JPH0450252A - Weather-resistant resin composition having improved scratch resistance and molded article thereof - Google Patents
Weather-resistant resin composition having improved scratch resistance and molded article thereofInfo
- Publication number
- JPH0450252A JPH0450252A JP15828490A JP15828490A JPH0450252A JP H0450252 A JPH0450252 A JP H0450252A JP 15828490 A JP15828490 A JP 15828490A JP 15828490 A JP15828490 A JP 15828490A JP H0450252 A JPH0450252 A JP H0450252A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- thermoplastic resin
- acid ester
- polymerization
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 15
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 13
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract description 13
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims abstract description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000005060 rubber Substances 0.000 claims abstract description 11
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 8
- 150000001993 dienes Chemical class 0.000 claims abstract description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 2
- SKKHNUKNMQLBTJ-QIIDTADFSA-N [(1s,4r)-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C(=C)C)C[C@@H]1C2 SKKHNUKNMQLBTJ-QIIDTADFSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000012815 thermoplastic material Substances 0.000 claims 1
- 238000013329 compounding Methods 0.000 abstract 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 229920000800 acrylic rubber Polymers 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 150000008360 acrylonitriles Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 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
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- RXPKAZWARAPDMU-UHFFFAOYSA-M [Na+].O=C.[O-]O.OSO.CC(C)C1=CC=CC=C1 Chemical compound [Na+].O=C.[O-]O.OSO.CC(C)C1=CC=CC=C1 RXPKAZWARAPDMU-UHFFFAOYSA-M 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- CJCGDEYGAIPAEN-UHFFFAOYSA-N (1-methylcyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C)CCCCC1 CJCGDEYGAIPAEN-UHFFFAOYSA-N 0.000 description 1
- UCBVELLBUAKUNE-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)NC(=O)N(CC=C)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- DAEXAGHVEUWODX-UHFFFAOYSA-N 1-fluoroethenylbenzene Chemical compound FC(=C)C1=CC=CC=C1 DAEXAGHVEUWODX-UHFFFAOYSA-N 0.000 description 1
- AOUSBQVEVZBMNI-UHFFFAOYSA-N 2-bromoethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCBr AOUSBQVEVZBMNI-UHFFFAOYSA-N 0.000 description 1
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-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
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-OPQQBVKSSA-N [(1s,3r,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@]2(C)[C@H](OC(=O)C=C)C[C@H]1C2(C)C PSGCQDPCAWOCSH-OPQQBVKSSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- IUMSESXEXDXETG-UHFFFAOYSA-N [Na].CCCCCCCCCCCC[S] Chemical compound [Na].CCCCCCCCCCCC[S] IUMSESXEXDXETG-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-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
- 238000011156 evaluation Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- CHPAZJVPFDXOAQ-UHFFFAOYSA-N fluoromethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCF CHPAZJVPFDXOAQ-UHFFFAOYSA-N 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- HVYCQBKSRWZZGX-UHFFFAOYSA-N naphthalen-1-yl 2-methylprop-2-enoate Chemical compound C1=CC=C2C(OC(=O)C(=C)C)=CC=CC2=C1 HVYCQBKSRWZZGX-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明上耐衝撃性、成形性及び成形品外ｌｌ！に優れ１
％に耐候性、耐熱性及び耐傷付き性に優れた熱可塑性樹
脂組成物及び成形品に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention provides impact resistance, moldability, and non-molded products! Excellent 1
The present invention relates to thermoplastic resin compositions and molded products that have excellent weather resistance, heat resistance, and scratch resistance.
（従来の技術）
耐候性樹脂としては、主鎖中に二重結合をほとんど有し
ない飽和ゴム状重合体を使用した樹脂が提案されておシ
、その代表的なものとしてアクリル系ゴムおよびエチレ
ンプロピレン系ゴムを使用したものが知られている。こ
れらの飽和ゴムは紫外線に対して安定であるため屋外で
便用する成形品に無塗装で使用されているが、塗装品に
比べて成形品に傷が付きやすいという欠点がありｇ塗装
で用いる耐候性樹脂としてはまだ十分ではない。(Prior art) As weather-resistant resins, resins using saturated rubber-like polymers that have almost no double bonds in their main chains have been proposed, and representative examples include acrylic rubber and ethylene propylene. Rubbers using rubber are known. These saturated rubbers are stable against ultraviolet rays, so they are used unpainted in molded products for outdoor use, but they have the disadvantage that molded products are more easily scratched than painted products, so they are used with g-painting. It is still not sufficient as a weather-resistant resin.
特に自動車部品用に使用する場合は目勧車洗車時等に傷
が付きにくい材料が要求されている。In particular, when used for automobile parts, materials that are resistant to scratches during car washes are required.
（発明が解決しようとする課題）
本発明者等は、従来のこのような耐候性樹脂の欠点の改
良について研究した結果、炭素原子数５〜２２個の脂環
式炭化水素基を有するメタクリル酸エステルを含む熱可
塑性樹脂を混合し、さらに特定粘度のジメチルポリシロ
キサンオイルを混合することによシ成形品の耐候性をそ
こなわずに。(Problems to be Solved by the Invention) As a result of research on improving the drawbacks of conventional weather-resistant resins, the present inventors discovered that methacrylic acid having an alicyclic hydrocarbon group having 5 to 22 carbon atoms By mixing thermoplastic resin containing ester and dimethylpolysiloxane oil with a specific viscosity, the weather resistance of molded products is not compromised.
しかも傷が付きにくい熱可塑性樹脂組成物を見出し１本
発明を完成するに至った。In addition, they discovered a thermoplastic resin composition that is resistant to scratches and completed the present invention.
（課題を解決するための手段） 本発明は、多官能性単量体０．１〜２０重数％。(Means for solving problems) In the present invention, the polyfunctional monomer is contained in an amount of 0.1 to 20% by weight.
炭素数１〜１３０アルキル基を有するアクリル酸エステ
ル５０〜９９．９重ｉ−％及び共重合可能な他のビニル
化合物θ〜３０重量％を配合して得られる重合性単量体
混合物ｆａ）９５〜６０］ｉ量部をジエン系重合体（ｂ
）５〜４０重数部の存在下に（ａ）と（ｂｌの合計が１
００重量部となるように配合し１重合率が５０〜９３％
まで乳化重合させた後１重合を停止させて得られるグラ
フト重合体ゴ噸に５〜５０重量部の存在下に、芳香族ビ
ニル化合物０〜１００重量％、メタクリル酸エステル０
〜１００重量％及びシアン化ビニル化合物０〜４０膚量
％からなる単量体（Ｂ）９５〜５０重量部を、（Ａ）と
（Ｂ）の合計が１００重量部となるように配合し１重合
させて得られる熱可塑性樹脂（Ｉ）２０〜９０重量部、
炭素原子数５〜２２個の脂環式炭化水素基を有するメタ
クリル酸エステル２０〜１００重量％及び共重合可能な
他の重合性単量体０〜８０重量％を重合させて得られる
熱可塑性樹脂（■）５〜４０重量部、並びに芳香族ビニ
ル化合物６５〜８５重量％及びシアン化ビニル化合物１
５〜３５重量％を重合させて得られる熱可塑性樹脂（１
１５〜４０重量部を（Ｉ）。Polymerizable monomer mixture fa)95 obtained by blending 50 to 99.9 weight % of an acrylic ester having an alkyl group with 1 to 130 carbon atoms and θ to 30 weight % of another copolymerizable vinyl compound ~60] i part of the diene polymer (b
) in the presence of 5 to 40 parts by weight, the sum of (a) and (bl) is 1
00 parts by weight, and the 1 polymerization rate is 50 to 93%.
