JP5457518B2 - Thermoplastic resin composition for vehicle lamp and molded product - Google Patents
Thermoplastic resin composition for vehicle lamp and molded product Download PDFInfo
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- JP5457518B2 JP5457518B2 JP2012164339A JP2012164339A JP5457518B2 JP 5457518 B2 JP5457518 B2 JP 5457518B2 JP 2012164339 A JP2012164339 A JP 2012164339A JP 2012164339 A JP2012164339 A JP 2012164339A JP 5457518 B2 JP5457518 B2 JP 5457518B2
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- 239000011342 resin composition Substances 0.000 title claims description 32
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 22
- 239000000178 monomer Substances 0.000 claims description 68
- 239000002131 composite material Substances 0.000 claims description 54
- 229920000578 graft copolymer Polymers 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 43
- 229920001971 elastomer Polymers 0.000 claims description 43
- 239000005060 rubber Substances 0.000 claims description 43
- 229920002554 vinyl polymer Polymers 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 29
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 24
- 229920000058 polyacrylate Polymers 0.000 claims description 16
- 230000008961 swelling Effects 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 229920003244 diene elastomer Polymers 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims 1
- 229920000126 latex Polymers 0.000 description 40
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 29
- 229920003048 styrene butadiene rubber Polymers 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000000034 method Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 239000004816 latex Substances 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 238000006467 substitution reaction Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
- 238000010079 rubber tapping Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 10
- 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
- 238000001035 drying Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 239000011790 ferrous sulphate Substances 0.000 description 7
- 235000003891 ferrous sulphate Nutrition 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- -1 4-t-butylphenyl Chemical group 0.000 description 5
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000005185 salting out Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000008101 lactose Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000003063 flame retardant Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229940096992 potassium oleate Drugs 0.000 description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-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
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-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
- FWEOQOXTVHGIFQ-UHFFFAOYSA-N 8-anilinonaphthalene-1-sulfonic acid Chemical compound C=12C(S(=O)(=O)O)=CC=CC2=CC=CC=1NC1=CC=CC=C1 FWEOQOXTVHGIFQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- KLIYQWXIWMRMGR-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate Chemical compound C=CC=C.COC(=O)C(C)=C KLIYQWXIWMRMGR-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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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Landscapes
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、耐衝撃性、流動性、耐侯性などの車両灯具用樹脂組成物として必要な性能バランスに優れるだけでなく、取り付け時のタッピング強度、とりわけ低温環境下でのタッピング強度に優れる車両灯具用熱可塑性樹脂組成物及び該樹脂組成物から得られた成形品に関するものである。 The present invention is not only excellent in the performance balance required as a resin composition for vehicle lamps such as impact resistance, fluidity and weather resistance, but also in vehicle lamps excellent in tapping strength at the time of mounting, particularly in a low temperature environment. The present invention relates to a thermoplastic resin composition and a molded product obtained from the resin composition.
一般的に車両用灯具は、リフレクターを有するランプハウジングの前面開口部を覆うようにしてレンズが装着され、ランプハウジングとレンズにより囲まれた灯室の中に光源バルブが設置された構造体である。通常、車両用灯具はランプハウジング裏側に形成されたタッピングボスに対し、車両ボディーを介してボルト締めすることにより固定されている。 In general, a vehicular lamp is a structure in which a lens is mounted so as to cover a front opening of a lamp housing having a reflector, and a light source bulb is installed in a lamp chamber surrounded by the lamp housing and the lens. . Usually, the vehicular lamp is fixed to a tapping boss formed on the back side of the lamp housing by bolting via a vehicle body.
このような車両用灯具は、光源バルブから発する光を有効に反射させるため、ランプハウジングの内面を一般的に銀色塗装、或いはアルミニウム蒸着を施し、リフレクターの反射面として作用させている。しかし、有機溶剤が環境に与える問題や、製造工程の簡略化等による生産性向上のため、塗装排除やアンダーコート処理工程の省略（いわゆるダイレクト蒸着）が行われている。これにより、リフレクターとしての高輝性を発現するためには、ランプハウジングを構成する樹脂材料として製品表面の平滑性が重要視される。 In such a vehicular lamp, in order to effectively reflect the light emitted from the light source bulb, the inner surface of the lamp housing is generally subjected to silver paint or aluminum deposition to act as a reflecting surface of the reflector. However, in order to improve the productivity due to the problem caused by the organic solvent and the simplification of the manufacturing process, the paint removal and the undercoat treatment process are omitted (so-called direct vapor deposition). Thereby, in order to express high brightness as a reflector, the smoothness of the product surface is regarded as important as a resin material constituting the lamp housing.
また、ランプハウジングとレンズ部品は、一般的に各種溶着方法によって樹脂を溶融させ接合するが、その溶着強度は一定レベル確保する必要があり、また溶着時の外観を重視され、糸引き・糸バリ（溶融樹脂カス）を発生させないような技術が必要とされている。 In general, the lamp housing and lens parts are joined by melting the resin by various welding methods. However, it is necessary to secure a certain level of welding strength, and the appearance during welding is emphasized. There is a need for a technique that does not generate (molten resin residue).
これら車両用灯具として必要とされる性能を備えた樹脂組成物については、例えば特許文献１〜３のような提案がなされている。 For example, Patent Documents 1 to 3 have been proposed for resin compositions having performance required for these vehicular lamps.
しかし、これら特許文献１〜３のように車両用灯具として必要とされる性能を備えた樹脂組成物で構成されていても、車両本体に取り付ける際のタッピング強度が不十分な場合、ボルト締結時のタッピングボス破損、或いはボルト締め付け時の強度不足による灯具脱落といった問題がみられる。特に寒冷地ではこのような不具合事象が発生しやすい環境であり、十分なタッピング強度を有する車両灯具用樹脂材料が求められている。 However, even if it is comprised with the resin composition provided with the performance required as a vehicle lamp like these patent documents 1-3, when tapping strength at the time of attaching to a vehicle body is inadequate, at the time of bolt fastening There is a problem that the tapping boss is broken or the lamp is dropped due to insufficient strength when tightening the bolt. Particularly in cold districts, such a malfunction is likely to occur, and there is a demand for a resin material for vehicle lamps having sufficient tapping strength.
本発明の目的は、耐衝撃性、流動性、耐侯性などの車両灯具用樹脂組成物として必要な性能バランスに優れるだけでなく、取り付け時のタッピング強度、とりわけ低温環境下でのタッピング強度に優れる車両灯具用熱可塑性樹脂組成物及び該樹脂組成物から得られた成形品を提供することである。 The object of the present invention is not only excellent in the performance balance required as a resin composition for vehicle lamps such as impact resistance, fluidity and weather resistance, but also excellent in tapping strength at the time of mounting, particularly in a low temperature environment. A thermoplastic resin composition for vehicle lamps and a molded product obtained from the resin composition are provided.
本発明者らは、上述の問題点を解決すべく鋭意検討を行った結果、特定のポリマー構成を持つ複合ゴムに、シアン化ビニル系単量体、芳香族ビニル系単量体等の単量体混合物を重合して得られるグラフト共重合体を用いることにより、上記目的を達成できることを見出し、本発明に到達した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the composite rubber having a specific polymer structure is a single monomer such as a vinyl cyanide monomer or an aromatic vinyl monomer. The inventors have found that the above object can be achieved by using a graft copolymer obtained by polymerizing a body mixture, and have reached the present invention.
すなわち、グラフト共重合体（Ａ）２０〜７０重量部、共重合体（Ｂ）３０〜８０重量部を含む熱可塑性樹脂組成物（グラフト共重合体（Ａ）と共重合体（Ｂ）の合計は１００重量部）であって、グラフト共重合体（Ａ）は共役ジエン系ゴム状重合体５〜５０重量％と架橋アクリル酸エステル系重合体５０〜９５重量％から構成される複合ゴム１０〜８０重量部に、芳香族ビニル系単量体、シアン化ビニル系単量体及びこれらと共重合可能な他のビニル系単量体から選ばれた少なくとも一種の単量体２０〜９０重量部をグラフト重合して得られるグラフト共重合体であり、複合ゴム１．０ｇをテトラヒドロフラン２０ｍｌに２４時間浸漬したときのテトラヒドロフラン可溶部のポリスチレン換算重量平均分子量が５００００〜１０００００、かつ複合ゴム０．２５ｇをトルエン１００ｍｌに４８時間浸漬したときのトルエンに対する膨潤度が７．０〜１３．０であることを特徴とするグラフト共重合体であり、共重合体（Ｂ）は芳香族ビニル系単量体とシアン化ビニル系単量体とを共重合することで得られる共重合体、または、芳香族ビニル系単量体とシアン化ビニル系単量体とその他の共重合可能な他のビニル系単量体とを共重合することで得られる共重合体であることを特徴とする車両灯具用熱可塑性樹脂組成物に関する。
That is, 20 to 70 parts by weight of the graft copolymer (A) and 30 to 80 parts by weight of the copolymer (B) (a total of the graft copolymer (A) and the copolymer (B) Is 100 parts by weight), and the graft copolymer (A) is a composite rubber composed of 5 to 50% by weight of a conjugated diene rubbery polymer and 50 to 95% by weight of a crosslinked acrylate polymer. 80 parts by weight of 20 to 90 parts by weight of at least one monomer selected from aromatic vinyl monomers, vinyl cyanide monomers and other vinyl monomers copolymerizable therewith graft-polymerized a graft copolymer obtained, a polystyrene-reduced weight average molecular weight of tetrahydrofuran-soluble fraction when immersed for 24 hours in tetrahydrofuran 20ml composite rubber 1.0g is 50,000 to 100,000, One composite rubber 0.25g a graft copolymer swelling degree in toluene when immersed for 48 hours in 100ml of toluene is characterized in that it is a 7.0 to 13.0, the copolymer (B) is an aromatic Copolymers obtained by copolymerizing aromatic vinyl monomers and vinyl cyanide monomers, or other copolymers with aromatic vinyl monomers and vinyl cyanide monomers The present invention relates to a thermoplastic resin composition for vehicle lamps, which is a copolymer obtained by copolymerizing with other vinyl monomers .
