塩を用いる必要があ
る。The graft copolymer (G) is coagulated into a slurry from the latex of the graft copolymer (G) obtained by emulsion graft polymerization by, for example, introducing it into hot water in which a pseudo-solidifying agent is dissolved. Of the graft copolymer (G) by spraying the graft copolymer (G) into the heating atmosphere or by spraying the graft copolymer (G) latex in a heated atmosphere. To be done. As the coagulant used in the wet recovery method, 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 can be used. The coagulant is selected in combination with the emulsifier used in the polymerization. That is, when only carboxylic acid soap such as fatty acid soap and rosin acid soap is used, it can be recovered by using any coagulant,
When an emulsifier showing a stable emulsifying power even in an acidic region such as sodium alkylbenzene sulfonate is contained, the above-mentioned inorganic acid is insufficient and it is necessary to use a metal salt.
【００３０】上記湿式回収法により得られたスラリー状
のグラフト共重合体（Ｇ）から乾燥状態のグラフト共重
合体（Ｇ）とするには、まず残存する乳化剤残渣を水中
に溶出させ、洗浄した後に、このスラリーを遠心もしく
はプレス脱水機で脱水した後に気流乾燥機等で乾燥する
方法、圧搾脱水機や押出機等で脱水と乾燥を同時に実施
する方法などのプロセスを経た後に、乾燥したグラフト
共重合体（Ｇ）を粉体または粒子状で得ることができ
る。また、この際、圧搾脱水機や押出機から排出したも
のを直接、熱可塑性樹脂組成物を製造する押出機や成形
機に送って成型品とすることも可能である。In order to prepare the graft copolymer (G) in a dry state from the slurry-like graft copolymer (G) obtained by the above-mentioned wet recovery method, first, the remaining emulsifier residue is eluted in water and washed. After that, after undergoing a process such as a method of dehydrating this slurry by centrifugation or a press dehydrator and then drying with a gas stream dryer, a method of simultaneously performing dehydration and drying with a press dehydrator, an extruder, etc., the dried graft copolymer The polymer (G) can be obtained in the form of powder or particles. Further, at this time, it is also possible to directly send the product discharged from the press dehydrator or the extruder to an extruder or a molding machine for producing the thermoplastic resin composition to obtain a molded product.
【００３１】本発明のグラフト共重合体（Ｇ）は、単独
で使用しても良いが、他の熱可塑性樹脂（Ｆ）を配合
し、必要に応じてさらに他のグラフト共重合体（Ｃ）を
公知の混練装置で混練することによって、本発明の熱可
塑性樹脂組成物に調製される。この熱可塑性樹脂組成物
は、グラフト共重合体（Ｇ）が１〜１００質量％、他の
グラフト共重合体（Ｃ）が９９〜０質量％、他の熱可塑
性樹脂（Ｆ）が９９〜１質量％の範囲で任意に適宜調製
される。The graft copolymer (G) of the present invention may be used alone, but may be blended with another thermoplastic resin (F) and, if necessary, further another graft copolymer (C). Is kneaded with a known kneading device to prepare the thermoplastic resin composition of the present invention. In this thermoplastic resin composition, the graft copolymer (G) is 1 to 100% by mass, the other graft copolymer (C) is 99 to 0% by mass, and the other thermoplastic resin (F) is 99 to 1%. It is arbitrarily and appropriately prepared in the range of mass%.
【００３２】上記樹脂組成物に配合される他のグラフト
共重合体（Ｃ）としては、ＡＢＳ樹脂（Ｃ−１）、エチ
レン−プロピレン−非共役ジエン系ゴムグラフト共重合
体（Ｃ−２）、ポリジメチルシロキサン／（メタ）アク
リル酸エステル複合ゴムグラフト共重合体（Ｃ−３）か
らなる群から選ばれる少なくとも１種のものが適してい
る。このＡＢＳ樹脂（Ｃ−１）としては、公知のものが
利用でき、ブタジエン系ゴムに対し芳香族アルケニル系
単位、シアン化ビニル系単位、（メタ）アクリル酸エス
テル単位から選ばれた少なくとも１種以上の単位を有す
る重合体がグラフトしたものが挙げられる。また、エチ
レン−プロピレン−非共役ジエン系ゴムグラフト共重合
体（Ｃ−２）は、ＥＰＤＭ（エチレン−プロピレン−非
共役ジエン系ゴム弾性体）に、芳香族アルケニル系単
位、（メタ）アクリル酸エステル単位、シアン化ビニル
系単位から選ばれた少なくとも１種以上の重合体がグラ
フトしたものである。ＥＰＤＭは、エチレン／プロピレ
ン質量比が８０／２０〜３０／７０であり、さらに、ジ
シクロペンタジエン、アルキリデンノルポルネン、１，
４−ヘキサジエン等の非共役ジエンの量が、０．５〜３
０モル％のものが望ましい。エチレン−プロピレン−非
共役ジエン系ゴムに対し芳香族アルケニル系単位、シア
ン化ビニル系単位、（メタ）アクリル酸エステル単位か
ら選ばれた少なくとも１種以上の単位を有する重合体が
グラフトしたものである。Other graft copolymers (C) blended in the above resin composition include ABS resin (C-1), ethylene-propylene-non-conjugated diene rubber graft copolymer (C-2), At least one selected from the group consisting of polydimethylsiloxane / (meth) acrylic acid ester composite rubber graft copolymer (C-3) is suitable. As the ABS resin (C-1), known resins can be used, and at least one selected from an aromatic alkenyl unit, a vinyl cyanide unit, and a (meth) acrylic acid ester unit with respect to butadiene rubber. The polymer grafted with the polymer having the unit of is mentioned. Further, the ethylene-propylene-non-conjugated diene rubber graft copolymer (C-2) is obtained by adding EPDM (ethylene-propylene-non-conjugated diene rubber elastic body) to aromatic alkenyl units and (meth) acrylic acid ester. Unit, and at least one polymer selected from vinyl cyanide units. EPDM has an ethylene / propylene mass ratio of 80/20 to 30/70, and further includes dicyclopentadiene, alkylidene norporne, 1,
The amount of non-conjugated diene such as 4-hexadiene is 0.5 to 3
0 mol% is preferable. A polymer obtained by grafting an ethylene-propylene-non-conjugated diene rubber with a polymer having at least one unit selected from aromatic alkenyl units, vinyl cyanide units and (meth) acrylic acid ester units. .
【００３３】また、ポリジメチルシロキサン／（メタ）
アクリル酸エステル複合ゴムグラフト共重合体（Ｃ−
３）は、ポリオルガノシロキサンに（メタ）アクリル酸
エステル系重合体が複合化された複合ゴム質重合体に対
して、芳香族アルケニル化合物、メタクリル酸エステ
ル、アクリル酸エステルおよびシアン化ビニル化合物か
ら選ばれる少なくとも１種の単量体がグラフト重合して
いるものである。Further, polydimethylsiloxane / (meth)
Acrylic ester composite rubber graft copolymer (C-
3) is selected from an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester and a vinyl cyanide compound for a composite rubbery polymer in which a (meth) acrylic acid ester-based polymer is composited with a polyorganosiloxane. At least one kind of monomer is graft-polymerized.