In the presence of 5 to 50 parts by weight, 0 to 100% by weight of an aromatic vinyl compound and 0 to 100% of a methacrylic acid ester are added to a graft polymer obtained by emulsion polymerization to 1 and then stopping the polymerization.
95 to 50 parts by weight of monomer (B) consisting of ~100% by weight and 0 to 40% by weight of a vinyl cyanide compound are blended so that the total of (A) and (B) is 100 parts by weight. 20 to 90 parts by weight of thermoplastic resin (I) obtained by polymerization,
Thermoplastic resin obtained by polymerizing 20 to 100% by weight of a methacrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms and 0 to 80% by weight of another copolymerizable monomer. (■) 5 to 40 parts by weight, and 65 to 85% by weight of aromatic vinyl compound and 1 part by weight of vinyl cyanide compound
Thermoplastic resin obtained by polymerizing 5 to 35% by weight (1
15 to 40 parts by weight of (I).
（ＩＩ）及び（Ｉ）の合計が１００重量部となるように
配合して得られる混合物に、２５℃における粘度が１０
００〜３００００センチストークスのジメチルポリノロ
キサンオイルを該混合物に対して０．１〜１０重量％混
合してなる耐傷付き性の改良された耐候性樹脂組成物、
並びに該耐候性樹脂組成物を用いて成形して得られる成
形品に関する。A mixture obtained by blending (II) and (I) in a total amount of 100 parts by weight has a viscosity of 10 parts by weight at 25°C.
A weather-resistant resin composition with improved scratch resistance, which is obtained by mixing 0.1 to 10% by weight of dimethylpolynoroxane oil of 0.00 to 30,000 centistokes with respect to the mixture;
The present invention also relates to a molded article obtained by molding the weather-resistant resin composition.
まず、熱可塑性樹脂（Ｉ）について説明する。First, the thermoplastic resin (I) will be explained.
重合性単量体混合物（ａｌの一成分である多官能性単量
体としては、トリアリルシアヌレート、トリアリルイン
シアヌレート、ジビニルベンゼン、トリアクリルホルマ
ール、エチレングリコールジメタクリレート等の多価ビ
ニル化合物や多価アリル化合物が使用できるが、この中
でも特に、トリアリルシアヌレートとトリアリルイソシ
アヌレートが最終的に得られる樹脂の耐衝撃性が最も優
れているので好ましい。多官能性単量体は９重合性単量
体混合物（ａ）中、０．１〜２０重量％、好ましくは０
．５〜１０重量％使用される。０．１重量％未満では架
橋度が不十分で耐衝撃性、成形品外観が劣り。Polyfunctional monomers that are a component of the polymerizable monomer mixture (al include polyvalent vinyl compounds such as triallyl cyanurate, triallyl in cyanurate, divinylbenzene, triacryl formal, and ethylene glycol dimethacrylate) Among these, triallyl cyanurate and triallyl isocyanurate are particularly preferred because the resulting resin has the best impact resistance.The polyfunctional monomer is 9 In the polymerizable monomer mixture (a), 0.1 to 20% by weight, preferably 0
．． 5-10% by weight is used. If it is less than 0.1% by weight, the degree of crosslinking will be insufficient and the impact resistance and appearance of the molded product will be poor.
２０重量Ｘを越えると架橋度が過剰となり耐衝撃性が低
下する。When the weight exceeds 20X, the degree of crosslinking becomes excessive and impact resistance decreases.
炭素数１〜１３０アルキル基を有するアクリル酸エステ
ルとして汀、エチルアクリレート、ブチルアクリレート
、２−エチルエキシルアクリレート等があり、このうち
ブチルアクリレートが特に好ましい。アクリル酸エステ
ルは１重合体混合物（ａ）中、５０〜９９．９重量％、
好ましくは６５〜９９．５重量％１吏用される。５０重
量％未満ではアクリルゴムの特性が低下し、９９．９重
量％を超えると耐衝撃性及び成形品外観に劣る。Examples of acrylic esters having an alkyl group having 1 to 130 carbon atoms include ethyl acrylate, butyl acrylate, 2-ethylexyl acrylate, and among these, butyl acrylate is particularly preferred. Acrylic acid ester is 50 to 99.9% by weight in the monopolymer mixture (a),
It is preferably used in an amount of 65 to 99.5% by weight. If it is less than 50% by weight, the properties of the acrylic rubber will deteriorate, and if it exceeds 99.9% by weight, the impact resistance and appearance of the molded product will be poor.
共重合可能な他のビニル化合物としてはアクリロニドＩ
Ｊル、スチレン等があり１重合性単量体混合物（ａ）中
、０〜３０重徽％好ましくは０〜２５重飯％の範囲で使
用される。３０重量％を越えるとアクリルゴムとしての
特性が充分得られない。Other copolymerizable vinyl compounds include acrylonide I
Polymeric monomers, styrene, etc. are used in the monomerizable monomer mixture (a) in an amount of 0 to 30% by weight, preferably 0 to 25% by weight. If it exceeds 30% by weight, sufficient properties as an acrylic rubber cannot be obtained.
ジエン系重合体（ｂ）としては、ポリブタジェン。The diene polymer (b) is polybutadiene.
ブタジェン−スチレン共重合体等が夏用できる。Butadiene-styrene copolymer etc. can be used in summer.
重合性単量体混合物（ａｊの９５〜６０重量部を。Polymerizable monomer mixture (95 to 60 parts by weight of aj.
ジエン系重合体（ｂ）５〜４０重量部の存在下に（ａ）
と（ｂ）の合計が１００重量部となるように配合し、乳
化重合される。ここで、ジエン系重合体（ｂｌが、５重
量部未満では、耐衝撃性、成形品外観が不充分であり、
４０重量部を超えると耐候性に劣る。(a) in the presence of 5 to 40 parts by weight of diene polymer (b)
and (b) are blended so that the total amount is 100 parts by weight, and emulsion polymerization is carried out. Here, if the diene polymer (bl) is less than 5 parts by weight, the impact resistance and appearance of the molded product will be insufficient,
If it exceeds 40 parts by weight, weather resistance will be poor.
グラフト重合体ゴム（Ａ）を得るためのこの乳化重合は
、当業者に一般的に仰られている方法で行うことができ
る。この乳化重合において１重合を重合率１００％まで
行わず、５０〜９３％、好ましくは６０〜９０％で停止
させることが高面撃性を得るための必須条件である。重
合率が５０％未満では、重合体（Ｂｌの重合の際に単量
体ＦＢ＋と共重合する比率が高くなり、熱変形＠度が低
下する。又。This emulsion polymerization to obtain the graft polymer rubber (A) can be carried out by methods commonly known to those skilled in the art. In this emulsion polymerization, it is an essential condition for obtaining high surface impact properties that one polymerization should not be carried out to a polymerization rate of 100%, but should be stopped at a polymerization rate of 50 to 93%, preferably 60 to 90%. If the polymerization rate is less than 50%, the ratio of copolymerization with the monomer FB+ during polymerization of the polymer (Bl) increases, and the degree of thermal deformation decreases.