本発明により、耐衝撃性、流動性、耐侯性などの車両灯具用樹脂組成物として必要な性能バランスに優れるだけでなく、取り付け時のタッピング強度、とりわけ低温環境下でのタッピング強度に優れる車両灯具用熱可塑性樹脂組成物及び該樹脂組成物から得られた成形品を提供することが出来る。 According to the present invention, the vehicle lamp not only has excellent performance balance required as a resin composition for vehicle lamps such as impact resistance, fluidity, and weather resistance, but also has excellent tapping strength at the time of mounting, particularly in a low temperature environment. The thermoplastic resin composition for use and a molded product obtained from the resin composition can be provided.
以下に、本発明の車両灯具用熱可塑性樹脂組成物につき詳細に説明する。
本発明は、グラフト共重合体（Ａ）２０〜７０重量部、共重合体（Ｂ）３０〜８０重量部を含む熱可塑性樹脂組成物である。
Below, it demonstrates in detail about the thermoplastic resin composition for vehicle lamps of this invention.
The present invention is a thermoplastic resin composition containing 20 to 70 parts by weight of the graft copolymer (A) and 30 to 80 parts by weight of the copolymer (B).
本発明において使用されるグラフト共重合体（Ａ）は、共役ジエン系ゴム状重合体と架橋アクリル酸エステル系重合体から構成される複合ゴムの存在下に芳香族ビニル系単量体、シアン化ビニル系単量体、及びこれらと共重合可能な他のビニル系単量体から選ばれた少なくとも１種の単量体をグラフト重合して得られた、グラフト共重合体である。 The graft copolymer (A) used in the present invention comprises an aromatic vinyl monomer, cyanide in the presence of a composite rubber composed of a conjugated diene rubbery polymer and a crosslinked acrylate polymer. A graft copolymer obtained by graft polymerization of at least one monomer selected from vinyl monomers and other vinyl monomers copolymerizable therewith.
本発明で使用される複合ゴムを構成する共役ジエン系ゴム状重合体としては、ポリブタジエンゴム、スチレン−ブタジエンゴム（ＳＢＲ）、スチレン−ブタジエン−スチレン（ＳＢＳ）ブロックコポリマー、スチレン−（エチレン−ブタジエン）−スチレン（ＳＥＢＳ）ブロックコポリマー、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、メチルメタクリレート−ブタジエンゴムが挙げられる。特に、ポリブタジエンゴム、スチレン−ブタジエンゴムが好ましい。 Examples of the conjugated diene rubber-like polymer constituting the composite rubber used in the present invention include polybutadiene rubber, styrene-butadiene rubber (SBR), styrene-butadiene-styrene (SBS) block copolymer, and styrene- (ethylene-butadiene). -Styrene (SEBS) block copolymer, acrylonitrile-butadiene rubber (NBR), methyl methacrylate-butadiene rubber. In particular, polybutadiene rubber and styrene-butadiene rubber are preferable.
共役ジエン系ゴム状重合体の重量平均粒子径に特に制限は無いが、物性バランスの観点から、０．１〜１．０μｍであることが好ましく、０．２〜０．５μｍであることがより好ましい。また、共役ジエン系ゴム状重合体の重量平均粒子径の調節は公知の方法が使用できるが、比較的小粒子径の共役ジエン系ゴム状重合体を予め製造し、凝集肥大化させることで目的とする重量平均粒子径とした、凝集肥大化共役ジエン系ゴム状重合体を用いることも可能である。 Although there is no restriction | limiting in particular in the weight average particle diameter of a conjugated diene type rubber-like polymer, From a viewpoint of a physical-property balance, it is preferable that it is 0.1-1.0 micrometer, and it is more preferable that it is 0.2-0.5 micrometer. preferable. The weight average particle diameter of the conjugated diene rubber-like polymer can be adjusted by a known method, but the purpose is to produce a conjugated diene rubber-like polymer having a relatively small particle diameter in advance and agglomerate it. It is also possible to use an agglomerated enlarged conjugated diene rubbery polymer having a weight average particle diameter of
本発明で使用される複合ゴムを構成する架橋アクリル酸エステル系重合体は、架橋剤の存在下にアルキル基の炭素数が１〜１６のアクリル酸エステル系単量体、例えばメチルアクリレート、エチルアクリレート、ブチルアクリレート、２−エチルヘキシルアクリレート等を一種又は二種以上、さらには必要に応じて他の共重合可能な単量体、例えばスチレン、アクリロニトリル、メチルメタクリレート等を一種又は二種以上を重合して得られる重合体である。 The crosslinked acrylate polymer constituting the composite rubber used in the present invention is an acrylate monomer having an alkyl group having 1 to 16 carbon atoms in the presence of a crosslinking agent, such as methyl acrylate or ethyl acrylate. , Butyl acrylate, 2-ethylhexyl acrylate, or the like, or, if necessary, other copolymerizable monomers such as styrene, acrylonitrile, methyl methacrylate, etc. The resulting polymer.
架橋アクリル酸エステル系重合体に用いられる架橋剤としては、例えばジビニルベンゼン、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジアリルフタレート、ジシクロペンタジエンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールヘキサ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、トリアリルシアヌレート、トリアリルイソシアヌレート等が挙げられる。 Examples of the crosslinking agent used in the crosslinked acrylic ester polymer include divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl phthalate, dicyclopentadiene di (meth) acrylate, trimethylolpropane tri ( Examples include meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, and the like.
本発明で使用される複合ゴムは、共役ジエン系ゴム状重合体の存在下で、架橋アクリル酸エステル系重合体を構成する単量体（混合物）を乳化重合することによって得ることができる。すなわち、本発明の複合ゴムは共役ジエン系ゴム状重合体がコアであり、架橋アクリル酸エステル系重合体がシェルであるコアシェル構造を有している。 The composite rubber used in the present invention can be obtained by emulsion polymerization of a monomer (mixture) constituting a crosslinked acrylate polymer in the presence of a conjugated diene rubber-like polymer. That is, the composite rubber of the present invention has a core-shell structure in which the conjugated diene rubber-like polymer is the core and the crosslinked acrylate polymer is the shell.
本発明で使用される複合ゴムを構成する、共役ジエン系ゴム状重合体と架橋アクリル酸エステル系重合体の比率は、共役ジエン系ゴム状重合体５〜５０重量％、架橋アクリル酸エステル系重合体５０〜９５重量％であることが必要であるが、物性バランスの観点から共役ジエン系ゴム状重合体が７〜４０重量％であることが好ましく、１０〜３０重量％であることがより好ましい。 The ratio of the conjugated diene rubbery polymer to the crosslinked acrylate polymer constituting the composite rubber used in the present invention is 5 to 50% by weight of the conjugated diene rubbery polymer, and the crosslinked acrylate polymer weight. The blend needs to be 50 to 95% by weight, but the conjugated diene rubber-like polymer is preferably 7 to 40% by weight, more preferably 10 to 30% by weight from the viewpoint of balance of physical properties. .
本発明で使用される複合ゴムは、該複合ゴムのテトラヒドロフラン可溶部のポリスチレン換算重量平均分子量が５００００以上、かつ複合ゴムのトルエンに対する膨潤度が７．０以上であることが必要である。重量平均分子量が５００００未満では得られる熱可塑性樹脂組成物の耐衝撃性、発色性及び耐候性に劣る。重量平均分子量が５５０００〜１０００００であることが好ましく、６３０００〜８００００であることがより好ましい。また、膨潤度が７．０未満でも得られる熱可塑性樹脂組成物の耐衝撃性、発色性及び耐候性が劣る。膨潤度が７．５〜１３．０であることが好ましく、８．５〜１１．０であることがより好ましい。 The composite rubber used in the present invention is required to have a polystyrene-equivalent weight average molecular weight of 50,000 or more in the tetrahydrofuran-soluble part of the composite rubber and a swelling degree of the composite rubber with respect to toluene of 7.0 or more. If the weight average molecular weight is less than 50000, the resulting thermoplastic resin composition is inferior in impact resistance, color development and weather resistance. The weight average molecular weight is preferably 55,000 to 100,000, and more preferably 63,000 to 80,000. Moreover, the impact resistance, color developability, and weather resistance of the thermoplastic resin composition obtained even when the degree of swelling is less than 7.0 are inferior. The swelling degree is preferably 7.5 to 13.0, and more preferably 8.5 to 11.0.
本発明で使用される複合ゴムのトルエン溶媒でのゲル含有量に特に制限はないが、物性バランスの観点から、複合ゴムのゲル含有量が９０％以上であることが好ましく、９５％以上であることがより好ましい。 The gel content in the toluene solvent of the composite rubber used in the present invention is not particularly limited, but from the viewpoint of physical properties balance, the gel content of the composite rubber is preferably 90% or more, and 95% or more. It is more preferable.
複合ゴムのテトラヒドロフラン可溶部のポリスチレン換算重量平均分子量及び複合ゴムのトルエンに対する膨潤度を調節する方法としては、いかなる方法であっても構わないが、例えば重合開始剤の種類及び量、重合温度、連鎖移動剤の種類及び量等を変更する方法が挙げられる。 As a method for adjusting the polystyrene-equivalent weight average molecular weight of the tetrahydrofuran-soluble part of the composite rubber and the swelling degree of the composite rubber with respect to toluene, any method may be used. For example, the type and amount of the polymerization initiator, the polymerization temperature, The method of changing the kind and quantity, etc. of a chain transfer agent is mentioned.