【００３４】上記他の熱可塑性樹脂（Ｆ）としては、特
に制限はなく、ポリメタクリル酸メチル、アクリロニト
リル−スチレン共重合体（ＡＳ樹脂）、アクリロニトリ
ル−スチレン−Ｎ−置換マレイミド三元共重合体、スチ
レン−無水マレイン酸共重合体、スチレン−無水マレイ
ン酸−Ｎ−置換マレイミド三元共重合体、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、ポリエチレン、ポリプロピレン等のポリ
オレフイン、スチレン−ブタジエンースチレン（ＳＢ
Ｓ）、スチレン−ブタジエン（ＳＢＲ）、水素添加ＳＢ
Ｓ、スチレン−イソプレン−スチレン（ＳＩＳ）等のス
チレン系エラストマー、各種オレフィン系エラストマ
ー、各種ポリエステル系エラストマー、ポリスチレン、
メタクリル酸メチル−スチレン共重合体（ＭＳ樹脂）、
アクリロニトリル−スチレン−メタクリル酸メチル共重
合体、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、ＰＰＳ樹脂、ＰＥＳ樹脂、ＰＥＥＫ樹脂、ポリアリ
レート、液晶ポリエステル樹脂およびポリアミド樹脂
（ナイロン）等が挙げられ、これらを単独で、または、
二種以上を併用して用いることができる。The above-mentioned other thermoplastic resin (F) is not particularly limited, and polymethylmethacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, Styrene-maleic anhydride copolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polyethylene, polypropylene Polyolefin, styrene-butadiene-styrene (SB
S), styrene-butadiene (SBR), hydrogenated SB
S, styrene elastomers such as styrene-isoprene-styrene (SIS), various olefin elastomers, various polyester elastomers, polystyrene,
Methyl methacrylate-styrene copolymer (MS resin),
Acrylonitrile-styrene-methyl methacrylate copolymer, polyacetal resin, modified polyphenylene ether (modified PPE resin), ethylene-vinyl acetate copolymer, PPS resin, PES resin, PEEK resin, polyarylate, liquid crystal polyester resin and polyamide resin ( Nylon) and the like, and these alone or
Two or more kinds can be used in combination.
【００３５】本発明の熱可塑性樹脂組成物は、さらに、
粉末、ビーズ、またはペレット状の熱可塑性樹脂（Ｆ）
とグラフト共重合体（Ｇ）、その他のグラフト共重合体
（Ｔ）の所定量を混合し、この混合物を溶融混練する方
法で製造できる。溶融混練する際には、押出機または、
バンバリーミキサー、加圧ニーダー、ロール等の混練機
等を用いる。グラフト共重合体（Ｇ）やこれを含む熱可
塑性樹脂組成物は、そのまま成形品の製造原料に供する
ことができる。また、必要に応じて、この熱可塑性樹脂
組成物に、染料、顔料、安定剤、補強剤、充填材、難燃
剤、発泡剤、滑剤、可塑剤、帯電防止剤等を配合するこ
とができる。そして、このようにして得られた熱可塑性
樹脂組成物は、射出成形法、押出成形法、ブロー成形
法、圧縮成形法、カレンダー成形法、インフレーション
成形法等の各種成形方法によって、目的の成形品とされ
る。The thermoplastic resin composition of the present invention further comprises
Powder, beads or pellets of thermoplastic resin (F)
And a graft copolymer (G) and other graft copolymers (T) are mixed in a predetermined amount, and the mixture is melt-kneaded. When melt-kneading, extruder or
A Banbury mixer, a pressure kneader, a kneader such as a roll, or the like is used. The graft copolymer (G) and the thermoplastic resin composition containing the same can be directly used as a raw material for producing a molded article. If necessary, a dye, a pigment, a stabilizer, a reinforcing agent, a filler, a flame retardant, a foaming agent, a lubricant, a plasticizer, an antistatic agent and the like can be added to the thermoplastic resin composition. Then, the thermoplastic resin composition obtained in this manner is a desired molded product by various molding methods such as injection molding method, extrusion molding method, blow molding method, compression molding method, calender molding method and inflation molding method. It is said that
【００３６】本発明のグラフト共重合体（Ｇ）を含む熱
可塑性樹脂組成物は様々な成形品に使用でき、工業的用
途例としては、車両部品、特に無塗装で使用される各種
外装・内装部品、壁材、窓枠等の建材部品、食器、玩
具、掃除機ハウジング、テレビジョンハウジング、エア
コンハウジング等の家電部品、インテリア部材、船舶部
材および通信機器ハウジング、ノートパソコンハウジン
グ、ＰＤＡハウジング、液晶プロジェクターハウジング
等の電機機器ハウジングが挙げられる。The thermoplastic resin composition containing the graft copolymer (G) of the present invention can be used for various molded articles, and as an industrial application example, vehicle parts, especially various exteriors and interiors used without coating. Parts, wall materials, building materials such as window frames, tableware, toys, vacuum cleaner housings, television housings, air conditioner housings and other home electric appliance parts, interior members, ship members and communication device housings, laptop computer housings, PDA housings, liquid crystal projectors An electrical equipment housing such as a housing may be used.
【００３７】[0037]
【実施例】以下、実施例および比較例により本発明をさ
らに具体的に説明するが、本発明はその要旨を越えない
限り、以下の例に限定されるものではない。なお、以下
の例中の％および部数は明記しない限り質量基準とす
る。The present invention will be described in more detail below 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 addition,% and the number of parts in the following examples are based on mass unless otherwise specified.
【００３８】［製造例１］前駆架橋アクリル酸エステル
系ゴム状重合体（Ｘ）の製造
試薬注入容器、冷却管、ジャケット加熱機、温度計およ
び攪拌装置を備えたガラス製反応器内に、
イオン交換水（以下、水と略記） １，４００部
ホウ酸 ３．５部
無水炭酸ナトリウム ０．３５部
を投入し、攪拌下で内温を窒素雰囲気下で８０℃に昇温
した。５分後、過硫酸カリウム１．３部および水１０部
からなる水溶液を添加した。さらに５分後、
アクリル酸ｎ−ブチル １００部
ｎ−オクチルメルカプタン ５部
からなる混合物を一括添加した。すぐに重合が開始し、
内温８０℃のままで９０分間保持し冷却した。固形分
５．７％、質量平均粒子径は２６０ｎｍである前駆架橋
アクリル酸エステル系ゴム状重合体（Ｘ）を得た。Production Example 1 Production of Precursor Acrylic Ester Rubber Polymer (X) In a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer and a stirrer, Exchanged water (hereinafter abbreviated as water) 1,400 parts Boric acid 3.5 parts Anhydrous sodium carbonate 0.35 parts were added, and the internal temperature was raised to 80 ° C. under a nitrogen atmosphere while stirring. After 5 minutes, an aqueous solution of 1.3 parts potassium persulfate and 10 parts water was added. After a further 5 minutes, a mixture of 100 parts of n-butyl acrylate and 5 parts of n-octyl mercaptan was added all at once. Polymerization starts immediately,
The internal temperature was kept at 80 ° C. for 90 minutes and cooled. A precursor crosslinked acrylate rubber polymer (X) having a solid content of 5.7% and a mass average particle diameter of 260 nm was obtained.
【００３９】［製造例２］架橋アクリル酸エステル系ゴ
ム状重合体（Ａ−１）の製造
試薬注入容器、冷却管、ジャケット加熱機、温度計およ
び攪拌装置を備えたガラス製反応器内に、
水 ３６０部
ホウ酸 １．０部
無水炭酸ナトリウム ０．１部
前駆架橋アクリル酸エステル系ゴム状重合体（Ｘ、固形分） ６．４部
からなる混合物に、室温、攪拌下にて
アクリル酸ｎ−ブチル ９３．６部
メタクリル酸アリル ０．３部
１，３−ブチレンジメタクリル酸エステル ０．１５部
からなる混合物を窒素雰囲気下、１８０分かけて滴下供
給した。終了後、内温を６５℃に昇温した。これに過硫
酸カリウム０．２部および水１０部からなる水溶液を添
加して重合を開始せしめた。この際、ジャケット温度を
制御して内温を９０℃を超えない様にコントロールし
た。発熱ピーク１５分後に、過硫酸カリウム０．１部お
よび水５部からなる水溶液を添加し、さらに内温を７５
℃になるように６０分間保持し、冷却した。冷却後、ラ
テックス安定化のために、アルケニルコハク酸ジカリウ
ム（花王（株）社製「ラテムルＡＳＫ」、以下同じ）を
１．０部添加し、架橋アクリル酸エステル系ゴム状重合
体（Ａ−１）を得た。質量平均粒子径は７６０ｎｍ、２
００ｎｍ以下の粒子の比率は３％であった。Production Example 2 Production of Crosslinked Acrylate Ester Rubber Polymer (A-1) In a glass reactor equipped with a reagent injection container, a cooling pipe, a jacket heater, a thermometer and a stirrer, Water 360 parts Boric acid 1.0 part Anhydrous sodium carbonate 0.1 part Precursor cross-linked acrylic acid ester rubber polymer (X, solid content) A mixture of 6.4 parts was added at room temperature under stirring to acrylic acid n. -Butyl 93.6 parts Allyl methacrylate 0.3 parts 1,3-butylenedimethacrylic acid ester 0.15 parts A mixture consisting of 0.15 parts was added dropwise under a nitrogen atmosphere over 180 minutes. After the completion, the internal temperature was raised to 65 ° C. An aqueous solution containing 0.2 part of potassium persulfate and 10 parts of water was added to this to initiate polymerization. At this time, the jacket temperature was controlled so that the internal temperature did not exceed 90 ° C. 15 minutes after the exothermic peak, an aqueous solution containing 0.1 part of potassium persulfate and 5 parts of water was added, and the internal temperature was adjusted to 75
It was kept at 60 ° C. for 60 minutes and cooled. After cooling, 1.0 part of dipotassium alkenyl succinate (“Latemur ASK” manufactured by Kao Corporation, the same applies hereinafter) was added to stabilize the latex, and a crosslinked acrylic ester rubbery polymer (A-1 ) Got. Mass average particle diameter is 760 nm, 2
The ratio of particles having a size of 00 nm or less was 3%.