重合率が９３％を越えると耐ｓＳ性の向上効果が充分得
られない。グラフト重合体ゴムｆＡ）を得るための乳化
重合に際し、少゛量の乳化剤としてオレイン酸ナトリウ
ム、ラウリル硫散ソーダ、ドデシルベンゼンスルホン酸
ソーダなどのアニオン系乳化剤やポリオキシエチレンセ
チルエーテルのようなノニオン系乳化剤を使用してもよ
い。また１重合開始剤としては１通常の乳化重合に用い
られる。If the polymerization rate exceeds 93%, a sufficient effect of improving sS resistance cannot be obtained. During emulsion polymerization to obtain the graft polymer rubber fA), a small amount of anionic emulsifier such as sodium oleate, sodium lauryl sulfur, sodium dodecylbenzenesulfonate, or a nonionic emulsifier such as polyoxyethylene cetyl ether is used as an emulsifier. Emulsifiers may also be used. Further, as a polymerization initiator, it is used in ordinary emulsion polymerization.
例えば過硫酸塩やキュメンハイドロパーオキサイド−ナ
トリウムホルムアルデヒドスルホキシレートで構成され
るレドックス系のものが愛用される。For example, redox compounds composed of persulfate and cumene hydroperoxide-sodium formaldehyde sulfoxylate are commonly used.
こうして得られるグラフト重合体ゴＡ（Ａ）５〜５０重
量部の存在下に、単量体（Ｂ）９５〜５０重量部を、（
Ａ）と（Ｂ）の合計が１００重敏部上なるように配合し
て重合し、熱可塑性樹脂（Ｉｌを製造する。ここで、グ
ラフト重合体ゴムｆＡ）が５重合部禾溝では最終的に得
られる樹脂の耐衝撃性が低下し、５００重合を越えると
機械的強度、熱変形温度が低下する。In the presence of 5 to 50 parts by weight of the thus obtained graft polymer GoA (A), 95 to 50 parts by weight of the monomer (B) (
A) and (B) are blended and polymerized so that the sum of them is more than 100 parts, to produce a thermoplastic resin (Il.Here, graft polymer rubber fA) is finally added to 5 polymer parts in the groove. The impact resistance of the resulting resin decreases, and if the polymerization exceeds 500%, the mechanical strength and heat distortion temperature decrease.
単量体（Ｂ）として用いられる芳香族ビニル化合物とし
ては、α−メチルスチレン、α−エチルスチＬ’７等ｆ
７）α−置換スチレン、クロロスチレン、ビニルトルエ
フ、 ｔ−ブチルスチレン等の核置換スチレン、スチ
レン等、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。Examples of the aromatic vinyl compound used as the monomer (B) include α-methylstyrene, α-ethylstyrene L'7, etc.
7) Nucleically substituted styrenes such as α-substituted styrene, chlorostyrene, vinyltoluev, t-butylstyrene, styrene, etc., vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, etc.
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、メタクリル酸ブチル等が使用できる
。なお、単量体（Ｂ＞中、シアン化ビニルが４０重量％
を超えると成形性が低下する。As the methacrylic ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. can be used. In addition, vinyl cyanide is 40% by weight of the monomer (B>
If it exceeds this value, moldability will decrease.
グラフト共重合体ゴム（Ａ）の存在下に単量体（Ｂ）を
重合させるには、乳化重合法、ｔｌｌ重重合法溶液重合
法等の重合法が採用できる。重合に際し、乳化剤、Ｊｉ
Ｌ合開合剤始剤鎖移動剤などが適宜添加される。重合開
始剤としては過硫酸塩やキュメンハイドロパーオキサイ
ド−ナトリウムホルムアルデヒドスルホキシレート等の
レドックス系開始剤が単量体ＦＢ）に対し好ましくは、
約０．１〜２重量％使用さｎる。連鎖移動剤としてに、
ｔ−ドデシルメルカプタンなどが単量体（Ｂ）に対して
好ましくは約１重量％以内の量で使用される。重合温度
は、２０〜ｉｏｏ℃、％に５０〜９０℃の範囲で行うの
が好ましい。なお、グラフト重合体ゴムの製造に際して
も同様の条件を採用すればよい。In order to polymerize the monomer (B) in the presence of the graft copolymer rubber (A), a polymerization method such as an emulsion polymerization method, a tll polymerization method, or a solution polymerization method can be employed. During polymerization, emulsifier, Ji
L-synthesis initiator, chain transfer agent, etc. are added as appropriate. As the polymerization initiator, redox initiators such as persulfate and cumene hydroperoxide-sodium formaldehyde sulfoxylate are preferably used for monomer FB).
About 0.1-2% by weight is used. As a chain transfer agent,
T-dodecyl mercaptan and the like are preferably used in an amount of up to about 1% by weight based on monomer (B). The polymerization temperature is preferably 20 to 100°C, 50 to 90°C. Note that similar conditions may be employed when producing the graft polymer rubber.
グラフト重合体ゴム入の存在下に重合させる単量体ＣＢ
）は、−回で全量重合したり、数回に分割して重合した
り、あるいは全単量体を滴下しながら重合する方法など
のいずれの重合方法を採用してもかまわないが、＠−段
目として、単量体（Ｂｌのうち５〜３０重量Ｘ重量台率
５０％以上になるまで重合させ九のち第二段目として単
量体（Ｂ）の残量を添加して重合させるのが好ましい。Monomer CB polymerized in the presence of graft polymer rubber
) may be polymerized by any polymerization method, such as polymerizing the entire amount in - times, polymerizing in several times, or polymerizing while dropping all the monomers, but @- In the second step, the monomer (Bl) is polymerized until it reaches 5 to 30% by weight x 50% or more, and then in the second step, the remaining amount of monomer (B) is added and polymerized. is preferred.
このような二段階重合方法を採用することにより、更に
流動性。By adopting such a two-step polymerization method, fluidity is further improved.
熱変形温度が高く、かつ、耐衝撃性の高い樹脂を得るこ
とができるので好ましい方法である。最初に重合させる
のは単量体（Ｂ）のうち５〜３０重量％の範囲が好まし
く、５重量％未満では全量を一段で重合させる場合と差
がなく、３０重量％を越えると単量体ＣＢ）を分割添加
して重合させることによる耐衝撃性向上効果および熱変
形温度の向上効果が少なくなる傾向にある。またこの時
１重合率が５０Ｘ以上進行したのち単量体［Ｂ）の残量
を添加し。This is a preferred method because it allows a resin with a high heat distortion temperature and high impact resistance to be obtained. It is preferable to initially polymerize the monomer (B) in a range of 5 to 30% by weight; if it is less than 5% by weight, there is no difference from polymerizing the entire amount in one step, and if it exceeds 30% by weight, the monomer (B) The effect of improving impact resistance and improving heat distortion temperature by adding CB) in portions and polymerizing tends to decrease. At this time, after the polymerization rate has progressed to 50X or more, the remaining amount of monomer [B) is added.