本発明で使用されるグラフト共重合体（Ａ）は、上述の複合ゴムの存在下に、芳香族ビニル系単量体、シアン化ビニル系単量体、及びこれらと共重合可能な他のビニル系単量体から選ばれた少なくとも１種の単量体をグラフト重合して得られるグラフト共重合体である。 The graft copolymer (A) used in the present invention includes an aromatic vinyl monomer, a vinyl cyanide monomer, and other vinyls copolymerizable with these in the presence of the above composite rubber. It is a graft copolymer obtained by graft polymerization of at least one monomer selected from the system monomers.
本発明で使用されるグラフト共重合体（Ａ）は該グラフト共重合体１００重量部中に複合ゴムが１０〜８０重量部含まれている必要がある。複合ゴム量が１０重量部より少ないと耐衝撃性、流動性に劣る。８０重量部を超えると耐衝撃性に劣る。複合ゴムの含有量は３０〜７０重量部であることが好ましく、４０〜６０重量部であることがより好ましい。 The graft copolymer (A) used in the present invention needs to contain 10 to 80 parts by weight of a composite rubber in 100 parts by weight of the graft copolymer. When the amount of the composite rubber is less than 10 parts by weight, the impact resistance and fluidity are poor. If it exceeds 80 parts by weight, the impact resistance is poor. The content of the composite rubber is preferably 30 to 70 parts by weight, and more preferably 40 to 60 parts by weight.
グラフト共重合体（Ａ）を構成する芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、パラメチルスチレン、ブロムスチレン等が挙げられ、一種又は二種以上用いることができる。特にスチレン、α−メチルスチレンが好ましい。 Examples of the aromatic vinyl monomer constituting the graft copolymer (A) include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and one or more of them can be used. In particular, styrene and α-methylstyrene are preferable.
シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル、エタクリロニトリル、フマロニトリル等が挙げられ、一種又は二種以上用いることができる。特にアクリロニトリルが好ましい。 Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and the like, and one or more of them can be used. Particularly preferred is acrylonitrile.
共重合可能な他のビニル系単量体としては、（メタ）アクリル酸エステル系単量体、マレイミド系単量体、アミド系単量体等が挙げられ、一種又は二種以上用いることができる。（メタ）アクリル酸エステル系単量体としては（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、アクリル酸２−エチルヘキシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸４−ｔ−ブチルフェニル、（メタ）アクリル酸（ジ）ブロモフェニル、（メタ）アクリル酸クロルフェニル等を例示でき、マレイミド系単量体としてはＮ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等を例示でき、アミド系単量体としてはアクリルアミド、メタクリルアミド等を例示できる。 Examples of other copolymerizable vinyl monomers include (meth) acrylic acid ester monomers, maleimide monomers, amide monomers, and the like, and one or more can be used. . (Meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, (meth) acrylic Examples include phenyl acid, 4-t-butylphenyl (meth) acrylate, (di) bromophenyl (meth) acrylic acid, chlorophenyl (meth) acrylate, and the maleimide monomer includes N-phenylmaleimide, N-cyclohexylmaleimide and the like can be exemplified, and examples of the amide monomer include acrylamide and methacrylamide.
複合ゴムとグラフト重合する、上述の単量体の組成比率に特に制限はないが、芳香族ビニル系単量体６０〜９０重量％、シアン化ビニル系単量体１０〜４０重量％及び共重合可能な他のビニル系単量体０〜３０重量％の組成比率、芳香族ビニル系単量体３０〜８０重量％、（メタ）アクリル酸エステル系単量体２０〜７０重量％及び共重合可能な他のビニル系単量体０〜５０重量％の組成比率、芳香族ビニル系単量体２０〜７０重量％、（メタ）アクリル酸エステル系単量体２０〜７０重量％、シアン化ビニル系単量体１０〜６０重量％及び共重合可能な他のビニル系単量体０〜３０重量％の組成比率等であることが好ましい。 There is no particular limitation on the composition ratio of the above-mentioned monomer that is graft-polymerized with the composite rubber, but the aromatic vinyl-based monomer is 60 to 90% by weight, the vinyl cyanide-based monomer is 10 to 40% by weight, and copolymerization Possible composition ratio of 0-30% by weight of other vinyl monomers, 30-80% by weight of aromatic vinyl monomers, 20-70% by weight of (meth) acrylate monomers, and copolymerizable Other vinyl monomer composition ratio of 0 to 50% by weight, aromatic vinyl monomer 20 to 70% by weight, (meth) acrylic acid ester monomer 20 to 70% by weight, vinyl cyanide The composition ratio is preferably 10 to 60% by weight of the monomer and 0 to 30% by weight of another copolymerizable vinyl monomer.
本発明で使用されるグラフト共重合体（Ａ）を重合するための手法に特に制限はなく、乳化重合法、懸濁重合法、塊状重合法等を用いることが出来る。乳化重合法を用いた場合、上述の複合ゴムに上述の単量体をグラフト重合することによって、グラフト共重合体（Ａ）のラテックスを得ることが出来る。グラフト共重合体（Ａ）のラテックスは、公知の方法により凝固され、洗浄、脱水、乾燥工程を経ることでグラフト共重合体（Ａ）のパウダーを得ることができる。 There is no restriction | limiting in particular in the method for superposing | polymerizing the graft copolymer (A) used by this invention, An emulsion polymerization method, suspension polymerization method, block polymerization method, etc. can be used. When the emulsion polymerization method is used, a latex of the graft copolymer (A) can be obtained by graft polymerization of the above-described monomer to the above-described composite rubber. The latex of the graft copolymer (A) is coagulated by a known method, and the powder of the graft copolymer (A) can be obtained through washing, dehydration, and drying steps.
本発明で使用されるグラフト共重合体（Ａ）のグラフト率（グラフト共重合体のアセトン可溶分量と不溶分量及びグラフト共重合体中の複合ゴムの重量から求める。）、及びアセトン可溶分の還元粘度（０．４ｇ/１００ｃｃ、Ｎ，Ｎジメチルホルムアミド溶液として３０℃で測定）に特に制限はなく、要求性能によって任意の構造のものを使用することができるが、物性バランスの観点から、グラフト率は５〜１５０％であることが好ましく、還元粘度は０．２〜２．０ｄｌ／ｇであることが好ましい。 Graft ratio of graft copolymer (A) used in the present invention (determined from the amount of acetone soluble and insoluble components of the graft copolymer and the weight of the composite rubber in the graft copolymer), and the acetone soluble component. There is no particular limitation on the reduced viscosity (measured at 30 ° C. as an N, N dimethylformamide solution) of 0.4 g / 100 cc, and any structure can be used depending on the required performance, but from the viewpoint of balance of physical properties, The graft ratio is preferably 5 to 150%, and the reduced viscosity is preferably 0.2 to 2.0 dl / g.
また、得られたグラフト共重合体（Ａ）は単独で使用できるが、必要に応じて芳香族ビニル系単量体、シアン化ビニル系単量体、必要に応じてその他の共重合可能な他のビニル系単量体を共重合することで得られる共重合体（Ｂ）と混合し、熱可塑性樹脂組成物として使用することもできる。共重合体（Ｂ）と混合する場合は熱可塑性樹脂組成物の複合ゴム含有量が３〜５０重量％とすることが物性バランスの観点から好ましく、１０〜３０重量％とすることがより好ましい。 The obtained graft copolymer (A) can be used alone, but if necessary, an aromatic vinyl monomer, a vinyl cyanide monomer, or other copolymerizable other if necessary. It can also be used as a thermoplastic resin composition by mixing with a copolymer (B) obtained by copolymerizing the vinyl monomer. When mixed with the copolymer (B), the composite rubber content of the thermoplastic resin composition is preferably 3 to 50% by weight, more preferably 10 to 30% by weight, from the viewpoint of balance of physical properties.
本発明で用いられる共重合体（Ｂ）は芳香族ビニル系単量体、シアン化ビニル系単量体、必要に応じてその他の共重合可能な他のビニル系単量体を共重合することで得られる共重合体である。 The copolymer (B) used in the present invention is a copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer, and other vinyl monomers that can be copolymerized as required. It is a copolymer obtained by.
共重合体（Ｂ）を構成する芳香族ビニル系単量体、シアン化ビニル系単量体、共重合可能な他の単量体としては、グラフト共重合体（Ａ）で用いられる単量体と同様のものを用いることができる。 As the aromatic vinyl monomer, vinyl cyanide monomer, and other copolymerizable monomers constituting the copolymer (B), monomers used in the graft copolymer (A) The same can be used.
本発明で用いられる共重合体（Ｂ）は従来公知の重合技術、例えば乳化重合法、塊状重合法、懸濁重合法、溶液重合法などの重合法により重合することができる。それぞれの重合方法で得られた重合体を組み合わせても良く、重合方法や組成比率の異なる一種又は二種以上の共重合体を組み合わせても良い。 The copolymer (B) used in the present invention can be polymerized by a conventionally known polymerization technique such as an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a solution polymerization method. The polymers obtained by the respective polymerization methods may be combined, or one or two or more types of copolymers having different polymerization methods and composition ratios may be combined.
共重合体（Ｂ）を構成する各単量体の比率に特に制限はないが、共重合体（Ｂ）を構成する単量体の合計量を１００重量部とした場合に、物性バランスの観点から芳香族ビニル系単量体は５０〜８５重量部、シアン化ビニル系単量体は１５〜５０重量部、共重合可能な他の単量体は０〜３５重量部であることが好ましい。 Although there is no restriction | limiting in particular in the ratio of each monomer which comprises a copolymer (B), When a total amount of the monomer which comprises a copolymer (B) is 100 weight part, it is a viewpoint of a physical-property balance. From 50 to 85 parts by weight of the aromatic vinyl monomer, from 15 to 50 parts by weight of the vinyl cyanide monomer, and from 0 to 35 parts by weight of the other copolymerizable monomer.