【００４０】［製造例３］架橋アクリル酸エステル系ゴ
ム状重合体（Ａ−２）の製造
前駆架橋アクリル酸エステル系ゴム状重合体（Ｘ）の量
を１部に、アクリル酸ｎ−ブチルの量を９９部に変更し
た以外は、製造例２と同様にして重合を行い、質量平均
粒子径が１，１５０ｎｍ、２００ｎｍ以下の粒子の比率
が２％の架橋アクリル酸エステル系ゴム状重合体（Ａ−
２）を得た。[Production Example 3] Production of Crosslinked Acrylate Ester Rubber Polymer (A-2) Pre-crosslinked acrylic ester rubber polymer (X) was added to 1 part of n-butyl acrylate. Polymerization was performed in the same manner as in Production Example 2 except that the amount was changed to 99 parts, and the cross-linked acrylic acid ester rubber-like polymer (mass average particle diameter of 1,150 nm and the proportion of particles of 200 nm or less was 2% ( A-
2) was obtained.
【００４１】［製造例４］架橋アクリル酸エステル系ゴ
ム状重合体（Ａ−３）の製造
前駆架橋アクリル酸エステル系ゴム状重合体（Ｘ）の量
を９部に、アクリル酸ｎ−ブチルの量を９１部に変更し
た以外は、製造例２と同様にして重合を行い、質量平均
粒子径が６６０ｎｍ、２００ｎｍ以下の粒子の比率が３
％の架橋アクリル酸エステル系ゴム状重合体（Ａ−３）
を得た。Production Example 4 Production of Crosslinked Acrylate Ester Rubber Polymer (A-3) The amount of the precursor crosslinked acrylic ester rubber polymer (X) was set to 9 parts, and n-butyl acrylate was added. Polymerization was performed in the same manner as in Production Example 2 except that the amount was changed to 91 parts, and the mass average particle diameter was 660 nm and the ratio of particles having a particle diameter of 200 nm or less was 3.
% Of cross-linked acrylic ester rubber polymer (A-3)
Got
【００４２】［製造例５］架橋アクリル酸エステル系ゴ
ム状重合体（Ａ−４）の製造
前駆架橋アクリル酸エステル系ゴム状重合体（Ｘ）の量
を１２部に、アクリル酸ｎ−ブチルの量を８８部に変更
した以外は、製造例２と同様にして重合を行い、質量平
均粒子径が４６０ｎｍ、２００ｎｍ以下の粒子の比率が
４％の架橋アクリル酸エステル系ゴム状重合体（Ａ−
４）を得た。[Production Example 5] Production of cross-linked acrylic acid ester-based rubbery polymer (A-4) The amount of the precursor cross-linked acrylic acid ester-based rubbery polymer (X) was adjusted to 12 parts, and n-butyl acrylate was added. Polymerization was performed in the same manner as in Production Example 2 except that the amount was changed to 88 parts, and the mass average particle diameter was 460 nm, and the ratio of particles having a particle diameter of 200 nm or less was 4%.
4) was obtained.
【００４３】［製造例６］架橋アクリル酸エステル系ゴ
ム状重合体（Ａ−５）の製造
試薬注入容器、冷却管、ジャケット加熱機、温度計およ
び攪拌装置を備えたガラス製反応器内に、
水 １９０部
ホウ酸 ０．３部
無水炭酸ナトリウム ０．０３部
を投入し、攪拌下で内温を窒素雰囲気下で８０℃に昇温
した。５分後、過硫酸カリウム０．０６部および水５部
からなる水溶液を添加した。さらに５分後、
アクリル酸ｎ−ブチル ７部
ｎ−オクチルメルカプタン ０．３５部
からなる混合物を一括添加した。すぐに重合が開始し、
内温８０℃のままで３０分間保持した。この時点での質
量平均粒子径は２８０ｎｍであった。さらに、
アクリル酸ｎ−ブチル ９３部
メタクリル酸アリル ０．３部
１，３−ブチレンジメタクリル酸エステル ０．１５部
からなる混合物、並びに過硫酸カリウム０．２部と水５
部からなる水溶液を別々の供給口から内温８０℃のまま
で１８０分かけて滴下供給した。滴下終了後、さらに６
０分間その温度のまま保持し、冷却後、ラテックス安定
化のために、アルケニルコハク酸ジカリウムを有効成分
として１．０部添加し、架橋アクリル酸エステル系ゴム
状重合体（Ａ−５）を得た。質量平均粒子径は５２０ｎ
ｍ、２００ｎｍ以下の粒子の比率は４％であった。[Production Example 6] Production of crosslinked acrylic acid ester rubbery polymer (A-5) In a glass reactor equipped with a reagent injection container, a cooling pipe, a jacket heater, a thermometer and a stirrer, 190 parts of water, 0.3 part of boric acid, 0.03 part of anhydrous sodium carbonate were added, and the internal temperature was raised to 80 ° C. under a nitrogen atmosphere while stirring. After 5 minutes, an aqueous solution consisting of 0.06 part potassium persulfate and 5 parts water was added. After a further 5 minutes, a mixture of 7 parts of n-butyl acrylate and 0.35 parts of n-octyl mercaptan was added all at once. Polymerization starts immediately,
The internal temperature was kept at 80 ° C. for 30 minutes. The mass average particle diameter at this point was 280 nm. Furthermore, a mixture of n-butyl acrylate 93 parts allyl methacrylate 0.3 parts 1,3-butylene dimethacrylate 0.15 parts, and 0.2 parts potassium persulfate and 5 parts water.
Part of the aqueous solution was supplied dropwise from separate supply ports over 180 minutes while keeping the internal temperature at 80 ° C. 6 more after dropping
After maintaining the temperature for 0 minutes and cooling, 1.0 part of dipotassium alkenyl succinate as an active ingredient was added to stabilize the latex to obtain a crosslinked acrylate rubber polymer (A-5). It was Mass average particle size is 520n
The ratio of m and particles of 200 nm or less was 4%.
【００４４】［製造例７］架橋アクリル酸エステル系ゴ
ム状重合体（Ａ−６）の製造
前段のアクリル酸ｎ−ブチルおよびｎ−オクチルメルカ
プタンの量をそれぞれ２部および０．１部に、後段のア
クリル酸ｎ−ブチルの量を９８部に変更した以外は、製
造例６と同様にして重合を行い、質量平均粒子径が２７
０ｎｍ、２００ｎｍ以下の粒子の比率が１３％の架橋ア
クリル酸エステル系ゴム状重合体（Ａ−６）を得た。[Production Example 7] Production of crosslinked acrylic acid ester-based rubbery polymer (A-6) The amounts of n-butyl acrylate and n-octyl mercaptan in the former stage were 2 parts and 0.1 part respectively, and the latter stage was 2 parts. Polymerization was performed in the same manner as in Production Example 6 except that the amount of n-butyl acrylate was changed to 98 parts, and the mass average particle diameter was 27.