重合させるのが好ましい。重合率５０％未満では熱変形
温度、耐衝撃性の向上効果が少なくなる傾向がある。Preferably, it is polymerized. If the polymerization rate is less than 50%, the effect of improving heat distortion temperature and impact resistance tends to decrease.
第一段目および第二段目に分割して使用される単量体（
ＢＡＦｉ、それぞれ
芳香族ビニル化合物 ０〜１００重ｆ％メタクリル
酸エステル ０〜１００重量％および
シアン化ビニル化合物 ０〜４０重量％であジ、かつ
全体が１００重奮％になるような割合で使用されるのが
好ましい。Monomers used separately in the first and second stages (
BAFi, aromatic vinyl compound 0 to 100% by weight, methacrylic acid ester 0 to 100% by weight and vinyl cyanide compound 0 to 40% by weight, respectively, and used in proportions such that the total is 100% by weight. It is preferable to
次に熱可塑性樹脂（ｎ）について説明する。Next, the thermoplastic resin (n) will be explained.
これに用いられる炭素原子数５〜２２個の脂環式炭化水
素基を有するメタクリル酸エステルとしては、メタクリ
ル酸ノルボニル、メタクリル酸ノルゲニルメチル、メタ
クリル酸トリシクロ〔５４１、０’−’ １デカ−８−
イル、メタクリル酸トリゾクａ ［ｓ、ｚｔ、ｏ”］］
デ１ｙ−３−ｉｆル、 メタクリル酸トリシクロ［５，
Ｚｌ、０”・１〕デカ−４−メチル等が好ましい。Examples of the methacrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms include norbornyl methacrylate, norgenylmethyl methacrylate, and tricyclo[541,0'-'1deca-8-
il, Trizoc methacrylate a [s, zt, o”]]
tricyclo methacrylate [5,
Zl, 0''.1]deca-4-methyl and the like are preferred.
なお、メタクリル酸エステルの脂環式炭化水素基の炭素
数が２２を超えると相溶性に劣る。またこれらメタクリ
ル酸エステルと共重合可能な他の重合性単量体としては
、不飽和脂肪酸エステル。Note that if the number of carbon atoms in the alicyclic hydrocarbon group of the methacrylic ester exceeds 22, the compatibility will be poor. Other polymerizable monomers that can be copolymerized with these methacrylic acid esters include unsaturated fatty acid esters.
芳香族ビニル化合物、シアン化ビニル化合物があり、こ
れらの一種または二種以上が使用される。There are aromatic vinyl compounds and vinyl cyanide compounds, and one or more of these may be used.
不飽和脂肪酸エステルとしては、アクリル散メチル、ア
クリル酸エチル、アクリル酸ブチル、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、アクリ
ル酸シクロヘキシル、アクリル酸メチルシクロヘキシル
、アクリル酸ボルニル、アクリル酸インボルニル、アク
リル酸アダマンチル等のアクリル酸シクロアルキルエス
テル。Examples of unsaturated fatty acid esters include acrylic acid alkyl esters such as methyl acrylic powder, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, cyclohexyl acrylate, methylcyclohexyl acrylate, bornyl acrylate, inbornyl acrylate, and acrylic acid. Acrylic acid cycloalkyl esters such as adamantyl.
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、メタクリル酸ブチル。Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
メタクリル酸２−エチルヘキシル等のメタクリル酸アル
キルエステル、メタクリル酸フェニル、メタクリル酸ベ
ンジル、メタクリル酸ナフチル等のメタクリル酸芳香族
エステル、メタクリル買フルオロメチル、メタクリル酸
フルオロエチル、メタクリル酸クロロエチル、メタクリ
ル醗ブロモエチル等のメタクリル酸ハロゲン化アルキル
エステル等がある。Alkyl methacrylates such as 2-ethylhexyl methacrylate, aromatic esters of methacrylic acid such as phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, fluoromethyl methacrylate, fluoroethyl methacrylate, chloroethyl methacrylate, bromoethyl methacrylate, etc. Examples include methacrylic acid halogenated alkyl esters.
芳香族ビニル化合物としては、スチレン、α−メチルス
チレン、α−エチルスチレン、α−フルオロスチレン、
α−クロロスチレン、フルオロスチレン、クロロスチレ
ン、ブロモスチレン、メチルスチレン、ブチルスチレン
等がある。Examples of aromatic vinyl compounds include styrene, α-methylstyrene, α-ethylstyrene, α-fluorostyrene,
Examples include α-chlorostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, butylstyrene, and the like.
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がある。Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.
炭素原子数５〜２２個の脂環式炭化水素基を有するメタ
クリル酸エステルは、２０〜１００重量％配合されるが
、２０重量％未満では耐傷付き性の向上が顕著でない。The methacrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms is blended in an amount of 20 to 100% by weight, but if it is less than 20% by weight, the scratch resistance is not significantly improved.
熱可塑性樹脂（ｎ）の製造は、乳化重合、懸濁重合。The thermoplastic resin (n) is manufactured by emulsion polymerization or suspension polymerization.
溶液重合等公知の重合法により行なうことができる。This can be carried out by a known polymerization method such as solution polymerization.
次に熱可塑性樹脂（ＩＩ［）について説明する。Next, the thermoplastic resin (II[) will be explained.
熱可塑性樹脂（ＩＮ）は、芳香族ビニル化合物６５〜８
５重量％、好ましくは７０〜８０重量％及びシアン化ビ
ニル化合物１５〜２５重量％、好ましくは２０〜３０重
量％を重合させて得られるが、ここで芳香族ビニル化合
物が７０重量％未満では流動性が悪くなり、一方８０重
量Ｘを超えると耐衝撃性、熱変形温度が低下する。芳香
族ビニル化合物及びシアン化ビニル化合物としては、前
記熱可塑性樹脂（ＩＩ）の説明で挙げたものが使用でき
る。The thermoplastic resin (IN) is an aromatic vinyl compound 65-8
It is obtained by polymerizing 5% by weight, preferably 70 to 80% by weight and 15 to 25% by weight, preferably 20 to 30% by weight of a vinyl cyanide compound, but if the aromatic vinyl compound is less than 70% by weight, it will not flow. On the other hand, if it exceeds 80 weight X, impact resistance and heat distortion temperature decrease. As the aromatic vinyl compound and vinyl cyanide compound, those mentioned in the description of the thermoplastic resin (II) can be used.
その他のビニル単量体を併用する場合には、これも含め
た量が１００重量％となるように配合さる。When other vinyl monomers are used together, they are blended in such a way that the amount including these is 100% by weight.
また、必要に応じてその他のビニル単量体を０〜２０重
量％併用することもできる。必要に応じて使用できるそ
の他のビニル単量体としては、メチルアクリル醒エステ
ル、エチルアクリル散エステル等のアクリル酸エステル
、アクリル酸、メタクリル［８のビニルカルボン酸、マ
レイミド、Ｎメチルマレイミド、Ｎ−エチルマレイミド
、Ｎ−ブチルマンイミド、Ｎ−シクロへキシルマレイミ
）”、Ｎ−フェニルマ１／イミド等のマレイミド系単量
体、アクリル酸アミド、メタクリル酸アミド等があげら
れる。Moreover, 0 to 20% by weight of other vinyl monomers can also be used in combination, if necessary. Other vinyl monomers that can be used as necessary include acrylic acid esters such as methyl acrylic ester and ethyl acrylic powder, acrylic acid, methacrylic [8] vinyl carboxylic acid, maleimide, N-methylmaleimide, N-ethyl Examples include maleimide monomers such as maleimide, N-butylmanimide, N-cyclohexylmaleimide, N-phenylmanimide, acrylamide, methacrylicamide, and the like.