本発明の車両灯具用熱可塑性樹脂組成物はグラフト共重合体（Ａ）と共重合体（Ｂ）の合計を１００重量部とした時に、グラフト共重合体（Ａ）が２０〜７０重量部、共重合体（Ｂ）が３０〜８０重量部の比率であることが必要である。グラフト共重合体（Ａ）が２０重量部未満では耐衝撃性に劣る。８０重量部を超えると流動性に劣る。耐衝撃性、流動性、タッピング強度等の物性と耐候性とのバランスの観点から、グラフト重合体（Ａ）が３０〜６０重量部、共重合体（Ｂ）が４０〜７０重量部であることが好ましい。また、車両灯具用熱可塑性樹脂組成物中に含有する複合ゴムの量は物性バランスの観点から３〜５０重量％とする事が好ましく、１０〜３０重量％とする事がより好ましい。 The thermoplastic resin composition for vehicle lamps of the present invention has a graft copolymer (A) of 20 to 70 parts by weight when the total of the graft copolymer (A) and the copolymer (B) is 100 parts by weight. It is necessary that the copolymer (B) has a ratio of 30 to 80 parts by weight. When the graft copolymer (A) is less than 20 parts by weight, the impact resistance is poor. If it exceeds 80 parts by weight, the fluidity is poor. From the viewpoint of the balance between physical properties such as impact resistance, fluidity, and tapping strength and weather resistance, the graft polymer (A) is 30 to 60 parts by weight and the copolymer (B) is 40 to 70 parts by weight. Is preferred. Further, the amount of the composite rubber contained in the thermoplastic resin composition for vehicle lamps is preferably 3 to 50% by weight, more preferably 10 to 30% by weight from the viewpoint of physical property balance.
本発明の車両灯具用熱可塑性樹脂組成物は、必要に応じてヒンダードアミン系の光安定剤、ヒンダードフェノール系、含硫黄有機化合物系、含リン有機化合物系等の酸化防止剤、フェノール系、アクリレート系等の熱安定剤、ベンゾエート系、ベンゾトリアゾール系、ベンゾフェノン系、サリシレート系の紫外線吸収剤、有機ニッケル系、高級脂肪酸アミド類等の滑剤、リン酸エステル類等の可塑剤、ポリブロモフェニルエーテル、テトラブロモビスフェノール−Ａ、臭素化エポキシオリゴマー、臭素化等の含ハロゲン系化合物、リン系化合物、三酸化アンチモン等の難燃剤・難燃助剤、臭気マスキング剤、カーボンブラック、酸化チタン、顔料、及び染料等を添加することもできる。更に、タルク、炭酸カルシウム、水酸化アルミニウム、ガラス繊維、ガラスフレーク、ガラスビーズ、炭素繊維、金属繊維等の補強剤や充填剤を添加することもできる。 The thermoplastic resin composition for vehicle lamps according to the present invention includes hindered amine light stabilizers, hindered phenol-based, sulfur-containing organic compound-based, phosphorus-containing organic compound-based antioxidants, phenol-based, acrylate as necessary. Heat stabilizers such as benzoate, benzotriazole, benzophenone, salicylate UV absorbers, lubricants such as organic nickel, higher fatty acid amides, plasticizers such as phosphate esters, polybromophenyl ether, Tetrabromobisphenol-A, brominated epoxy oligomers, halogenated compounds such as brominated compounds, phosphorus compounds, flame retardants and flame retardants such as antimony trioxide, odor masking agents, carbon black, titanium oxide, pigments, and Dye etc. can also be added. Furthermore, reinforcing agents and fillers such as talc, calcium carbonate, aluminum hydroxide, glass fibers, glass flakes, glass beads, carbon fibers, and metal fibers can be added.
本発明の車両灯具用熱可塑性樹脂組成物は、その目的を損なわない範囲内において、他の熱可塑性樹脂と混合して使用することもできる。このような他の熱可塑性樹脂として、例えば、ポリカーボネートなどのポリカーボネート系樹脂、ポリメチルメタクリレートなどのアクリル系樹脂、ナイロン６、ナイロン６６、ナイロン１１、ナイロン１２などのポリアミド系樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂、ポリ乳酸などのポリエステル系樹脂等を使用する事が出来る。 The thermoplastic resin composition for vehicle lamps of the present invention can be used by mixing with other thermoplastic resins as long as the purpose is not impaired. Examples of such other thermoplastic resins include polycarbonate resins such as polycarbonate, acrylic resins such as polymethyl methacrylate, polyamide resins such as nylon 6, nylon 66, nylon 11, and nylon 12, polybutylene terephthalate resin, Polyester resins such as polyethylene terephthalate resin and polylactic acid can be used.
本発明の車両灯具用熱可塑性樹脂組成物は、上述の成分を混合することで得ることができる。混合するために、例えば、押出し機、ロール、バンバリーミキサー、ニーダー等の公知の混練装置を用いることができる。 The thermoplastic resin composition for a vehicle lamp of the present invention can be obtained by mixing the above-described components. In order to mix, well-known kneading apparatuses, such as an extruder, a roll, a Banbury mixer, a kneader, can be used, for example.
以下に実施例を示して本発明を具体的に説明するが、本発明はこれらによって何ら制限されるものではない。なお、実施例中にて示す「部」及び「％」は重量に基づくものである。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” are based on weight.
小粒子径スチレン−ブタジエンゴムラテックスの製造
１０リットルの耐圧容器の内部を窒素で置換後、１，３−ブタジエン９５重量部、スチレン５重量部、ｎ−ドデシルメルカプタン０．５重量部、過硫酸カリウム０．３重量部、不均化ロジン酸ナトリウム１．８重量部、水酸化ナトリウム０．１重量部、脱イオン水１４５重量部を仕込み、攪拌しつつ７０℃で８時間反応させた。その後、不均化ロジン酸ナトリウム０．２重量部、水酸化ナトリウム０．１重量部及び脱イオン水５重量部を添加した。さらに温度を７０℃に維持しながら６時間攪拌を継続して反応を終了した。その後、減圧して残存している１，３−ブタジエンを除去し、スチレン−ブタジエンゴムラテックスを得た。得られたスチレン−ブタジエンゴムラテックスを、四酸化オスミウム（ＯｓＯ４）で染色し、乾燥後に透過型電子顕微鏡で写真撮影した。画像解析処理装置（装置名：旭化成（株）製 ＩＰ−１０００ＰＣ）を用いて１０００個のゴム粒子の面積を計測し、その円相当径（直径）を求め、スチレン−ブタジエンゴムの重量平均粒子径を算出した結果、重量平均粒子径は１２０ｎｍであった
Production of small particle size styrene-butadiene rubber latex After replacing the inside of a 10 liter pressure vessel with nitrogen, 95 parts by weight of 1,3-butadiene, 5 parts by weight of styrene, 0.5 parts by weight of n-dodecyl mercaptan, potassium persulfate 0.3 parts by weight, disproportionated sodium rosinate 1.8 parts by weight, sodium hydroxide 0.1 parts by weight, and deionized water 145 parts by weight were charged and reacted at 70 ° C. for 8 hours with stirring. Thereafter, 0.2 parts by weight of disproportionated sodium rosinate, 0.1 parts by weight of sodium hydroxide and 5 parts by weight of deionized water were added. Further, stirring was continued for 6 hours while maintaining the temperature at 70 ° C. to complete the reaction. Thereafter, the remaining 1,3-butadiene was removed under reduced pressure to obtain a styrene-butadiene rubber latex. The obtained styrene-butadiene rubber latex was dyed with osmium tetroxide (OsO 4 ), dried, and photographed with a transmission electron microscope. Using an image analysis processor (apparatus name: IP-1000PC manufactured by Asahi Kasei Co., Ltd.), the area of 1000 rubber particles was measured, the circle equivalent diameter (diameter) was determined, and the weight average particle diameter of styrene-butadiene rubber As a result, the weight average particle size was 120 nm.
凝集肥大化スチレン−ブタジエンゴムラテックスの製造
１０リットルの耐圧容器に、上記で得られたスチレン−ブタジエンゴムラテックス２７０重量部、ドデシルベンゼンスルホン酸ナトリウム０．１重量部を添加して１０分間攪拌混合した後、５％リン酸水溶液２０重量部を１０分間にわたり添加した。次いで１０％水酸化カリウム水溶液１０重量部を添加し、凝集肥大化したスチレン−ブタジエンゴムラテックス（１）を得た。
上述の方法で、凝集肥大化スチレン−ブタジエンゴムの重量平均粒子径を算出した結果、重量平均粒子径は３３０ｎｍであった。
Production of agglomerated styrene-butadiene rubber latex 270 parts by weight of the styrene-butadiene rubber latex obtained above and 0.1 part by weight of sodium dodecylbenzenesulfonate were added to a 10-liter pressure vessel and stirred for 10 minutes. Thereafter, 20 parts by weight of 5% aqueous phosphoric acid solution was added over 10 minutes. Subsequently, 10 parts by weight of a 10% aqueous potassium hydroxide solution was added to obtain an agglomerated styrene-butadiene rubber latex (1).
As a result of calculating the weight average particle diameter of the agglomerated styrene-butadiene rubber by the above-described method, the weight average particle diameter was 330 nm.
１０リットルの耐圧容器に、上記で得られたスチレン−ブタジエンゴムラテックス２７０重量部、ドデシルベンゼンスルホン酸ナトリウム０．３重量部を添加して１０分間攪拌混合した後、５％リン酸水溶液２０重量部を１０分間にわたり添加した。次いで１０％水酸化カリウム水溶液１０重量部を添加し、凝集肥大化したスチレン−ブタジエンゴムラテックス（２）を得た。
上述の方法で、凝集肥大化スチレン−ブタジエンゴムの重量平均粒子径を算出した結果、重量平均粒子径は２５０ｎｍであった。
To a 10 liter pressure vessel, 270 parts by weight of the styrene-butadiene rubber latex obtained above and 0.3 parts by weight of sodium dodecylbenzenesulfonate were added and stirred and mixed for 10 minutes, and then 20 parts by weight of 5% aqueous phosphoric acid solution. Was added over 10 minutes. Next, 10 parts by weight of a 10% aqueous potassium hydroxide solution was added to obtain an agglomerated styrene-butadiene rubber latex (2).