A crosslinked acrylic acid ester rubber polymer (A-6) having a particle ratio of 0 nm and 200 nm or less of 13% was obtained.
【００４５】
［製造例８］ポリオルガノシロキサン（Ｓ−１）ラテックスの製造
オクタメチルシクロテトラシロキサン ９８部
γ−メタクリロイルオキシプロピルジメトキシメチルシラン ２部
を混合してシロキサン系混合物１００部を得た。これに、
ドデシルベンゼンスルホン酸ナトリウム ０．６７部
水 ３００部
からなる水溶液を添加し、ホモミキサーにて１００００
回転／分で２分間攪拌した後、ホモジナイザーに２０Ｍ
ＰＡの圧力で１回通し、安定な予備混合オルガノシロキ
サンラテックスを得た。一方、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内に、
ドデシルベンゼンスルホン酸 １０部
水 ９０部
を投入し、１０％のドデシルベンゼンスルホン酸水溶液
を調製した。この水溶液を８５℃に加熱した状態で、予
備混合したオルガノシロキサンラテックスを４時間に亘
って滴下し、滴下終了後１時間温度を維持し、冷却し
た。次いでこの反応物を苛性ソーダ水溶液で中和した。
このようにして得られたポリオルガノシロキサン（Ｓ−
１）ラテックスを１７０℃で３０分間乾燥して固形分を
求めたところ、１７．７％であった。また、ラテックス
中のポリオルガノシロキサン（Ｓ−１）の重量平均粒子
径は５０ｎｍであった。Production Example 8 Production of Polyorganosiloxane (S-1) Latex Octamethylcyclotetrasiloxane 98 parts γ-methacryloyloxypropyldimethoxymethylsilane 2 parts were mixed to obtain 100 parts of a siloxane-based mixture. An aqueous solution of sodium dodecylbenzenesulfonate 0.67 parts and water 300 parts was added to this, and the mixture was mixed with a homomixer at 10,000
After stirring for 2 minutes at rotation / minute, add 20M to the homogenizer.
It was passed once under the pressure of PA to obtain a stable premixed organosiloxane latex. On the other hand, reagent injection container, cooling pipe,
Into a reactor equipped with a jacket heater and a stirrer, 10 parts of dodecylbenzenesulfonic acid and 90 parts of water were added to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. With the aqueous solution heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the completion of the addition, the temperature was maintained for 1 hour and cooled. The reaction was then neutralized with aqueous sodium hydroxide solution.
The polyorganosiloxane (S-
1) The latex was dried at 170 ° C. for 30 minutes to determine the solid content, which was 17.7%. The weight average particle diameter of the polyorganosiloxane (S-1) in the latex was 50 nm.
【００４６】
［製造例９］ポリオルガノシロキサン（Ｓ−２）ラテックスの製造
オクタメチルシクロテトラシロキサン ９７．５部
γ−メタクリロイルオキシプロピルジメトキシメチルシラン ０．５部
テトラエトキシシラン ２部
を混合してシロキサン系混合物１００部を得た。これに
ドデシルベンゼンスルホン酸 １部
ドデシルベンゼンスルホン酸ナトリウム １部
水 ２００部
からなる水溶液を添加し、ホモミキサーにて１００００
回転／分で２分間攪拌した後、ホモジナイザーに２０Ｍ
ＰＡの圧力で１回通し、安定な予備混合オルガノシロキ
サンラテックスを得た。この予備混合オルガノシロキサ
ンラテックスを、冷却管、ジャケット加熱器および攪拌
装置を備えた反応器内に入れ、攪拌混合しながら８０℃
で５時間加熱した後約２０℃に冷却し、そのまま４８時
間放置した。次いでこの反応物を苛性ソーダ水溶液でｐ
Ｈ７．０に中和し重合を完結した。このようにして得ら
れたポリオルガノシロキサン（Ｓ−２）ラテックスを１
７０℃で３０分間乾燥して固形分を求めたところ、３
６．５重量％であった。また、ラテックス中のポリオル
ガノシロキサンの重量平均粒子径は１６０ｎｍであっ
た。[Production Example 9] Production of polyorganosiloxane (S-2) latex Octamethylcyclotetrasiloxane 97.5 parts γ-methacryloyloxypropyldimethoxymethylsilane 0.5 parts Tetraethoxysilane 2 parts are mixed to obtain siloxane. 100 parts of system mixture are obtained. An aqueous solution consisting of 1 part of dodecylbenzene sulfonic acid 1 part of sodium dodecylbenzene sulfonate 1 part of water 200 parts was added to this, and a homomixer was used for 10000
After stirring for 2 minutes at rotation / minute, add 20M to the homogenizer.
It was passed once under the pressure of PA to obtain a stable premixed organosiloxane latex. This premixed organosiloxane latex was placed in a reactor equipped with a cooling tube, a jacket heater and a stirrer, and stirred at 80 ° C. while mixing.
After heating for 5 hours at 50 ° C., it was cooled to about 20 ° C. and left for 48 hours. Then, this reaction product was added with a caustic soda aqueous solution to p.
The polymerization was completed by neutralizing to H7.0. 1 of the polyorganosiloxane (S-2) latex thus obtained was used.
When the solid content was determined by drying at 70 ° C for 30 minutes, it was 3
It was 6.5% by weight. The weight average particle diameter of the polyorganosiloxane in the latex was 160 nm.
【００４７】
［製造例１０］ポリオルガノシロキサン（Ｓ−３）ラテックスの製造
オクタメチルシクロテトラシロキサン ９７．５部
γ−メタクリロイルオキシプロピルジメトキシメチルシラン ０．５部
テトラエトキシシラン ２部
を混合してシロキサン系混合物１００部を得た。これに
ドデシルベンゼンスルホン酸 １部
ドデシルベンゼンスルホン酸ナトリウム １部
濃硫酸 ０．５部
水 ２００部
からなる水溶液を添加し、ホモミキサーにて１００００
回転／分で２分間攪拌した後、ホモジナイザーに２０Ｍ
ＰＡの圧力で１回通し、安定な予備混合オルガノシロキ
サンラテックスを得た。この予備混合オルガノシロキサ
ンラテックスを、冷却管、ジャケット加熱器および攪拌
装置を備えた反応器内に入れ、攪拌混合しながら８０℃
で５時間加熱した後約２０℃に冷却し、そのまま４８時
間放置した。次いでこの反応物を苛性ソーダ水溶液でｐ
Ｈ７．０に中和し重合を完結した。このようにして得ら
れたポリオルガノシロキサン（Ｓ−３）ラテックスを１
７０℃で３０分間乾燥して固形分を求めたところ、２
９．１質量％であった。また、ラテックス中のポリオル
ガノシロキサンの重量平均粒子径は４１０ｎｍであっ
た。[Production Example 10] Production of polyorganosiloxane (S-3) latex Octamethylcyclotetrasiloxane 97.5 parts γ-methacryloyloxypropyldimethoxymethylsilane 0.5 parts Tetraethoxysilane 2 parts are mixed to obtain siloxane. 100 parts of system mixture are obtained. To this was added an aqueous solution consisting of 1 part of dodecylbenzene sulfonic acid, 1 part of sodium dodecylbenzene sulfonate, 1 part of concentrated sulfuric acid, 0.5 part of water and 200 parts of a homomixer.
After stirring for 2 minutes at rotation / minute, add 20M to the homogenizer.
It was passed once under the pressure of PA to obtain a stable premixed organosiloxane latex. This premixed organosiloxane latex was placed in a reactor equipped with a cooling tube, a jacket heater and a stirrer, and stirred at 80 ° C. while mixing.
After heating for 5 hours at 50 ° C., it was cooled to about 20 ° C. and left for 48 hours. Then, this reaction product was added with a caustic soda aqueous solution to p.