熱可塑性樹脂（ＩＩＩ）の製造は、乳化重合、！！！！
濁重合。The thermoplastic resin (III) is produced by emulsion polymerization! ! ! !
Turbid polymerization.
溶液重合等公知の重合法により行なうことができる。This can be carried out by a known polymerization method such as solution polymerization.
本発明において９以上説明した熱可塑性樹脂（１）。Thermoplastic resin (1) described above in the present invention.
（ＩＩ）及び（Ｉ）（以下、各々単に（Ｉ）成分、（■
）成分、 （ＩＩＩ）成分とする）は、（Ｉ）成分２０
〜９０重量部、（■）成分５〜４０重量部、 （ｌｉｔ
）成分５〜４０重量部を９合計が１００重量部となるよ
うに配合して混合物とする。(II) and (I) (hereinafter each simply the (I) component, (■
) component, (III) component) is (I) component 20
~90 parts by weight, (■) component 5-40 parts by weight, (lit
) A mixture is prepared by blending 5 to 40 parts by weight of the components so that the total of the 9 components is 100 parts by weight.
ここで、（１）成分及び（ＩＩＩ）成分のいずれかがこ
の範囲外であれば得られる組成物は、耐熱性９耐衝撃性
等に劣る。また、（■）成分が５重を部未満では得られ
る樹脂組成物の耐傷付き性が低下し、４０重量部を超え
ると得られる樹脂組成司の耐衝撃性及び熱変形温度が低
下する。Here, if either component (1) or component (III) is outside this range, the resulting composition will be inferior in heat resistance, impact resistance, etc. Furthermore, if the component (■) is less than 5 parts by weight, the scratch resistance of the resulting resin composition will be reduced, and if it exceeds 40 parts by weight, the impact resistance and heat distortion temperature of the resulting resin composition will be reduced.
なお、（■）成分は、好ましくは２０〜４０重量部配合
される。Note that the component (■) is preferably blended in an amount of 20 to 40 parts by weight.
さらに１本発明においては、２５℃における粘度が１０
００〜３００００センチストークス（Ｃ８）のジメチル
ポリシロキサンオイルが混合される。Furthermore, in the present invention, the viscosity at 25°C is 10
00 to 30,000 centistokes (C8) dimethylpolysiloxane oil is mixed.
ジメチルポリシロキサンオイルの混合量は前記熱可塑性
樹脂の混合物に対して０．１〜１０１１量％である。０
．１重量％未満では耐傷付き性向上の効果がなく、ま九
１０重量Ｘを超えると耐衝撃性が低下する。好ましくは
０．３〜３重量％である。またジメチルポリシロキサン
オイルの粘度は１０００〜３００００センチストークス
（Ｃ８）のものである。１０００センチストークス（Ｃ
８’）未満では耐傷付き性の効果が低下する。また３０
０００センチストークス（Ｃ８）を超えると樹脂との相
容性が低下し、耐傷付き性の効果が低下する。The amount of dimethylpolysiloxane oil mixed is 0.1 to 1011% by weight based on the thermoplastic resin mixture. 0
．． If it is less than 1% by weight, there is no effect of improving scratch resistance, and if it exceeds 10% by weight, impact resistance will decrease. Preferably it is 0.3 to 3% by weight. The viscosity of the dimethylpolysiloxane oil is 1,000 to 30,000 centistokes (C8). 1000 centistokes (C
If it is less than 8'), the scratch resistance effect will decrease. 30 again
If it exceeds 000 centistokes (C8), the compatibility with the resin decreases, and the scratch resistance effect decreases.
本発明の耐傷付き性の改良された耐候性樹脂組成物は９
以上の各成分を常法により混合して得られる。The weather-resistant resin composition of the present invention with improved scratch resistance is 9
It can be obtained by mixing the above components in a conventional manner.
ま几、成形材料として使用する場合は１通常のフェノー
ル系酸化防止剤、成形加工性の向上から滑剤、紫外線吸
収剤等の安定化剤を併用することも可能である。When used as a molding material, it is also possible to use a usual phenolic antioxidant, a lubricant to improve molding processability, a stabilizer such as an ultraviolet absorber, etc.
得られる樹脂組成物は、射出成形等公知の成形法により
成形され、各種成形品とされる。得られる成形品は、自
動車部品、屋外用等として優れた特性を示す。The resulting resin composition is molded by a known molding method such as injection molding into various molded products. The resulting molded product exhibits excellent properties for use as automobile parts, outdoor use, etc.
（実施例）
次に実施例によって本発明をさらに具体的に説明するが
１本発明はこれらに制限されるものではなり０なお、以
下の実施例および比較例において「部」および「％」は
１％に断らない限シ、それぞれ「重量部」および「重量
％」を意味する。(Example) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these. In addition, in the following Examples and Comparative Examples, "part" and "%" are 1% means "part by weight" and "% by weight", respectively, unless otherwise specified.
（１） アクリル系グラフト重合体ゴム因の製造内容
積４１の攪拌機付き反応容器中にポリブタジェンラテッ
クス（住友ノーガタック■製、５Ｎ−８００）３００部
および均一に溶解した脂肪酸カリウム８部、亜硫酸ナト
リウム０．０９部、イオン交換水２０００部を仕込み混
合攪拌したのち。(1) Production of acrylic graft polymer rubber 300 parts of polybutadiene latex (manufactured by Sumitomo Naugatac, 5N-800), 8 parts of fatty acid potassium uniformly dissolved, and sulfurous acid were placed in a reaction vessel with an internal volume of 41 cm and equipped with a stirrer. After 0.09 parts of sodium and 2000 parts of ion-exchanged water were mixed and stirred.
均一に溶解したアクリル酸ブチル７００ｍ、）ジアリル
イソシアヌレート１４部を添加する。この乳化溶液を窒
素置換し、その後側の容器に用意しておいた過硫酸カリ
ウム０．５部とイオン交換水３００部の水容液を添加混
合して６０〜６５℃に昇温した。重合は６０〜６５℃で
約３時間行ない。Add 700 m of butyl acrylate, 14 parts of diallylisocyanurate, homogeneously dissolved. This emulsified solution was purged with nitrogen, and an aqueous solution of 0.5 parts of potassium persulfate and 300 parts of ion-exchanged water prepared in a container on the rear side was added and mixed, and the temperature was raised to 60 to 65°C. Polymerization is carried out at 60-65°C for about 3 hours.
冷却して重合を停止させた。この時の重合率は７１％で
あった。Polymerization was stopped by cooling. The polymerization rate at this time was 71%.