As a result of calculating the weight average particle size of the agglomerated styrene-butadiene rubber by the above-mentioned method, the weight average particle size was 250 nm.
架橋アクリル酸ブチルゴムラテックスの製造
窒素置換したガラスリアクターに、脱イオン水１８０重量部、アクリル酸ブチル１５重量部、メタクリル酸アリル０．１重量部、アルケニルコハク酸ジカリウム０．１６重量部（固形分換算）、過硫酸カリウム０．１５重量部を仕込み、６５℃で１時間反応させた。その後、アクリル酸ブチル８５重量部、メタクリル酸アリル０．５３重量部の混合液及び脱イオン水２０重量部にアルケニルコハク酸ジカリウム０．６４重量部（固形分換算）を溶解した乳化剤水溶液を３時間かけて連続的に添加した。滴下後、３時間保持して、架橋アクリル酸ブチルゴムラテックスを得た。
Production of cross-linked butyl acrylate rubber latex In a nitrogen-replaced glass reactor, 180 parts by weight of deionized water, 15 parts by weight of butyl acrylate, 0.1 parts by weight of allyl methacrylate, 0.16 parts by weight of dipotassium alkenyl succinate (in terms of solid content) ), 0.15 part by weight of potassium persulfate was added and reacted at 65 ° C. for 1 hour. Thereafter, an emulsifier aqueous solution in which 0.64 parts by weight of dipotassium alkenyl succinate (in terms of solid content) was dissolved in 85 parts by weight of butyl acrylate and 0.53 parts by weight of allyl methacrylate and 20 parts by weight of deionized water was added for 3 hours. Over time. After dripping, it was kept for 3 hours to obtain a crosslinked butyl acrylate rubber latex.
得られた架橋アクリル酸ブチルゴムラテックスの重量平均粒子径を下記に記載する方法で算出した。得られた架橋アクリル酸ブチルゴムラテックスを１５部（固形分）、スチレンを６４部、アクリロニトリルを２１部用いてグラフト共重合を行い、グラフト共重合体を得た。グラフト共重合体のパウダーを溶融混練してペレットを得た。得られたペレットを、クライオミクロトームを用いて−８５℃の雰囲気下で超薄切片を切り出し、四酸化ルテニウム（ＲｕＯ４）で染色し、透過型電子顕微鏡（ＪＥＭ−１４００：日本電子製）で写真撮影した。画像解析装置（旭化成 ＩＰ−１０００ＰＣ）を用いて、１０００個の複合ゴム粒子の面積を計測し、その円相当径（直径）を求め、架橋アクリル酸ブチルゴムラテックスの重量平均粒子径を算出した結果、重量平均粒子径は２００ｎｍであった。 The weight average particle diameter of the obtained crosslinked butyl acrylate rubber latex was calculated by the method described below. Graft copolymerization was performed using 15 parts (solid content) of the obtained crosslinked butyl acrylate rubber latex, 64 parts of styrene, and 21 parts of acrylonitrile to obtain a graft copolymer. The graft copolymer powder was melt-kneaded to obtain pellets. From the obtained pellet, an ultrathin section was cut out at −85 ° C. using a cryomicrotome, stained with ruthenium tetroxide (RuO 4 ), and photographed with a transmission electron microscope (JEM-1400: manufactured by JEOL Ltd.). I took a picture. Using an image analyzer (Asahi Kasei IP-1000PC), the area of 1000 composite rubber particles was measured, the equivalent circle diameter (diameter) was determined, and the weight average particle diameter of the crosslinked butyl acrylate rubber latex was calculated. The weight average particle diameter was 200 nm.
複合ゴム（ａ−１）の製造
１０Ｌのガラスリアクターに、上記の凝集肥大化スチレン−ブタジエンゴムラテックス（１）を２０重量部（固形分）、脱イオン水を１４０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し３５℃に到達したところで脱イオン水２０重量部にナトリウムホルムアルデヒド・スルホキシレート０．０５重量部、エチレンジアミン四酢酸ナトリウム０．０１重量部及び硫酸第１鉄０．００１重量部を溶解した水溶液を添加した。さらに、アクリル酸ブチル１６重量部、メタクリル酸アリル０．１重量部を添加した。槽内の温度が４０℃に到達した後、１時間保持し、脱イオン水２５重量部にアルケニルコハク酸ジカリウム０．９重量部、過硫酸カリウム０．０９重量部を溶解した水溶液とアクリル酸ブチル６４重量部、メタクリル酸アリル０．４重量部を３時間かけて連続的に滴下した。滴下後、３時間保持して、肥大化スチレン−ブタジエンゴムと架橋アクリル酸ブチル重合体から構成される複合ゴムラテックスを得た。
Manufacture of composite rubber (a-1) A 10-liter glass reactor is charged with 20 parts by weight (solid content) of the above-mentioned agglomerated styrene-butadiene rubber latex (1) and 140 parts by weight of deionized water, and nitrogen replacement is performed. It was. After nitrogen substitution, when the temperature inside the tank reached 35 ° C., 20 parts by weight of deionized water, 0.05 parts by weight of sodium formaldehyde sulfoxylate, 0.01 parts by weight of sodium ethylenediaminetetraacetate and ferrous sulfate 0 An aqueous solution in which 0.001 part by weight was dissolved was added. Furthermore, 16 parts by weight of butyl acrylate and 0.1 parts by weight of allyl methacrylate were added. After the temperature in the tank reaches 40 ° C., hold for 1 hour, an aqueous solution of butyl acrylate with 0.9 parts by weight of dipotassium alkenyl succinate and 0.09 parts by weight of potassium persulfate dissolved in 25 parts by weight of deionized water 64 parts by weight and 0.4 parts by weight of allyl methacrylate were continuously added dropwise over 3 hours. After dropping, the mixture was held for 3 hours to obtain a composite rubber latex composed of an enlarged styrene-butadiene rubber and a crosslinked butyl acrylate polymer.
得られた複合ゴムラテックスを乾燥後、１．０ｇをテトラヒドロフラン２０ｍｌに２４時間浸漬した後に、３００メッシュの金網で不溶部を除去し、さらに孔径０．４５μｍのディスポーサブルフィルターでろ過したものをＧＰＣ（ゲルパーミエーションクロマトグラフィー）で測定することで、テトラヒドロフラン可溶部のポリスチレン換算重量平均分子量を求めた。この方法より得られた複合ゴム（ａ−１）のテトラヒドロフラン可溶部の重量平均分子量は６５０００であった。 After drying the obtained composite rubber latex, 1.0 g was immersed in 20 ml of tetrahydrofuran for 24 hours, then the insoluble part was removed with a 300-mesh wire mesh, and further filtered through a disposable filter with a pore size of 0.45 μm. The weight average molecular weight in terms of polystyrene of the tetrahydrofuran-soluble part was determined by measuring with permeation chromatography. The weight average molecular weight of the tetrahydrofuran-soluble part of the composite rubber (a-1) obtained by this method was 65,000.
複合ゴムのトルエンに対する膨潤度は、上述の複合ゴムラテックスを乾燥後、０．２５ｇをトルエン１００ｍｌに４８時間浸漬させた後に、３００メッシュの金網で濾過することで、不溶部の重量（Ｗ１）、不溶部を乾燥した後の重量（Ｗ２）を測定し、下記の式より求めた。
膨潤度＝Ｗ１／Ｗ２
この方法より得られた複合ゴム（Ａ−１）の膨潤度は、９．５であった。
The degree of swelling of the composite rubber with respect to toluene was determined by drying the composite rubber latex described above, immersing 0.25 g in 100 ml of toluene for 48 hours, and filtering through a 300-mesh wire mesh (W 1 ). The weight (W 2 ) after drying the insoluble part was measured and determined from the following formula.
Swelling degree = W 1 / W 2
The swelling degree of the composite rubber (A-1) obtained by this method was 9.5.
複合ゴム（ａ−２）の製造
１０Ｌのガラスリアクターに、上記の凝集肥大化スチレン−ブタジエンゴムラテックス（１）を１０重量部（固形分）、脱イオン水を１４０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し３５℃に到達したところで脱イオン水２０重量部にナトリウムホルムアルデヒド・スルホキシレート０．０５重量部、エチレンジアミン四酢酸ナトリウム０．０１重量部及び硫酸第１鉄０．００１重量部を溶解した水溶液を添加した。さらに、アクリル酸ブチル１６重量部、メタクリル酸アリル０．１重量部を添加した。槽内の温度が４０℃に到達した後、１時間保持し、脱イオン水２５重量部にアルケニルコハク酸ジカリウム０．９重量部、過硫酸カリウム０．０９重量部を溶解した水溶液とアクリル酸ブチル７４重量部、メタクリル酸アリル０．４６重量部を３時間かけて連続的に滴下した。滴下後、３時間保持して、肥大化スチレン−ブタジエンゴムと架橋アクリル酸ブチル重合体から構成される複合ゴムラテックスを得た。
上記方法により得られた、テトラヒドロフラン可溶部のポリスチレン換算重量平均分子量は６８０００、トルエンに対する膨潤度は１０．３であった。
Manufacture of composite rubber (a-2) A 10 L glass reactor was charged with 10 parts by weight (solid content) of the above-mentioned agglomerated styrene-butadiene rubber latex (1) and 140 parts by weight of deionized water, followed by nitrogen replacement. It was. After nitrogen substitution, when the temperature inside the tank reached 35 ° C., 20 parts by weight of deionized water, 0.05 parts by weight of sodium formaldehyde sulfoxylate, 0.01 parts by weight of sodium ethylenediaminetetraacetate and ferrous sulfate 0 An aqueous solution in which 0.001 part by weight was dissolved was added. Furthermore, 16 parts by weight of butyl acrylate and 0.1 parts by weight of allyl methacrylate were added. After the temperature in the tank reaches 40 ° C., hold for 1 hour, an aqueous solution of butyl acrylate with 0.9 parts by weight of dipotassium alkenyl succinate and 0.09 parts by weight of potassium persulfate dissolved in 25 parts by weight of deionized water 74 parts by weight and 0.46 parts by weight of allyl methacrylate were continuously added dropwise over 3 hours. After dropping, the mixture was held for 3 hours to obtain a composite rubber latex composed of an enlarged styrene-butadiene rubber and a crosslinked butyl acrylate polymer.