The polymerization was completed by neutralizing to H7.0. The polyorganosiloxane (S-3) latex thus obtained was
When the solid content was determined by drying at 70 ° C for 30 minutes, 2
It was 9.1 mass%. The weight average particle size of the polyorganosiloxane in the latex was 410 nm.
【００４８】［製造例１１］複合ゴム状重合体（Ｒ−
１）の製造
試薬注入容器、冷却管、ジャケット加熱機、温度計およ
び攪拌装置を備えたガラス製反応器内に、製造例２で調
製した、
架橋アクリル酸エステル系ゴム状重合体（Ａ−２、固形分） １０部
ポリオルガノシロキサン（Ｓ−１、固形分） １０部
アルケニルコハク酸ジカリウム（実量として） ０．２部
水（Ａ−２中の水を含む） ４１０部
を仕込み、これに室温、攪拌下で、
アクリル酸ｎ−ブチル ８０部
メタクリル酸アリル ０．３部
１，３−ブチレングリコールジメタクリレート ０．１５部
ターシャリーブチルヒドロパーオキサイド ０．２部
からなる混合物を添加した。この反応器に窒素気流を通
じることによって、雰囲気の窒素置換を行い、ジャケッ
トを６０℃まで昇温した。内部の液温が５０℃となった
時点で、
硫酸第一鉄七水塩 ０．０００１５部
エチレンジアミン四酢酸二ナトリウム塩 ０．０００４４部
ロンガリット ０．４部
水 １０部
からなる水溶液を添加ラジカル重合を開始させ、内温を
７５℃に上昇させた。１時間この状態を維持しアクリル
酸エステル成分の重合を完結させ、架橋アクリル酸エス
テル系ゴム状重合体（Ａ−１）およびポリオルガノシロ
キサン（Ｓ−１）と（メタ）アクリル酸エステル系単量
体混合物（Ｂ）との複合ゴム状重合体（Ｒ−１）ラテッ
クスを得た。この質量平均粒子径は１９０ｎｍで、全質
量中の２００ｎｍ未満の粒子の質量割合は４２％であっ
た。[Production Example 11] Composite rubber-like polymer (R-
Production of 1) In a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer, and a stirrer, the crosslinked acrylic ester type rubbery polymer (A-2) prepared in Production Example 2 was prepared. , Solid content 10 parts Polyorganosiloxane (S-1, solid content) 10 parts Dipotassium alkenyl succinate (as actual amount) 0.2 parts Water (including water in A-2) 410 parts are charged to this. A mixture consisting of n-butyl acrylate 80 parts allyl methacrylate 0.3 parts 1,3-butylene glycol dimethacrylate 0.15 parts tertiary butyl hydroperoxide 0.2 parts was added at room temperature with stirring. The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and the jacket was heated to 60 ° C. When the internal liquid temperature reached 50 ° C, an aqueous solution containing ferrous sulfate heptahydrate 0.00015 part ethylenediaminetetraacetic acid disodium salt 0.00044 part Rongalit 0.4 part water 10 parts was added and radical polymerization was performed. It was started and the internal temperature was raised to 75 ° C. This state is maintained for 1 hour to complete the polymerization of the acrylic acid ester component, and the crosslinked acrylic acid ester-based rubber-like polymer (A-1) and polyorganosiloxane (S-1) and (meth) acrylic acid ester-based monomer A composite rubber-like polymer (R-1) latex with the body mixture (B) was obtained. The mass average particle diameter was 190 nm, and the mass ratio of particles less than 200 nm in the total mass was 42%.
【００４９】［製造例１２］複合ゴム状重合体（Ｒ−
２）〜（Ｒ−２０）の製造
架橋アクリル酸エステル系ゴム状重合体（Ａ）およびポ
リオルガノシロキサン（Ｓ）の種類と量とを表１に示す
ごとく変更し、それに応じて複合化させるアクリル酸ｎ
−ブチルの量を変更させる以外は、製造例１１と同様に
して重合を行い、複合ゴム状重合体（Ｒ−２）〜（Ｒ−
２０）ラテックスを得た。それらの質量平均粒子径およ
び２００ｎｍ未満の粒子比率を表１に示した。[Production Example 12] Composite rubber-like polymer (R-
2) Production of (R-20) An acrylic compound in which the type and amount of the crosslinked acrylic acid ester rubber-like polymer (A) and polyorganosiloxane (S) are changed as shown in Table 1 and compounded accordingly. Acid n
Polymerization was performed in the same manner as in Production Example 11 except that the amount of butyl was changed, and the composite rubber-like polymers (R-2) to (R-
20) A latex was obtained. Table 1 shows their mass average particle diameters and particle ratios of less than 200 nm.
【００５０】［製造例 １３］ゴム状重合体（Ｋ−１）
の製造
架橋アクリル酸エステル系ゴム状重合体（Ａ）を使用せ
ず、アクリル酸ｎ−ブチルの量を１００部とした以外
は、製造例８と同様にして重合を行い、架橋アクリル酸
エステル系ゴム状重合体（Ａ）を使用しないゴム状重合
体（Ｋ−１）ラテックスを得た。それらの質量平均粒子
径および２００ｎｍ未満の粒子比率を表１に示した。[Production Example 13] Rubber-like polymer (K-1)
The polymerization was carried out in the same manner as in Production Example 8 except that the crosslinked acrylic acid ester-based rubbery polymer (A) was not used and the amount of n-butyl acrylate was 100 parts. A rubber-like polymer (K-1) latex without using the rubber-like polymer (A) was obtained. Table 1 shows their mass average particle diameters and particle ratios of less than 200 nm.
【００５１】[0051]
【表１】 [Table 1]
【００５２】［実施例１］グラフト共重合体（Ｇ−１）
の製造
試薬注入容器、冷却管、ジャケット加熱機、温度計およ
び攪拌装置を備えたガラス製反応器内に、
複合ゴム状重合体（Ｒ−１）ラテックス（固形分） ５０部
水（複合ゴム状重合体（Ｒ）ラテックス中の水を含む） ２１０部
アルケニルコハク酸ジカリウム ０．７部
ロンガリット ０．１５部
を攪拌下にて混合し、内温を７０℃に昇温した。その後、
アクリロニトリル ３部
スチレン ９部
ｔ−ハイドロパーオキサイド ０．１部
からなる混合物を３０分間かけて滴下供給させ重合せしめた。１５分間保持後、
ロンガリット ０．１５部
硫酸第一鉄七水塩 ０．００１部
エチレンジアミン四酢酸二ナトリウム塩 ０．００３部
水 ５部
からなる水溶液を添加し、続けて、
アクリロニトリル ９．５部
スチレン ２８．５部
ｔ−ハイドロパーオキサイド ０．３部
からなる混合物を１２０分かけて滴下供給して重合せし
め、７０℃のまま３０分間保持した後内容物を冷却し
た。得られたグラフト共重合体（Ｇ−１）ラテックス
を、その５０℃である１．５倍量の１％硫酸アルミニウ
ム水溶液中に捜拝下で投入し、さらに７０℃に昇温して
５分間保持し、さらに９０℃に昇温してさらに５分間保
持した。脱水、洗浄を繰り返して最後は気流下にて一昼
夜乾燥させ、白色粉末状であるグラフト共重合体（Ｇ−
１）を得た。このグラフト共重合体（Ｇ−１）のアセト
ン可溶分の還元粘度は０．６１ｄｌ／ｇであった。[Example 1] Graft copolymer (G-1)
In a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer and a stirrer, a composite rubber-like polymer (R-1) latex (solid content) 50 parts water (composite rubber-like Polymer (R) including water in latex) 210 parts Dipotassium alkenyl succinate 0.7 parts Rongalit 0.15 parts were mixed with stirring and the internal temperature was raised to 70 ° C. Then, a mixture consisting of 3 parts of acrylonitrile, 9 parts of styrene and 0.1 part of t-hydroperoxide was added dropwise over 30 minutes for polymerization. After holding for 15 minutes, an aqueous solution consisting of Rongalit 0.15 parts, ferrous sulfate heptahydrate 0.001 parts ethylenediaminetetraacetic acid disodium salt 0.003 parts water 5 parts was added, followed by acrylonitrile 9.5 parts styrene. A mixture of 28.5 parts of t-hydroperoxide (0.3 parts) was added dropwise over 120 minutes to polymerize the mixture, and the mixture was kept at 70 ° C. for 30 minutes and then cooled. The obtained graft copolymer (G-1) latex is put into a 1.5% amount of 1% aluminum sulfate aqueous solution which is 50 ° C. under scrutiny, and the temperature is further raised to 70 ° C. for 5 minutes. The temperature was maintained, the temperature was further raised to 90 ° C., and the temperature was further maintained for 5 minutes. Dehydration and washing were repeated, and finally, the product was dried under an air stream for a whole day and night to give a white powdery graft copolymer (G-
1) was obtained. The reduced viscosity of the acetone-soluble component of this graft copolymer (G-1) was 0.61 dl / g.