（２）熱可塑性樹脂（Ｉ）の乳化重合
内容積４１の攪拌機付き反応容器中に（１）で製造した
アクリル系ゴム重合体（Ａ）４００部にラウリル硫酸ナ
トリウム１部、脂肪酸カリウム５部およびイオン交換水
６５０部を均一に溶解する。これに均一に溶解したキュ
メンハイドロパーオキサイド０．２５部、アクリロニト
リル２３部、スチレン４７部を混合、攪拌しながら添加
し、窒素置換し。(2) Emulsion polymerization of thermoplastic resin (I) 400 parts of the acrylic rubber polymer (A) produced in (1), 1 part of sodium lauryl sulfate, 5 parts of potassium fatty acid and Uniformly dissolve 650 parts of ion-exchanged water. To this, 0.25 parts of cumene hydroperoxide, 23 parts of acrylonitrile, and 47 parts of styrene uniformly dissolved were added while stirring and the mixture was replaced with nitrogen.
その後ナトリウムホルムアルデヒドスルホキシレート３
部をイオン交換水７０部に溶解したものを添加して６５
℃に昇温し、約１時間保温し９重合率を７０％にする。Then sodium formaldehyde sulfoxylate 3
65 parts dissolved in 70 parts of ion-exchanged water.
The temperature was raised to ℃ and kept for about 1 hour to bring the polymerization rate to 70%.
その量刑の３個の容器を用意しておき、１個めの容器に
は炭酸カリウム７部とイオン交換水６０部を入れ、２個
めの容器ては脂肪酸カリウム１０部とイオン交換水４５
０部を入れ、３個めの容器にはキュメンハイドロパーオ
キサイド１．５部、ターシャリドデシルメルカプタン１
．７部、アクリロニトリル１５０部およびスチレン３８
０部を入れ、それぞれ溶解しておく。その後この３個の
溶液を混合し、約２時間かけて反応容器内に滴下し６５
℃で重合させる。６５℃で約５時間重合させ重合率が８
５〜９０％になった所で過硫酸カリウム１．２部をイオ
ン交換水５０部に溶解した水溶液を添加して１重合温度
を８０℃に昇温しで約２時間重合させて重合を完結させ
る。Prepare three containers for this purpose, and in the first container, put 7 parts of potassium carbonate and 60 parts of ion-exchanged water, and in the second container, put 10 parts of fatty acid potassium and 45 parts of ion-exchanged water.
In the third container, add 1.5 parts of cumene hydroperoxide and 1 part of tertiary dodecyl mercaptan.
．． 7 parts, 150 parts of acrylonitrile and 38 parts of styrene
Add 0 parts and dissolve each. After that, these three solutions were mixed and dropped into the reaction container over about 2 hours.
Polymerize at °C. Polymerization was carried out at 65℃ for about 5 hours until the polymerization rate was 8.
When the concentration reached 5 to 90%, an aqueous solution of 1.2 parts of potassium persulfate dissolved in 50 parts of ion-exchanged water was added, and the polymerization temperature was raised to 80°C for about 2 hours to complete the polymerization. let
この時の重合率は９８％であった。ここで得られたラテ
ックス状の反応溶液をカリミョウバンｔｇ解した熱水中
で塩析し、脱水乾燥して粉末状の熱可塑性樹脂（Ｉ）を
得た。The polymerization rate at this time was 98%. The latex-like reaction solution obtained here was salted out in hot water containing tg of potassium alum, and dehydrated and dried to obtain a powdery thermoplastic resin (I).
（３）熱可塑性樹脂（■）（メタクリル酸エステル共重
合体）の製造
内容積４１の攪拌機およびコンデンサーを備えたセパラ
ブルフラスコに塩基性リン酸カルシウム１０％水溶液４
２部およびドデシルベンゼンスルホン酸ナトリウム０．
００２部、硫酸ナトリウム０．５部、イオン交換水１２
００部を入れ攪拌混合して懸濁媒体とした。これに、過
酸化ラウロイル４部およびｎ−オクチルメルカプタン１
部を溶解したメタクリル酸トリシクロ（５，Ｚｌ、０２
，６〕デカ−８−イル３００部およびメタクリル酸メチ
ル７００部を加え攪拌し窒素雰囲気下で６０℃３時間重
合後重合℃で４時間重合させて得られた重合体粒子を水
洗、脱水、乾燥して熱可塑性樹脂（Ｕ）（メタクリル酸
エステル共重合体粒子）を得た。(3) Production of thermoplastic resin (■) (methacrylic acid ester copolymer) A 10% aqueous solution of basic calcium phosphate in a separable flask equipped with a stirrer and a condenser with an internal volume of 41
2 parts and 0.0 parts sodium dodecylbenzenesulfonate.
002 parts, sodium sulfate 0.5 parts, ion exchange water 12
00 parts were added and mixed with stirring to prepare a suspension medium. To this are added 4 parts of lauroyl peroxide and 1 part of n-octyl mercaptan.
Tricyclomethacrylate (5, Zl, 02
, 6] Add 300 parts of dec-8-yl and 700 parts of methyl methacrylate, stir, and polymerize at 60°C for 3 hours under a nitrogen atmosphere. Polymerization The polymer particles obtained by polymerizing at °C for 4 hours are washed with water, dehydrated, and dried. A thermoplastic resin (U) (methacrylic acid ester copolymer particles) was obtained.
（４）熱可塑性樹脂（■）（芳香族系共重合体）の製造
内容積４１の攪拌機付き反応容器に塩基性リン酸カルシ
ウム１０％水溶液３０部、ドデシルベンゼンスルホン酸
ソーダ０．５部およびイオン交換水１２００部を入れ攪
拌する。これに均一に溶解したスチレン７４０部、アク
リロニトリル２６０部。(4) Production of thermoplastic resin (■) (aromatic copolymer) Place 30 parts of a 10% aqueous basic calcium phosphate solution, 0.5 part of sodium dodecylbenzenesulfonate, and ion-exchanged water in a reaction vessel with an internal volume of 41 and equipped with a stirrer. Add 1200 parts and stir. 740 parts of styrene and 260 parts of acrylonitrile were uniformly dissolved in this.
過酸化ラウロイル５部、ターシャリドデシルメルカプタ
ン３部およびビスーターシャリブチルパーオギシシクａ
ヘキサン０．５５部を添加して６５℃１０時間、その後
１０５℃で２時間重合して重合を完結した。この時の重
合率は９８％であった。5 parts lauroyl peroxide, 3 parts tert-dodecyl mercaptan and bis-tertiary butyl peroxide a
After adding 0.55 parts of hexane, the mixture was polymerized at 65° C. for 10 hours, and then at 105° C. for 2 hours to complete the polymerization. The polymerization rate at this time was 98%.
ここで得られた重合体粒子を水洗、脱水、乾燥して熱可
塑性樹脂（ｆｆｉ （芳香族系共重合体粒子）を得た。The polymer particles obtained here were washed with water, dehydrated, and dried to obtain a thermoplastic resin (ffi (aromatic copolymer particles)).