The weight average molecular weight in terms of polystyrene of the tetrahydrofuran-soluble part obtained by the above method was 68,000, and the degree of swelling with respect to toluene was 10.3.
複合ゴム（ａ−３）の製造
１０Ｌのガラスリアクターに、上記の凝集肥大化スチレン−ブタジエンゴムラテックス（１）を３０重量部（固形分）、脱イオン水を１４０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し３５℃に到達したところで脱イオン水２０重量部にナトリウムホルムアルデヒド・スルホキシレート０．０５重量部、エチレンジアミン四酢酸ナトリウム０．０１重量部及び硫酸第１鉄０．００１重量部を溶解した水溶液を添加した。さらに、アクリル酸ブチル１６重量部、メタクリル酸アリル０．１重量部を添加した。槽内の温度が４０℃に到達した後、１時間保持し、脱イオン水２５重量部にアルケニルコハク酸ジカリウム０．９重量部、過硫酸カリウム０．０７重量部を溶解した水溶液とアクリル酸ブチル５４重量部、メタクリル酸アリル０．３４重量部を３時間かけて連続的に滴下した。滴下後、３時間保持して、肥大化スチレン−ブタジエンゴムと架橋アクリル酸ブチル重合体から構成される複合ゴムラテックスを得た。
上記方法により得られたテトラヒドロフラン可溶部のポリスチレン換算重量平均分子量は６１０００、トルエンに対する膨潤度は７．５であった。
Manufacture of composite rubber (a-3) A 10 L glass reactor was charged with 30 parts by weight (solid content) of the above-mentioned agglomerated styrene-butadiene rubber latex (1) and 140 parts by weight of deionized water, followed by nitrogen substitution. It was. After nitrogen substitution, when the temperature inside the tank reached 35 ° C., 20 parts by weight of deionized water, 0.05 parts by weight of sodium formaldehyde sulfoxylate, 0.01 parts by weight of sodium ethylenediaminetetraacetate and ferrous sulfate 0 An aqueous solution in which 0.001 part by weight was dissolved was added. Furthermore, 16 parts by weight of butyl acrylate and 0.1 parts by weight of allyl methacrylate were added. After the temperature in the tank reaches 40 ° C., hold for 1 hour, an aqueous solution of butyl acrylate with 0.9 parts by weight of dipotassium alkenyl succinate and 0.07 parts by weight of potassium persulfate dissolved in 25 parts by weight of deionized water 54 parts by weight and 0.34 parts by weight of allyl methacrylate were continuously added dropwise over 3 hours. After dropping, the mixture was held for 3 hours to obtain a composite rubber latex composed of an enlarged styrene-butadiene rubber and a crosslinked butyl acrylate polymer.
The tetrahydrofuran-soluble part obtained by the above method had a polystyrene-reduced weight average molecular weight of 61,000 and a swelling degree with respect to toluene of 7.5.
複合ゴム（ａ−４）の製造
１０Ｌのガラスリアクターに、上記の凝集肥大化スチレン−ブタジエンゴムラテックス（２）を２０重量部（固形分）、脱イオン水を１４０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し３５℃に到達したところで脱イオン水２０重量部にナトリウムホルムアルデヒド・スルホキシレート０．０５重量部、エチレンジアミン四酢酸ナトリウム０．０１重量部及び硫酸第１鉄０．００１重量部を溶解した水溶液を添加した。さらに、アクリル酸ブチル１６重量部、メタクリル酸アリル０．１重量部を添加した。槽内の温度が４０℃に到達した後、１時間保持し、脱イオン水２５重量部にアルケニルコハク酸ジカリウム０．９重量部、過硫酸カリウム０．０９重量部を溶解した水溶液とアクリル酸ブチル６４重量部、メタクリル酸アリル０．４重量部を３時間かけて連続的に滴下した。滴下後、３時間保持して、肥大化スチレン−ブタジエンゴムと架橋アクリル酸ブチル重合体から構成される複合ゴムラテックスを得た。
上記方法により得られたテトラヒドロフラン可溶部のポリスチレン換算重量平均分子量は６４０００、トルエンに対する膨潤度は９．７であった。
Manufacture of composite rubber (a-4) A 10-liter glass reactor was charged with 20 parts by weight (solid content) of the above-mentioned agglomerated styrene-butadiene rubber latex (2) and 140 parts by weight of deionized water, followed by nitrogen substitution. It was. After nitrogen substitution, when the temperature inside the tank reached 35 ° C., 20 parts by weight of deionized water, 0.05 parts by weight of sodium formaldehyde sulfoxylate, 0.01 parts by weight of sodium ethylenediaminetetraacetate and ferrous sulfate 0 An aqueous solution in which 0.001 part by weight was dissolved was added. Furthermore, 16 parts by weight of butyl acrylate and 0.1 parts by weight of allyl methacrylate were added. After the temperature in the tank reaches 40 ° C., hold for 1 hour, an aqueous solution of butyl acrylate with 0.9 parts by weight of dipotassium alkenyl succinate and 0.09 parts by weight of potassium persulfate dissolved in 25 parts by weight of deionized water 64 parts by weight and 0.4 parts by weight of allyl methacrylate were continuously added dropwise over 3 hours. After dropping, the mixture was held for 3 hours to obtain a composite rubber latex composed of an enlarged styrene-butadiene rubber and a crosslinked butyl acrylate polymer.
The weight average molecular weight in terms of polystyrene of the tetrahydrofuran-soluble part obtained by the above method was 64000, and the degree of swelling with respect to toluene was 9.7.
複合ゴム（ａ−５）の製造
１０Ｌのガラスリアクターに、上記の凝集肥大化スチレン−ブタジエンゴムラテックス（１）を２０重量部（固形分）、脱イオン水を１４０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し６５℃に到達したところでアクリル酸ブチル１６重量部、メタクリル酸アリル０．１重量部を添加し、槽内の温度が７０℃に到達した後、１時間保持し、脱イオン水２５重量部にアルケニルコハク酸ジカリウム０．９重量部、過硫酸カリウム０．０９重量部を溶解した水溶液とアクリル酸ブチル６４重量部、メタクリル酸アリル０．４重量部を３時間かけて連続的に滴下した。滴下後、３時間保持して、肥大化スチレン−ブタジエンゴムと架橋アクリル酸ブチル重合体から構成される複合ゴムラテックスを得た。
上記方法により得られたテトラヒドロフラン可溶部のポリスチレン換算重量平均分子量は６２０００、トルエンに対する膨潤度は６．１であった。
Manufacture of composite rubber (a-5) A 10 L glass reactor was charged with 20 parts by weight (solid content) of the above-mentioned agglomerated styrene-butadiene rubber latex (1) and 140 parts by weight of deionized water, followed by nitrogen substitution. It was. After nitrogen substitution, when the temperature in the tank reached 65 ° C., 16 parts by weight of butyl acrylate and 0.1 part by weight of allyl methacrylate were added, and the temperature in the tank reached 70 ° C. and held for 1 hour. An aqueous solution prepared by dissolving 0.9 parts by weight of dipotassium alkenyl succinate and 0.09 parts by weight of potassium persulfate in 25 parts by weight of deionized water, 64 parts by weight of butyl acrylate, and 0.4 parts by weight of allyl methacrylate were added for 3 hours. It was dripped continuously over time. After dropping, the mixture was held for 3 hours to obtain a composite rubber latex composed of an enlarged styrene-butadiene rubber and a crosslinked butyl acrylate polymer.
The weight average molecular weight in terms of polystyrene of the tetrahydrofuran-soluble part obtained by the above method was 62000, and the degree of swelling with respect to toluene was 6.1.
複合ゴム（ａ−６）の製造
１０Ｌのガラスリアクターに、上記の凝集肥大化スチレン−ブタジエンゴムラテックス（１）を２０重量部（固形分）、脱イオン水を１４０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し６５℃に到達したところでアクリル酸ブチル１６重量部、メタクリル酸アリル０．１重量部を添加し、槽内の温度が７０℃に到達した後、１時間保持し、脱イオン水２５重量部にアルケニルコハク酸ジカリウム０．９重量部、過硫酸カリウム０．２重量部を溶解した水溶液とアクリル酸ブチル６４重量部、メタクリル酸アリル０．４重量部を３時間かけて連続的に滴下した。滴下後、３時間保持して、肥大化スチレン−ブタジエンゴムと架橋アクリル酸ブチル重合体から構成される複合ゴムラテックスを得た。
上記方法により得られたテトラヒドロフラン可溶部のポリスチレン換算重量平均分子量は４３０００、トルエンに対する膨潤度は５．２であった。
Manufacture of composite rubber (a-6) A 10 L glass reactor was charged with 20 parts by weight (solid content) of the above-mentioned agglomerated styrene-butadiene rubber latex (1) and 140 parts by weight of deionized water, and nitrogen substitution was performed. It was. After nitrogen substitution, when the temperature in the tank reached 65 ° C., 16 parts by weight of butyl acrylate and 0.1 part by weight of allyl methacrylate were added, and the temperature in the tank reached 70 ° C. and held for 1 hour. An aqueous solution in which 0.9 parts by weight of dipotassium alkenyl succinate and 0.2 parts by weight of potassium persulfate are dissolved in 25 parts by weight of deionized water, 64 parts by weight of butyl acrylate, and 0.4 parts by weight of allyl methacrylate are added for 3 hours. It was dripped continuously over time. After dropping, the mixture was held for 3 hours to obtain a composite rubber latex composed of an enlarged styrene-butadiene rubber and a crosslinked butyl acrylate polymer.