【００５３】［実施例２〜１７、比較例１〜７］グラフ
ト共重合体（Ｇ−２）〜（Ｇ−２４）の製造
複合ゴム状重合体（Ｒ−１）を複合ゴム状重合体（Ｒ−
２）〜（Ｒ−２０）、ゴム状重合体（Ｋ−１）に、また
グラフト重合の用いる単量体または単量体混合物の組成
を表２記載のごとく変更した以外は、実施例１と同様に
して重合を行い、グラフト共重合体（Ｇ−２）〜（Ｇ−
２４）を得た。これらグラフト共重合体（Ｇ）のアセト
ン可溶分の還元粘度を表２に示した。[Examples 2 to 17, Comparative Examples 1 to 7] Production of graft copolymers (G-2) to (G-24) The composite rubber-like polymer (R-1) was replaced with the composite rubber-like polymer ( R-
2) to (R-20), the rubber-like polymer (K-1), and Example 1 except that the composition of the monomer or monomer mixture used in the graft polymerization was changed as shown in Table 2. Polymerization is performed in the same manner, and the graft copolymers (G-2) to (G-
24) was obtained. Table 2 shows the reduced viscosities of the acetone-soluble components of these graft copolymers (G).
【００５４】[0054]
【表２】 [Table 2]
【００５５】［製造例１４］他の熱可塑性樹脂（Ｆ−
１）の製造
アクリロニトリル２９部およびスチレン７１部よりな
り、Ｎ，Ｎ−ジメチルホルムアミド溶液から２５℃で測
定した還元粘度が０．６０ｄｌ／ｇであるアクリロニト
リル−スチレン共重合体（Ｆ−１）を公知の懸濁重合に
より製造した。[Production Example 14] Another thermoplastic resin (F-
Production of 1) Acrylonitrile-styrene copolymer (F-1) comprising 29 parts of acrylonitrile and 71 parts of styrene and having a reduced viscosity of 0.60 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution is known. Was prepared by suspension polymerization.
【００５６】［製造例１５］他の熱可塑性樹脂（Ｆ−
２）の製造
アクリロニトリル７部、スチレン２３部、メタクリル酸
メチル７０部よりなり、Ｎ，Ｎ−ジメチルホルムアミド
溶液から２５℃で測定した還元粘度が０．３８ｄｌ／ｇ
であるアクリロニトリル−スチレン−メタクリル酸メチ
ル三元共重合体（Ｆ−２）を公知の懸濁重合により製造
した。[Production Example 15] Another thermoplastic resin (F-
Production of 2) Consists of 7 parts of acrylonitrile, 23 parts of styrene and 70 parts of methyl methacrylate, and has a reduced viscosity of 0.38 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution.
Acrylonitrile-styrene-methyl methacrylate terpolymer (F-2) was produced by known suspension polymerization.
【００５７】［製造例１６］他の熱可塑性樹脂（Ｆ−
３）の製造
アクリロニトリル２０部，スチレン５２部そしてＮ−フ
ェニルマレイミド２８部よりなり、Ｎ，Ｎ−ジメチルホ
ルムアミド溶液から２５℃で測定した還元粘度が０．６
５ｄｌ／ｇであるアクリロニトリルースチレン−Ｎ−フ
ェニルマレイミド三元共重合体（Ｆ−３）を公知の連続
溶液重合により製造した。[Production Example 16] Another thermoplastic resin (F-
3) Preparation of 20 parts of acrylonitrile, 52 parts of styrene and 28 parts of N-phenylmaleimide, and a reduced viscosity of 0.6 measured from an N, N-dimethylformamide solution at 25 ° C.
Acrylonitrile-styrene-N-phenylmaleimide terpolymer (F-3) having a concentration of 5 dl / g was produced by a known continuous solution polymerization.
【００５８】［製造例１７］他の熱可塑性樹脂（Ｆ−
４）の製造
メタクリル酸メチル９９部およびアクリル酸メチル１部
からなり、Ｎ，Ｎ−ジメチルホルムアミド溶液から２５
℃で測定した還元粘度が０．２５ｄｌ／ｇであるアクリ
ル樹脂（Ｆ−４）を公知の懸濁重合により製造した。[Production Example 17] Another thermoplastic resin (F-
4) Preparation of 99 parts of methyl methacrylate and 1 part of methyl acrylate, 25 parts from N, N-dimethylformamide solution
An acrylic resin (F-4) having a reduced viscosity of 0.25 dl / g measured at 0 ° C. was produced by known suspension polymerization.
【００５９】［実施例１８〜５８、比較例８〜２９］熱
可塑性樹脂組成物の製造とその性能評価
実施例１〜１７および比較例１〜７で製造した各グラフ
ト共重合体（Ｇ−１〜２４）、その他の熱可塑性樹脂
（Ｆ−１）〜（Ｆ−４）、ステアリン酸バリウム部０．
３、エチレンビスステアリルアミド０．４部、カーボン
ブラック（三菱化学（株）製＃９６０）０．８部を表３
〜表５に示す比率にてヘンシェルミキサーを用いて混合
し、この混合物を２３０〜２６０℃に加熱した脱気式押
出機（池貝鉄工（株）製ＰＣＭ−３０）に供給し、混練
してペレットを得た。得られたペレットを用いて測定し
たアイゾット衝撃強度、成形光沢、顔料着色性、耐候性
の評価結果を表３〜表５に示す。また、これらの特性評
価は以下の方法にて行った。[Examples 18 to 58, Comparative Examples 8 to 29] Production of thermoplastic resin composition and its performance evaluation Each graft copolymer (G-1 produced in Examples 1 to 17 and Comparative Examples 1 to 7). To 24), other thermoplastic resins (F-1) to (F-4), barium stearate part 0.
3, 0.4 parts of ethylenebisstearylamide and 0.8 parts of carbon black (# 960 manufactured by Mitsubishi Chemical Corporation) are shown in Table 3.
~ Mixing was performed using a Henschel mixer at the ratios shown in Table 5, and this mixture was supplied to a degassing extruder (PCM-30 manufactured by Ikegai Tekko KK) heated to 230 to 260 ° C, kneaded, and pelletized. Got Tables 3 to 5 show the evaluation results of Izod impact strength, molding gloss, pigment colorability, and weather resistance measured using the obtained pellets. Moreover, these characteristics were evaluated by the following methods.
【００６０】（１）アイゾット衝撃強度の測定
ＡＳＴＭ Ｄ−２５６に準拠した方法で行った。低温雰
囲気下でのアイゾット衝撃強度は、−３０℃雰囲気下で
１２時間以上アイゾット試験片を放置した後に測定し
た。
（２）ビカット軟化温度
シリンダー温度２４０℃の２オンス射出成型機で成形し
た試片を用い、ＡＳＴＭ Ｄ−１５２５（４９Ｎ荷重）
に準拠して測定した。(1) Measurement of Izod impact strength The Izod impact strength was measured by the method according to ASTM D-256. The Izod impact strength in a low temperature atmosphere was measured after leaving the Izod test piece for 12 hours or more in an atmosphere of −30 ° C. (2) Vicat softening temperature Using a test piece molded by a 2 ounce injection molding machine with a cylinder temperature of 240 ° C, ASTM D-1525 (49N load)
It was measured according to.