実施例１
前記製造法で得た熱可塑性樹脂（Ｉ） ５００部、熱可
塑性樹脂（Ｎ） ２００部及び熱可塑性樹脂（ＩＩＩ）
３００部の混合物に２５℃における粘度が１００００
センチストークス（Ｃ８）のジメチルポリシロキサンオ
イルを１０部混合し、他にカーボッ３部ト安定剤（ヒン
ダードフェノール系醸化防止剤、ヒンダードアミン系光
安定剤及びベンゾトリアゾール系紫外線吸収剤よりなる
）５部を混合したものを３９ ｍｍφ押出機で押出しペ
レット状にした。Example 1 500 parts of thermoplastic resin (I) obtained by the above manufacturing method, 200 parts of thermoplastic resin (N), and thermoplastic resin (III)
300 parts of the mixture has a viscosity of 10,000 at 25°C.
Mix 10 parts of centistokes (C8) dimethylpolysiloxane oil, and 3 parts of carb stabilizer (consisting of a hindered phenol-based fermentation inhibitor, a hindered amine-based light stabilizer, and a benzotriazole-based ultraviolet absorber) 5 The mixture was extruded into pellets using a 39 mmφ extruder.
このペレットを用いて射出成形機でＡＳＴＭに記載され
る所定の成形品（試験片）を作成し。Using this pellet, a predetermined molded product (test piece) as specified in ASTM was created using an injection molding machine.
この試験片を用いて耐傷付き性試験及び機械的特性を評
価した。その結果を第１表に示す。This test piece was used to evaluate scratch resistance and mechanical properties. The results are shown in Table 1.
評価方法
耐傷付き性試験：３００Ｗｌの高さより１２０メツシユ
スルーの砂を成形品に連続して３分落下させ、その後エ
チルアルコールに浸シたガーゼで表面を軽くふきとりそ
の時の傷の付き方を目視判定した（■傷付きなし、■多
少傷付きあす、■全面に傷発生）。Evaluation method Scratch resistance test: 120 mesh through sand was continuously dropped on the molded product from a height of 300 Wl for 3 minutes, and then the surface was lightly wiped with gauze soaked in ethyl alcohol and the extent of scratches was visually judged. (■ No scratches, ■ Some scratches, ■ Scratches on the entire surface).
アイゾツト衝撃強さ：ＡＳＴＭ Ｄ２５６に従いｌ／♂
ノツチ付で測定した。Izot impact strength: l/♂ according to ASTM D256
Measured with a notch.
熱変形温度：ＡＳＴＭ Ｄ６４８に従い１／２’。Heat distortion temperature: 1/2' according to ASTM D648.
２６４ Ｐｓｉで耐熱性を測定した。Heat resistance was measured at 264 Psi.
メルトフローレート：ＪＩＳ Ｋ ７３１０に従い２２
０℃ １０に９で流動性を測定した。Melt flow rate: 22 according to JIS K 7310
Fluidity was measured at 0°C and 9 to 10.
表面光沢：サンシャインウェザ−メータによる耐候性促
進試験を行ない、それぞｎｏ、６００゜１０００．２０
００時間照射後の成形品の表面光沢（反射率）をグロス
メーターを用い。Surface gloss: accelerated weather resistance test using sunshine weather meter, no, 600° 1000.20 respectively
Measure the surface gloss (reflectance) of the molded product after 00 hours of irradiation using a gloss meter.
入射角６０°１反射角６０°で測定した。Measurements were made at an incident angle of 60° and a reflection angle of 60°.
実施例２〜４
２５℃における粘度が１００００センチストークス（Ｃ
８）のジメチルポリシロキサンオイル３部、１５部、３
０部混合する他は実施例１と同様にして試験片を作成し
評価し文。Examples 2 to 4 Viscosity at 25°C is 10,000 centistokes (C
8) dimethylpolysiloxane oil 3 parts, 15 parts, 3
Test pieces were prepared and evaluated in the same manner as in Example 1, except that 0 parts were mixed.
比較例１．２
比較例１ｉｄジメチルポリシロキサンオイルｔｉ合しな
い場合、比較例２は２５℃における粘度が１００００Ｃ
８のジメチルポリシロキサンオイルを２０部混合した他
は実施例１と同様にして試験片を作成し、評価した。そ
の結果を、＠１表に示す。Comparative Example 1.2 Comparative Example 1id If dimethylpolysiloxane oil ti is not combined, Comparative Example 2 has a viscosity of 10000C at 25°C.
A test piece was prepared and evaluated in the same manner as in Example 1, except that 20 parts of dimethylpolysiloxane oil No. 8 was mixed therein. The results are shown in Table @1.
実施例５〜７
２５℃における粘度が１０００センチストークス（Ｃ８
）、５０００センチストークス（Ｃ８）。Examples 5 to 7 Viscosity at 25°C is 1000 centistokes (C8
), 5000 centistokes (C8).
１２５００センチストークス（Ｃ８）のジメチルポリシ
ロキサンオイルを１温湿合する他は実施例１と同様にし
て試験片を作成し評価した。その結果を第２表に示す。A test piece was prepared and evaluated in the same manner as in Example 1, except that dimethylpolysiloxane oil of 12,500 centistokes (C8) was wetted at one temperature. The results are shown in Table 2.
比較例３〜５
２５℃における粘度が１００センチストークス（Ｃ８）
、５００センチストークス（Ｃ８）。Comparative Examples 3 to 5 Viscosity at 25°C is 100 centistokes (C8)
, 500 centistokes (C8).
６００００センチストークス（Ｃ８）のジメチルポリシ
ロキサンオイルを１温湿合した他は実施例１と同様にし
て試験片を作成し評価した。その結果を第２表に示す。A test piece was prepared and evaluated in the same manner as in Example 1, except that dimethylpolysiloxane oil of 60,000 centistokes (C8) was wetted at one temperature. The results are shown in Table 2.
実施例８
熱可塑性樹脂（Ｉ） ５００部、熱可塑性樹脂（Ｉｔ）
３００部及び熱可塑性樹脂（ＩＩＩ） ２００部を混合
した他は実施例１と同様にして試験片を作成し評価した
。その結果を第３表に示す。Example 8 500 parts of thermoplastic resin (I), thermoplastic resin (It)
A test piece was prepared and evaluated in the same manner as in Example 1, except that 300 parts of the thermoplastic resin (III) and 200 parts of the thermoplastic resin (III) were mixed. The results are shown in Table 3.
実施例９
熱可塑性樹脂（Ｉ） ５００部、熱可塑性樹脂（ＩＩ）
４００部及び熱可塑性樹脂（ｉｌｌ）１００部を混合し
た他は実施例１と同様にして試験片を作成し評価した。Example 9 500 parts of thermoplastic resin (I), thermoplastic resin (II)
A test piece was prepared and evaluated in the same manner as in Example 1, except that 400 parts of the thermoplastic resin (ill) and 100 parts of the thermoplastic resin (ill) were mixed.
その結果を第３表に示す。The results are shown in Table 3.
比較例６
熱可塑性樹脂（Ｉｊ ５００部、熱可塑性樹脂（Ｉｒ１
５００部を混合した他は実施例１と同様にして試験片を
作成し評価した。その結果を第３表に示す。Comparative Example 6 Thermoplastic resin (Ij 500 parts, thermoplastic resin (Ir1
Test pieces were prepared and evaluated in the same manner as in Example 1, except that 500 parts were mixed. The results are shown in Table 3.