The tetrahydrofuran-soluble part obtained by the above method had a polystyrene-reduced weight average molecular weight of 43,000 and a swelling degree with respect to toluene of 5.2.
複合ゴム（ａ−７）の製造
１０Ｌのガラスリアクターに、上記の凝集肥大化スチレン−ブタジエンゴムラテックス（１）を１０重量部（固形分）、脱イオン水を１４０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し６５℃に到達したところでアクリル酸ブチル１６重量部、メタクリル酸アリル０．１重量部を添加し、槽内の温度が７０℃に到達した後、１時間保持し、脱イオン水２５重量部にアルケニルコハク酸ジカリウム０．９重量部、過硫酸カリウム０．２重量部を溶解した水溶液とアクリル酸ブチル７４重量部、メタクリル酸アリル０．４６重量部を３時間かけて連続的に滴下した。滴下後、３時間保持して、肥大化スチレン−ブタジエンゴムと架橋アクリル酸ブチル重合体から構成される複合ゴムラテックスを得た。
上記方法により得られたテトラヒドロフラン可溶部のポリスチレン換算重量平均分子量は４５０００、トルエンに対する膨潤度は５．５であった。
Manufacture of composite rubber (a-7) A 10 L glass reactor was charged with 10 parts by weight (solid content) of the above-mentioned agglomerated styrene-butadiene rubber latex (1) and 140 parts by weight of deionized water, and the nitrogen was replaced. It was. After nitrogen substitution, when the temperature in the tank reached 65 ° C., 16 parts by weight of butyl acrylate and 0.1 part by weight of allyl methacrylate were added, and the temperature in the tank reached 70 ° C. and held for 1 hour. Then, an aqueous solution prepared by dissolving 0.9 parts by weight of dipotassium alkenyl succinate and 0.2 parts by weight of potassium persulfate in 25 parts by weight of deionized water, 74 parts by weight of butyl acrylate, and 0.46 parts by weight of allyl methacrylate are added for 3 hours. It was dripped continuously over time. After dropping, the mixture was held for 3 hours to obtain a composite rubber latex composed of an enlarged styrene-butadiene rubber and a crosslinked butyl acrylate polymer.
The tetrahydrofuran-soluble part obtained by the above method had a polystyrene-reduced weight average molecular weight of 45,000 and a degree of swelling with respect to toluene of 5.5.
グラフト共重合体（Ａ−１）の製造
ガラスリアクターに、複合ゴムラテックス（ａ−１）５０重量部（固形分）を仕込み窒素置換を行った。窒素置換後、槽内を昇温し６５℃に到達したところで、ラクトース０．２重量部、無水ピロリン酸ナトリウム０．１重量部及び硫酸第１鉄０．００５重量部を脱イオン水１０重量部に溶解した水溶液を添加した。７０℃に到達後、アクリロニトリル１５重量部、スチレン３５重量部、ターシャリードデシルメルカプタン０．０５部、クメンハイドロパーオキサイド０．３重量部の混合液及び脱イオン水２０重量部にオレイン酸カリウム１．０重量部を溶解した乳化剤水溶液を４時間かけて連続的に滴下した。滴下後、３時間保持してグラフト共重合体ラテックス（Ａ−１）を得た。その後、塩析・脱水・乾燥し、グラフト重合体（Ａ−１）のパウダーを得た。
Production of Graft Copolymer (A-1) Into a glass reactor, 50 parts by weight (solid content) of the composite rubber latex (a-1) was charged and nitrogen substitution was performed. After nitrogen substitution, when the temperature inside the tank reached 65 ° C., 0.2 parts by weight of lactose, 0.1 parts by weight of anhydrous sodium pyrophosphate and 0.005 parts by weight of ferrous sulfate were added to 10 parts by weight of deionized water. An aqueous solution dissolved in was added. After reaching 70 ° C., a mixture of 15 parts by weight of acrylonitrile, 35 parts by weight of styrene, 0.05 part by weight of tartarid decyl mercaptan and 0.3 parts by weight of cumene hydroperoxide and 20 parts by weight of deionized water was mixed with 1. An aqueous emulsifier solution in which 0 part by weight was dissolved was continuously added dropwise over 4 hours. After dropping, the mixture was held for 3 hours to obtain a graft copolymer latex (A-1). Thereafter, salting out, dehydration, and drying were performed to obtain a powder of the graft polymer (A-1).
グラフト共重合体（Ａ−２）〜（Ａ−７）の製造
複合ゴムラテックス（ａ−１）から複合ゴム（ａ−２）〜（ａ−７）に変更した以外はグラフト共重合体（Ａ−１）と同様に製造し、グラフト共重合体ラテックス（Ａ−２）〜（Ａ−７）を得た。その後、塩析・脱水・乾燥し、グラフト重合体（Ａ−２）〜（Ａ−７）のパウダーを得た。
Production of graft copolymer (A-2) to (A-7) Graft copolymer (A-2) except that the composite rubber latex (a-1) was changed to the composite rubber (a-2) to (a-7). -1) to obtain graft copolymer latexes (A-2) to (A-7). Thereafter, salting out, dehydration and drying were performed to obtain powders of graft polymers (A-2) to (A-7).
グラフト共重合体（Ａ−８）の製造
ガラスリアクターに、凝集肥大化スチレン−ブタジエンゴムラテックス（１）を固形分換算で５０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し６５℃に到達したところで、ラクトース０．２重量部、無水ピロリン酸ナトリウム０．１重量部及び硫酸第１鉄０．００５重量部を脱イオン水１０重量部に溶解した水溶液を添加した後に、７０℃に昇温した。その後、アクリロニトリル１５重量部、スチレン３５重量部、ターシャリードデシルメルカプタン０．０５部、クメンハイドロパーオキサイド０．３重量部の混合液及び脱イオン水２０重量部にオレイン酸カリウム１．０重量部を溶解した乳化剤水溶液を４時間かけて連続的に滴下した。滴下後、３時間保持してグラフト共重合体ラテックス（Ａ−８）を得た。その後、塩析・脱水・乾燥し、グラフト重合体（Ａ−８）のパウダーを得た。
Production of Graft Copolymer (A-8) A glass reactor was charged with 50 parts by weight of agglomerated and enlarged styrene-butadiene rubber latex (1) in terms of solid content, followed by nitrogen substitution. After nitrogen substitution, when the temperature inside the tank reached 65 ° C., 0.2 parts by weight of lactose, 0.1 parts by weight of anhydrous sodium pyrophosphate and 0.005 parts by weight of ferrous sulfate were added to 10 parts by weight of deionized water. After the aqueous solution dissolved in the solution was added, the temperature was raised to 70 ° C. Thereafter, 1.0 part by weight of potassium oleate is added to 15 parts by weight of acrylonitrile, 35 parts by weight of styrene, 0.05 part of tertiary decyl mercaptan, 0.3 part by weight of cumene hydroperoxide and 20 parts by weight of deionized water. The dissolved aqueous emulsifier solution was continuously added dropwise over 4 hours. After dropping, the mixture was held for 3 hours to obtain a graft copolymer latex (A-8). Thereafter, salting-out, dehydration and drying were performed to obtain a graft polymer (A-8) powder.
グラフト共重合体（Ａ−９）の製造
ガラスリアクターに、凝集肥大化スチレン−ブタジエンゴムラテックス（１）を固形分換算で１０重量部、架橋アクリル酸ブチルゴムラテックスを固形分換算で４０重量部仕込み、窒素置換を行った。窒素置換後、槽内を昇温し６５℃に到達したところで、ラクトース０．２重量部、無水ピロリン酸ナトリウム０．１重量部及び硫酸第１鉄０．００５重量部を脱イオン水１０重量部に溶解した水溶液を添加した後に、７０℃に昇温した。その後、アクリロニトリル１５重量部、スチレン３５重量部、ターシャリードデシルメルカプタン０．０５部、クメンハイドロパーオキサイド０．３重量部の混合液及び脱イオン水２０重量部にオレイン酸カリウム１．０重量部を溶解した乳化剤水溶液を４時間かけて連続的に滴下した。滴下後、３時間保持してグラフト共重合体ラテックス（Ａ−９）を得た。その後、塩析・脱水・乾燥し、グラフト重合体（Ａ−９）のパウダーを得た。
Production of Graft Copolymer (A-9) A glass reactor was charged with 10 parts by weight of agglomerated and enlarged styrene-butadiene rubber latex (1) in terms of solids and 40 parts by weight of crosslinked butyl acrylate rubber latex in terms of solids. Nitrogen replacement was performed. After nitrogen substitution, when the temperature inside the tank reached 65 ° C., 0.2 parts by weight of lactose, 0.1 parts by weight of anhydrous sodium pyrophosphate and 0.005 parts by weight of ferrous sulfate were added to 10 parts by weight of deionized water. After the aqueous solution dissolved in the solution was added, the temperature was raised to 70 ° C. Thereafter, 1.0 part by weight of potassium oleate is added to 15 parts by weight of acrylonitrile, 35 parts by weight of styrene, 0.05 part of tertiary decyl mercaptan, 0.3 part by weight of cumene hydroperoxide and 20 parts by weight of deionized water. The dissolved aqueous emulsifier solution was continuously added dropwise over 4 hours. After dropping, the mixture was held for 3 hours to obtain a graft copolymer latex (A-9). Thereafter, salting out, dehydration, and drying were performed to obtain a graft polymer (A-9) powder.