【００６１】（３）熱可塑性樹脂組成物の光沢度
日本製鋼所（株）製射出成形機「Ｊ８５−ＥＬII」を用
いて、シリンダー設定温度２３０℃または２８０℃、金
型温度６０℃、インジェクションスピード５０％の条件
で、１００ｍｍ×１００ｍｍ×３ｍｍ板を成形した。こ
の成形板の光沢度を村上色彩研究所（株）製光沢計「Ｇ
Ｍ−２６Ｄ」で測定した。
（４）熱可塑性樹脂組成物の顔料着色性評価
日本製鋼所（株）製射出成形機「Ｊ８５−ＥＬII」を用
いて、シリンダー設定温度２３０℃、金型温度６０℃、
インジェクションスピード５０％の条件で、１００ｍｍ
×１００ｍｍ×３ｍｍ板を成形した。この黒着色成形板
の色相測定（Ｌ＊測定）を村上色彩研究所（株）製高速
分光光度計「ＣＭＳ−１５００」を用いてＪＩＳ Ｚ８
７２９に準拠して行った。(3) Glossiness of thermoplastic resin composition Using an injection molding machine "J85-ELII" manufactured by Japan Steel Works, Ltd., a cylinder set temperature of 230 ° C or 280 ° C, a mold temperature of 60 ° C, an injection speed. A 100 mm × 100 mm × 3 mm plate was molded under the condition of 50%. The glossiness of this molded plate is measured by Murakami Color Research Laboratory Co., Ltd. “G
M-26D ". (4) Evaluation of Pigment Coloring Property of Thermoplastic Resin Composition Using an injection molding machine "J85-ELII" manufactured by Japan Steel Works, Ltd., a cylinder set temperature is 230 ° C, a mold temperature is 60 ° C,
100 mm at 50% injection speed
A × 100 mm × 3 mm plate was molded. Hue measurement (L * measurement) of this black colored molded plate was performed using a high-speed spectrophotometer “CMS-1500” manufactured by Murakami Color Research Institute Co., Ltd. according to JIS Z8.
It carried out according to 729.
【００６２】（５）耐候性評価
１００ｍｍ×１００ｍｍ×３ｍｍ白着色板をサンシャイ
ンウエザーメーター（スガ試験機（株）製）でブラック
パネル温度６３℃、サイクル条件６０分（降雨：１２
分）にて１，０００時間処理した。その場合の色差計で
測定した変色の度合い（ΔＥ）により評価した。(5) Evaluation of weather resistance A 100 mm × 100 mm × 3 mm white colored plate was placed on a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) with a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall: 12
Min) for 1,000 hours. In that case, the degree of color change (ΔE) measured by a color difference meter was evaluated.
【００６３】[0063]
【表３】 [Table 3]
【００６４】[0064]
【表４】 [Table 4]
【００６５】[0065]
【表５】 [Table 5]
【００６６】以上、各実施例および比較例の結果から次
のことが明らかとなった。
実施例１〜１７で製造したグラフト共重合体（Ｇ−
１）〜（Ｇ−５）、（Ｇ−７）、（Ｇ−８）、（Ｇ−１
０）〜（Ｇ−１５）、（Ｇ−１７）、（Ｇ−２２）〜
（Ｇ−２４）を含有する実施例１８〜５８の樹脂組成物
は、いずれも良好な常温並びに低温でのアイゾット衝撃
強度、光沢度、着色性、そして優れた耐候性を示した。
このような材料は工業的利用価値が極めて高い。
特に、グラフト共重合体（Ｇ−１）、（Ｇ−３）、
（Ｇ−５）、（Ｇ−１４）を含む樹脂組成物は、いずれ
の評価項目においても優れた性能を示した。As described above, the following is clear from the results of the examples and comparative examples. The graft copolymer produced in Examples 1 to 17 (G-
1) to (G-5), (G-7), (G-8), (G-1)
0)-(G-15), (G-17), (G-22)-
The resin compositions of Examples 18 to 58 containing (G-24) all showed good Izod impact strength at room temperature and low temperature, glossiness, colorability, and excellent weather resistance.
Such materials have extremely high industrial utility value. In particular, the graft copolymers (G-1), (G-3),
The resin composition containing (G-5) and (G-14) showed excellent performance in all evaluation items.
【００６７】架橋アクリル酸エステル系ゴム状重合体
（Ａ）の質量平均粒子径が１，０００ｎｍを超えるグラ
フト共重合体（Ｇ−２）を含む樹脂組成物はさらに優れ
たアイゾット衝撃強度を示すものの光沢度および着色性
がやや低下した。また、逆に架橋アクリル酸エステル系
ゴム状重合体（Ａ）の質量平均粒子径が５００ｎｍ未満
であるグラフト共重合体（Ｇ−４）を含む樹脂組成物は
逆に良好な光沢度および着色性を示すもののアイゾット
衝撃強度がやや低下する傾向にあった。The resin composition containing the graft copolymer (G-2) in which the mass average particle diameter of the crosslinked acrylic acid ester rubber polymer (A) exceeds 1,000 nm shows more excellent Izod impact strength. Gloss and colorability were slightly reduced. On the contrary, the resin composition containing the graft copolymer (G-4) in which the cross-linked acrylic acid ester-based rubber-like polymer (A) has a mass average particle diameter of less than 500 nm has good gloss and colorability. However, the Izod impact strength tended to decrease slightly.
【００６８】複合ゴム状重合体中の架橋アクリル酸エ
ステル系ゴム状重合体（Ａ）またはポリオルガノシロキ
サン（Ｓ）のいずれかの比率が低いグラフト共重合体
（Ｇ−７）、（Ｇ−１２）、（Ｇ−１３）を含む樹脂組
成物、または逆に比率の高いグラフト共重合体（Ｇ−
８）、（Ｇ−１５）を含む樹脂組成物は、いずれかの項
目においてやや劣る傾向にあった。
架橋アクリル酸エステル系ゴム状重合体（Ａ）が３０
０ｎｍ未満であるグラフト共重合体（Ｇ−６）、もしく
は架橋アクリル酸エステル系ゴム状重合体（Ａ）を含ま
ないグラフト共重合体（Ｇ−１９）、（Ｇ−２１）を含
む樹脂組成物は、低温でのアイゾット衝撃強度が低かっ
た。Graft copolymers (G-7) and (G-12) in which the ratio of the crosslinked acrylic acid ester rubber polymer (A) or polyorganosiloxane (S) in the composite rubber polymer is low. ), A resin composition containing (G-13), or conversely a high proportion of the graft copolymer (G-
The resin composition containing 8) and (G-15) tended to be slightly inferior in any of the items. Crosslinked acrylic acid ester rubber-like polymer (A) is 30
A resin composition containing a graft copolymer (G-6) having a particle size of less than 0 nm, or a graft copolymer (G-19) not containing the crosslinked acrylic acid ester rubbery polymer (A), (G-21). Had a low Izod impact strength at low temperatures.
【００６９】ポリオルガノシロキサン（Ｓ）を含まな
いグラフト共重合体（Ｇ−１８）を含む樹脂組成物は、
低温でのアイゾット衝撃強度が低かった。
比較例２、３で製造した架橋アクリル酸エステル系ゴ
ム状重合体（Ａ）またはポリオルガノシロキサン（Ｓ）
の比率が複合ゴム状重合体１００質量部中５０質量％と
多いグラフト共重合体（Ｇ−９）、（Ｇ−１６）を含有
する樹脂組成物は、常温でのアイゾット衝撃強度が低
く、なおかつ光沢度と着色性も劣った。The resin composition containing the graft copolymer (G-18) containing no polyorganosiloxane (S) is
The Izod impact strength at low temperature was low. Crosslinked acrylic acid ester-based rubbery polymer (A) or polyorganosiloxane (S) produced in Comparative Examples 2 and 3.
The resin composition containing the graft copolymers (G-9) and (G-16) whose ratio is as high as 50% by mass in 100 parts by mass of the composite rubber-like polymer has low Izod impact strength at room temperature, and The gloss and colorability were also poor.