第
表
（発明の効果）
本発明の耐候性樹脂組成物は、耐衝重性、成形性、耐熱
性、成形品外観及び耐候性が浸れており。Table 1 (Effects of the Invention) The weather-resistant resin composition of the present invention is excellent in impact resistance, moldability, heat resistance, molded product appearance, and weather resistance.
加えて特に成形品の傷付き性が優れているので自動車部
品用や屋外で使用される用途の成形品に最適である。In addition, molded products have excellent scratch resistance, making them ideal for molded products used in automobile parts and outdoors.
Claims (1)
３０アルキル基を有するアクリル酸エステル５０〜９９
．９重量％及び共重合可能な他のビニル化合物０〜３０
重量％を配合して得られる重合性単量体混合物（ａ）９
５〜６０重量部をジエン系重合体（ｂ）５〜４０重量部
の存在下に、（ａ）と（ｂ）の合計が１００重量部とな
るように配合し、重合率が５０〜９３％まで乳化重合さ
せた後、重合を停止させて得られるグラフト重合体ゴム
（Ａ）５〜５０重量部の存在下に、芳香族ビニル化合物
０〜１００重量％メタクリル酸エステル０〜１００重量
％及びシアン化ビニル化合物０〜４０重量％からなる単
量体（Ｂ）９５〜５０重量部を、（Ａ）と（Ｂ）の合計
が１００重量部となるように配合し、重合させて得られ
る熱可塑性樹脂（１）２０〜９０重量部、炭素原子数５
〜２２個の脂環式炭化水素基を有するメタクリル酸エス
テル２０〜１００重量％及び共重合可能な他の重合性単
量体０〜８０重量％を重合させて得られる熱可塑性樹脂
（II）５〜４０重量部、並びに芳香族ビニル化合物６５
〜８５重量％及びシアン化ビニル化合物１５〜３５重量
％を重合させて得られる熱可塑性樹脂（III）５〜４０
重量部を（ I ）、（II）及び（III）の合計が１００重
量部となるように配合して得られる混合物に、２５℃に
おける粘度が１０００〜３００００センチストークスの
ジメチルポリシロキサンオイルを該混合物に対して０．
１〜１０重量％混合してなる耐傷付き性の改良された耐
候性樹脂組成物。 ２、重合性単量体混合物（ａ）の多官能性単量体がトリ
アリルイソシアヌレートまたはトリアリルシアヌレート
である請求項１記載の耐候性樹脂組成物。 ３、熱可塑性樹脂（II）の炭素原子数５〜２２個の脂環
式炭化水素基を有するメタクリル酸エステルが、メタク
リル酸ノルボニル、メタクリル酸ノルボニルメチル、メ
タクリル酸トリシクロ〔５，２，１，０＾２＾，＾６〕
デカ−８−イル、メタクリル酸トリシクロ〔５，２，１
，０＾２＾，＾６〕デカ−３−メチル及びメタクリル酸
トリシクロ〔５，２，１，０＾２＾，＾６〕デカ−４−
メチルから選択される少なくとも１種のメタクリル酸エ
ステルである請求項１または２記載の耐候性樹脂組成物
。 ４、請求項１、２または３記載の耐候性樹脂組成物を用
いて成形して得られる成形品。[Claims] 1. 0.1 to 20% by weight of polyfunctional monomer, 1 to 1 carbon number
Acrylic acid ester having 30 alkyl groups 50-99
．． 9% by weight and 0-30% of other copolymerizable vinyl compounds
Polymerizable monomer mixture (a) 9 obtained by blending % by weight
5 to 60 parts by weight of diene polymer (b) is blended in the presence of 5 to 40 parts by weight so that the total of (a) and (b) is 100 parts by weight, and the polymerization rate is 50 to 93%. In the presence of 5 to 50 parts by weight of the graft polymer rubber (A) obtained by emulsion polymerization until the polymerization is terminated, 0 to 100 parts by weight of an aromatic vinyl compound, 0 to 100 parts by weight of a methacrylic acid ester, and cyanide are added. A thermoplastic material obtained by blending 95 to 50 parts by weight of a monomer (B) consisting of 0 to 40 parts by weight of a vinyl compound so that the total of (A) and (B) is 100 parts by weight, and polymerizing the mixture. Resin (1) 20 to 90 parts by weight, number of carbon atoms 5
Thermoplastic resin (II) obtained by polymerizing 20 to 100% by weight of a methacrylic acid ester having ~22 alicyclic hydrocarbon groups and 0 to 80% by weight of another copolymerizable monomer (II) 5 ~40 parts by weight, and 65 parts by weight of aromatic vinyl compound
Thermoplastic resin (III) obtained by polymerizing ~85% by weight and 15-35% by weight of a vinyl cyanide compound 5-40
Add dimethylpolysiloxane oil having a viscosity of 1,000 to 30,000 centistokes at 25°C to a mixture obtained by blending parts by weight of (I), (II), and (III) so that the total is 100 parts by weight. 0.
A weather-resistant resin composition with improved scratch resistance formed by mixing 1 to 10% by weight. 2. The weather-resistant resin composition according to claim 1, wherein the polyfunctional monomer of the polymerizable monomer mixture (a) is triallyl isocyanurate or triallyl cyanurate. 3. The methacrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms of the thermoplastic resin (II) can be used as norbornyl methacrylate, norbornylmethyl methacrylate, or tricyclo[5,2,1, 0^2^,^6〕
Dec-8-yl, tricyclo methacrylate [5,2,1
,0^2^,^6]deca-3-methyl and methacrylic acid tricyclo[5,2,1,0^2^,^6]deca-4-
The weather-resistant resin composition according to claim 1 or 2, which is at least one methacrylic ester selected from methyl. 4. A molded article obtained by molding the weather-resistant resin composition according to claim 1, 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15828490A JPH0450252A (en) | 1990-06-15 | 1990-06-15 | Weather-resistant resin composition having improved scratch resistance and molded article thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15828490A JPH0450252A (en) | 1990-06-15 | 1990-06-15 | Weather-resistant resin composition having improved scratch resistance and molded article thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0450252A true JPH0450252A (en) | 1992-02-19 |
Family
ID=15668235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15828490A Pending JPH0450252A (en) | 1990-06-15 | 1990-06-15 | Weather-resistant resin composition having improved scratch resistance and molded article thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0450252A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010106095A (en) * | 2008-10-29 | 2010-05-13 | Mitsubishi Rayon Co Ltd | Water-based coating material and production method of emulsion |
| CN112566977A (en) * | 2018-06-18 | 2021-03-26 | 英力士苯领集团股份公司 | Thermoplastic composition with improved resistance to ultraviolet light |
-
1990
- 1990-06-15 JP JP15828490A patent/JPH0450252A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010106095A (en) * | 2008-10-29 | 2010-05-13 | Mitsubishi Rayon Co Ltd | Water-based coating material and production method of emulsion |
| CN112566977A (en) * | 2018-06-18 | 2021-03-26 | 英力士苯领集团股份公司 | Thermoplastic composition with improved resistance to ultraviolet light |
| US11965066B2 (en) | 2018-06-18 | 2024-04-23 | Ineos Styrolution Group Gmbh | Thermoplastic compositions with improved UV resistance |
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