共重合体（Ｂ）の製造
窒素置換したガラスリアクターに、脱イオン水１５０重量部、スチレン７重量部、アクリロニトリル３重量部、ターシャリードデシルメルカプタン０．０２重量部、ドデシルベンゼンスルホン酸ナトリウム０．５部（固形分換算）及び過硫酸カリウム０．３重量部を仕込み、６５℃で１時間重合した。その後、スチレン６３重量部、アクリロニトリル２７重量部、ターシャリードデシルメルカプタン０．１８重量部及びドデシルベンゼンスルホン酸ナトリウム２.５重量部（固形分換算）を含む乳化剤水溶液３０重量部を各々３時間かけて連続的に滴下した。滴下後２時間保持して、共重合体ラテックス（Ｂ）を得た。その後、塩析・脱水・乾燥し、共重合体（Ｂ）のパウダーを得た。
Production of Copolymer (B) A nitrogen-replaced glass reactor was charged with 150 parts by weight of deionized water, 7 parts by weight of styrene, 3 parts by weight of acrylonitrile, 0.02 parts by weight of tarsiad decyl mercaptan, 0.5% sodium dodecylbenzenesulfonate. Part (in terms of solid content) and 0.3 part by weight of potassium persulfate were charged and polymerized at 65 ° C. for 1 hour. Thereafter, 30 parts by weight of an emulsifier aqueous solution containing 63 parts by weight of styrene, 27 parts by weight of acrylonitrile, 0.18 parts by weight of tarsiad decyl mercaptan and 2.5 parts by weight of sodium dodecylbenzenesulfonate (in terms of solid content) was added over 3 hours. It was dripped continuously. After dropping, the mixture was held for 2 hours to obtain a copolymer latex (B). Thereafter, salting out, dehydration and drying were performed to obtain a powder of the copolymer (B).
添加剤
光安定剤：ＡＤＥＫＡ（株）製 アデカスタブ ＬＡ７７Ｙ
紫外線吸収剤：住友化学（株）製 スミソーブ２００
Additive light stabilizer: ADEKA Corporation ADK STAB LA77Y
UV absorber: Sumitomo 200 manufactured by Sumitomo Chemical Co., Ltd.
＜実施例１〜５及び比較例１〜７＞
表１に示すグラフト共重合体（Ａ）、共重合体（Ｂ）及び添加剤を混合した後、４０ｍｍ二軸押出機を用いて２４０℃にて溶融混練してペレットを得た。得られたペレットより、２５０℃に設定した射出成形機にて種々の成形品を成形し、物性評価を行った。評価結果を表１に示す。なお、それぞれの評価方法を以下に示す。
<Examples 1-5 and Comparative Examples 1-7>
After the graft copolymer (A), copolymer (B) and additives shown in Table 1 were mixed, pellets were obtained by melting and kneading at 240 ° C. using a 40 mm twin screw extruder. Various molded products were molded from the obtained pellets with an injection molding machine set at 250 ° C., and physical properties were evaluated. The evaluation results are shown in Table 1. In addition, each evaluation method is shown below.
耐衝撃性
各実施例及び比較例で得られたペレットを用いＩＳＯ試験方法２９４に準拠して各種試験片を成形し、耐衝撃性を測定した。
耐衝撃性はＩＳＯ１７９に準拠し、４ｍｍ厚みで、ノッチ付きシャルピー衝撃値を測定した。単位：ｋＪ／ｍ２
Impact Resistance Various test pieces were molded according to ISO test method 294 using the pellets obtained in each Example and Comparative Example, and impact resistance was measured.
The impact resistance was in conformity with ISO 179, and a Charpy impact value with a notch was measured at a thickness of 4 mm. Unit: kJ / m 2
流動性
各実施例及び比較例で得られたペレットを用い、ＩＳＯ１１３３に準拠して、２２０℃、１０ｋｇ荷重の条件でメルトボリュームフローレイトを測定した。単位；ｃｍ３／１０分
The pellets obtained in Examples and Comparative Examples fluidity, in compliance with ISO 1133, 220 ° C., was measured melt volume flow rate under the condition of 10kg load. Unit; cm 3/10 minutes
耐候性
耐候性の評価には、各実施例及び比較例で得られたペレットを用い、射出成形機（山城精機製作所製 ＳＡＶ−３０−３０ シリンダー温度：２１０℃ 金型温度：５０℃）にて成形された成形品（９０ｍｍ×５５ｍｍ×２．５ｍｍ）を用いた。スガ試験機（株）製サンシャインスーパーロングライフウェザーメーター、ＷＥＬ−ＳＵＮ−ＨＣＨ−Ｂを使用し、６３℃、雨ありの条件下で５００時間の加速曝露試験を行った。その後測色計を用い、曝露前と曝露後の色差（ΔＥ）を測定した。
For evaluation of weather resistance, the pellets obtained in each of Examples and Comparative Examples were used, and injection molding machine (SAV-30-30 manufactured by Yamashiro Seiki Seisakusho, cylinder temperature: 210 ° C, mold temperature: 50 ° C) was used. A molded product (90 mm × 55 mm × 2.5 mm) was used. Using a Sunshine Super Long Life Weather Meter, WEL-SUN-HCH-B, manufactured by Suga Test Instruments Co., Ltd., an accelerated exposure test was conducted for 500 hours under conditions of 63 ° C. and rain. Thereafter, the color difference (ΔE) before and after exposure was measured using a colorimeter.
タッピング強度
内径３．２ｍｍ、外径９．０ｍｍ、高さ２５ｍｍのボス部を中央に有する成形品（直径１３０ｍｍ、厚さ３ｍｍの円板状）を射出成形機により成形する。この成形品のボス部に、マイナス１０℃の環境下でＪＩＳ２種Ｍ４×１２ｍｍのセルフタッピングネジと１ｍｍ厚のワッシャーを入れ、トルク１．５Ｎｍで締付けた際のボス部のクラックの発生有無を目視により確認した。
○：割れ、クラック発生なし
△：僅かにクラック発生
×：著しいクラック、割れ発生
A molded product (a disk shape having a diameter of 130 mm and a thickness of 3 mm) having a boss portion having a tapping strength of an inner diameter of 3.2 mm, an outer diameter of 9.0 mm, and a height of 25 mm in the center is molded by an injection molding machine. Insert a JIS Class 2 M4 × 12 mm self-tapping screw and 1 mm thick washer into the boss part of this molded product in an environment of minus 10 ° C., and visually check for cracks in the boss part when tightened with a torque of 1.5 Nm. Confirmed by
○: No crack or crack occurred △: Slightly cracked ×: Significant crack or crack occurred
表１に示すように、実施例１〜５は本発明に関わる車両灯具用熱可塑性樹脂組成物の例であり、耐衝撃性、流動性、耐候性などの車両灯具用樹脂組成物として必要な性能バランスに優れるだけでなく、低温環境下でのタッピング強度に優れている。 As shown in Table 1, Examples 1 to 5 are examples of the thermoplastic resin composition for vehicle lamps according to the present invention, and are necessary as a resin composition for vehicle lamps such as impact resistance, fluidity, and weather resistance. In addition to excellent performance balance, it also excels in tapping strength in low temperature environments.
表１に示すように、比較例１〜５はグラフト共重合体の使用量、複合ゴムのテトラヒドロフラン可溶分の重量平均分子量、膨潤度が本発明の範囲外であり、耐衝撃性、流動性、耐侯性、及びタッピング強度のバランスに劣っていた。比較例６はグラフト共重合体としてＡＢＳ樹脂を用いているため耐候性に劣っていた。比較例７では共役ジエン系ゴム状重合体とアクリル酸エステル系重合体が複合ゴムとして存在していないため、耐候性に劣る結果であった。 As shown in Table 1, in Comparative Examples 1 to 5, the amount of graft copolymer used, the weight-average molecular weight of the tetrahydrofuran-soluble component of the composite rubber, and the degree of swelling are outside the scope of the present invention. The balance between weather resistance and tapping strength was inferior. Since the comparative example 6 used ABS resin as a graft copolymer, it was inferior in weather resistance. In Comparative Example 7, the conjugated diene rubbery polymer and the acrylate polymer were not present as a composite rubber, and thus the weather resistance was poor.
以上のとおり、本発明の車両灯具用樹脂組成物は、耐衝撃性、流動性、耐候性などの車両灯具用樹脂組成物として必要な性能バランスに優れるだけでなく、車両用灯具製品取り付け時のタッピング強度、とりわけ低温環境下でのタッピング強度に優れることから、車両灯具用樹脂組成物としての付加価値が高く、車両用灯具製品としての利用価値が高い。 As described above, the vehicle lamp resin composition of the present invention not only has excellent performance balance required as a vehicle lamp resin composition, such as impact resistance, fluidity, and weather resistance, but also when a vehicle lamp product is attached. Since it is excellent in tapping strength, particularly tapping strength in a low temperature environment, it has high added value as a resin composition for vehicle lamps and high utility value as a vehicle lamp product.
Claims (3)
A thermoplastic resin composition containing 20 to 70 parts by weight of the graft copolymer (A) and 30 to 80 parts by weight of the copolymer (B) (the total of the graft copolymer (A) and the copolymer (B) is 100). The graft copolymer (A) is a composite rubber composed of 5 to 50% by weight of a conjugated diene rubbery polymer and 50 to 95% by weight of a crosslinked acrylate polymer. 20 to 90 parts by weight of at least one monomer selected from aromatic vinyl monomers, vinyl cyanide monomers, and other vinyl monomers copolymerizable therewith a graft copolymer obtained by polystyrene-reduced weight average molecular weight of tetrahydrofuran-soluble fraction when immersed for 24 hours in tetrahydrofuran 20ml composite rubber 1.0g is 50,000 to 100,000, and the composite Gore A graft copolymer swelling degree of 0.25g in toluene when immersed for 48 hours in 100ml of toluene is characterized in that it is a 7.0 to 13.0, the copolymer (B) is an aromatic vinyl-based Copolymers obtained by copolymerizing monomers and vinyl cyanide monomers, or other copolymerizable aromatic vinyl monomers and vinyl cyanide monomers A thermoplastic resin composition for a vehicle lamp, which is a copolymer obtained by copolymerizing a vinyl monomer .
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