【００７０】[0070]
【発明の効果】以上詳細に説明したように、本発明の特
定の複合ゴム状重合体を使用したグラフト共重合体
（Ｇ）を含有する熱可塑性樹脂組成物は、常温並びに低
温での耐衝撃性、耐候性に優れ、かつ光沢度および着色
性に優れていることが、極めて成形外観に優れた成形品
を得ることができる。特に、耐衝撃性、耐候性、成形外
観の優れた特性バランスは、従来知られている（メタ）
アクリル酸エステルゴムを構成成分とするグラフト共重
合体を含有する樹脂組成物では得られない極めて高いレ
ベルにある。したがって、本発明の熱可塑性樹脂組成物
は、各種工業材料とりわけ耐候性材料としての工業的利
用価値は極めて高い。As described in detail above, the thermoplastic resin composition containing the graft copolymer (G) using the specific composite rubber-like polymer of the present invention has an impact resistance at room temperature and low temperature. A molded article having excellent properties and weather resistance, and excellent glossiness and colorability makes it possible to obtain a molded article having an excellent molded appearance. In particular, the excellent property balance of impact resistance, weather resistance, and molding appearance has been known (meta).
It is at an extremely high level that cannot be obtained with a resin composition containing a graft copolymer having an acrylic ester rubber as a constituent component. Therefore, the thermoplastic resin composition of the present invention has an extremely high industrial utility value as various industrial materials, especially as a weather resistant material.
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Claims (10)
ｎｍの架橋アクリル酸エステル系ゴム状重合体（Ａ）及
びポリオルガノシロキサン（Ｓ）の合計３〜５０重量部
の存在下に、（メタ）アクリル酸エステルと架橋剤およ
び／またはグラフト交叉剤を必須成分とする単量体混合
物（Ｂ）５０〜９７重量部を重合してなる複合ゴム状重
合体（Ｒ）に、さらにビニル系単量体を重合してなるグ
ラフト共重合体（Ｇ）。1. A mass average particle diameter of 300 nm to 2000.
(meth) acrylic acid ester and a cross-linking agent and / or a graft crossing agent are essential in the presence of a total of 3 to 50 parts by weight of the cross-linked acrylic acid ester-based rubbery polymer (A) and the polyorganosiloxane (S) of 3 nm. A graft copolymer (G) obtained by further polymerizing a vinyl monomer on the composite rubber polymer (R) obtained by polymerizing 50 to 97 parts by weight of the monomer mixture (B) as a component.
（Ａ）が、質量平均粒子径５００ｎｍ〜１０００ｎｍで
ある請求項１記載のグラフト共重合体（Ｇ）。2. The graft copolymer (G) according to claim 1, wherein the crosslinked acrylic acid ester rubber-like polymer (A) has a mass average particle diameter of 500 nm to 1000 nm.
（Ａ）が、ソープフリー重合法により製造されたもので
ある請求項１又は請求項２に記載のいずれかのグラフト
共重合体（Ｇ）。3. The graft copolymer (G) according to claim 1, wherein the crosslinked acrylic ester type rubbery polymer (A) is produced by a soap-free polymerization method. .
均粒子径が、３０ｎｍ〜５００ｎｍのものである請求項
１〜請求項３に記載のいずれかのグラフト共重合体
（Ｇ）。4. The graft copolymer (G) according to claim 1, wherein the polyorganosiloxane (S) has a mass average particle diameter of 30 nm to 500 nm.
以下の粒子径の割合が１０〜９０質量％のものである請
求項１〜請求項４に記載のいずれかのグラフト共重合体
（Ｇ）。5. The composite rubber-like polymer (R) has a thickness of 200 nm.
The graft copolymer (G) according to any one of claims 1 to 4, wherein the ratio of the following particle diameters is 10 to 90% by mass.
タクリレート系化合物である請求項１〜請求項５に記載
のいずれかのグラフト共重合体（Ｇ）。6. The graft copolymer (G) according to any one of claims 1 to 5, wherein the crosslinking agent in the monomer mixture (B) is a dimethacrylate compound.
が、アリル系化合物である請求項１〜請求項６に記載の
いずれかのグラフト共重合体（Ｇ）。7. The graft copolymer (G) according to any one of claims 1 to 6, wherein the graft crossing agent in the monomer mixture (B) is an allyl compound.
チルホルムアミド溶媒１００ｃｃに溶解した溶液（２５
℃）の還元粘度が０．３〜０．９ｄｌ／ｇである請求項
１〜請求項７に記載のいずれかのグラフト共重合体
（Ｇ）。8. A solution (25 g of an acetone-soluble matter dissolved in 100 cc of N, N-dimethylformamide solvent).
8. The graft copolymer (G) according to any one of claims 1 to 7, having a reduced viscosity of 0.3 to 0.9 dl / g.
グラフト共重合体（Ｇ）と他の熱可塑性樹脂（Ｆ）とを
含有することを特徴とする熱可塑性樹脂組成物。9. A thermoplastic resin composition comprising the graft copolymer (G) according to any one of claims 1 to 8 and another thermoplastic resin (F).
を成形してなる成形品。10. A molded product obtained by molding the thermoplastic resin composition according to claim 9.
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|---|---|---|---|
| JP2001360071A JP4060064B2 (en) | 2001-11-26 | 2001-11-26 | Graft copolymer and thermoplastic resin composition containing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001360071A JP4060064B2 (en) | 2001-11-26 | 2001-11-26 | Graft copolymer and thermoplastic resin composition containing the same |
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| Publication Number | Publication Date |
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| JP2003160624A true JP2003160624A (en) | 2003-06-03 |
| JP4060064B2 JP4060064B2 (en) | 2008-03-12 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005194298A (en) * | 2003-12-26 | 2005-07-21 | Kaneka Corp | (meth)acrylic resin composition |
| WO2006004058A1 (en) * | 2004-07-07 | 2006-01-12 | Techno Polymer Co., Ltd. | Rubber reinforced resin, process for producing the same, and rubber reinforced resin composition |
| US7868063B2 (en) * | 2005-06-07 | 2011-01-11 | Lg Chem, Ltd. | Polymeric lubricant having multi layer structure and manufacturing method thereof |
| WO2012108485A1 (en) * | 2011-02-09 | 2012-08-16 | 三菱レイヨン株式会社 | Polyorganosiloxane latex and graft copolymer, thermoplastic resin composition and molded body using same |
| JP2020015835A (en) * | 2018-07-26 | 2020-01-30 | テクノＵｍｇ株式会社 | Graft copolymer and thermoplastic resin composition |
-
2001
- 2001-11-26 JP JP2001360071A patent/JP4060064B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005194298A (en) * | 2003-12-26 | 2005-07-21 | Kaneka Corp | (meth)acrylic resin composition |
| WO2006004058A1 (en) * | 2004-07-07 | 2006-01-12 | Techno Polymer Co., Ltd. | Rubber reinforced resin, process for producing the same, and rubber reinforced resin composition |
| US7868063B2 (en) * | 2005-06-07 | 2011-01-11 | Lg Chem, Ltd. | Polymeric lubricant having multi layer structure and manufacturing method thereof |
| WO2012108485A1 (en) * | 2011-02-09 | 2012-08-16 | 三菱レイヨン株式会社 | Polyorganosiloxane latex and graft copolymer, thermoplastic resin composition and molded body using same |
| JP5848699B2 (en) * | 2011-02-09 | 2016-01-27 | 三菱レイヨン株式会社 | Polyorganosiloxane latex, graft copolymer using the same, thermoplastic resin composition, and molded article |
| US9550896B2 (en) | 2011-02-09 | 2017-01-24 | Mitsubishi Rayon Co., Ltd. | Polyorganosiloxane latex, graft copolymer using the same, thermoplastic resin composition, and molded body |
| JP2020015835A (en) * | 2018-07-26 | 2020-01-30 | テクノＵｍｇ株式会社 | Graft copolymer and thermoplastic resin composition |
| JP7195798B2 (en) | 2018-07-26 | 2022-12-26 | テクノＵｍｇ株式会社 | Method for producing graft copolymer |
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