JP2013189606A - Thermoplastic resin composition and molded article thereof - Google Patents
Thermoplastic resin composition and molded article thereof Download PDFInfo
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- JP2013189606A JP2013189606A JP2012058813A JP2012058813A JP2013189606A JP 2013189606 A JP2013189606 A JP 2013189606A JP 2012058813 A JP2012058813 A JP 2012058813A JP 2012058813 A JP2012058813 A JP 2012058813A JP 2013189606 A JP2013189606 A JP 2013189606A
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- vinyl
- mass
- copolymer
- compound
- resin composition
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- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 129
- -1 vinyl cyanide compound Chemical class 0.000 claims abstract description 105
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 95
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 64
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 45
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims description 47
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 14
- 238000010559 graft polymerization reaction Methods 0.000 claims description 7
- 239000005060 rubber Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001463 antimony compounds Chemical class 0.000 abstract description 8
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000002244 precipitate Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000010557 suspension polymerization reaction Methods 0.000 description 11
- 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 9
- 238000000034 method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 229920006358 Fluon Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920006361 Polyflon Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 239000011324 bead Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007333 cyanation reaction Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- FMAMSYPJXSEYSW-VOTSOKGWSA-N (4e)-hepta-1,4-diene Chemical compound CC\C=C\CC=C FMAMSYPJXSEYSW-VOTSOKGWSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OGJJVYFQXFXJKU-UHFFFAOYSA-N 3-methylbicyclo[2.2.1]hepta-2,5-diene Chemical compound C1C2C(C)=CC1C=C2 OGJJVYFQXFXJKU-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-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
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- KUFDSEQTHICIIF-UHFFFAOYSA-N 6-methylhepta-1,5-diene Chemical compound CC(C)=CCCC=C KUFDSEQTHICIIF-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-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
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- UQLNWWMPQBMGOI-UHFFFAOYSA-N pentadeca-2,12-diene Chemical compound C(C)C=CCCCCCCCCC=CC UQLNWWMPQBMGOI-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 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 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
Description
本発明は熱可塑性樹脂組成物に係り、詳しくは、ハロゲン系難燃剤、リン系難燃剤などの難燃剤やアンチモン化合物のような難燃助剤を配合することなく、薄肉厚み（０．５８ｍｍ）における米国ＵＬ規格９４ＨＢに適合する優れた安全性を有し、しかも、外観に優れた成形品を与える熱可塑性樹脂組成物に関する。
本発明はまた、この熱可塑性樹脂組成物を成形してなる成形品に関する。
The present invention relates to a thermoplastic resin composition, and more specifically, a thin thickness (0.58 mm) without blending a flame retardant such as a halogen flame retardant or a phosphorus flame retardant or a flame retardant aid such as an antimony compound. The present invention relates to a thermoplastic resin composition which has excellent safety conforming to US UL standard 94HB and gives a molded article having an excellent appearance.
The present invention also relates to a molded article formed by molding this thermoplastic resin composition.
ＨＩＰＳ（高耐衝撃性ポリスチレン）、ＡＢＳ（アクリロニトリル・ブタジエン・スチレン）樹脂などのスチレン系樹脂は、成形性、寸法安定性、耐衝撃性、剛性に優れているため、電気機器部品、自動車部品、建材等の構成材料として広く利用されている一方で、近年、その製品に対するコストおよび軽量化の意識が高く、その薄肉化が求められ、薄肉化を図った上での安全性の確保が要望されている。 Styrenic resins such as HIPS (high impact resistant polystyrene) and ABS (acrylonitrile butadiene styrene) resins are excellent in moldability, dimensional stability, impact resistance, and rigidity. While it is widely used as a component material for building materials, etc., in recent years, there is a high awareness of cost and weight reduction of its products, and there is a demand for its thinning, and there is a demand for ensuring safety after reducing its thickness. ing.
米国ＵＬ規格のうち９４ＨＢ（水平燃焼試験）では、試験片の厚み３ｍｍを境に以下の燃焼速度が規定されている。
試験片厚みが３．０ｍｍから１３ｍｍの場合：試験片の標線間７５ｍｍでの燃焼速度が１分当り４０ｍｍを超えないこと。
試験片厚みが３．０ｍｍより薄い場合：試験片の標線間７５ｍｍでの燃焼速度が１分当り７５ｍｍを超えないこと。
以上の事より、３．０ｍｍから１３ｍｍ厚みの試験片の場合、試験片の標線間７５ｍｍを１１２．５秒以上の燃焼時間が必要で、３．０ｍｍ以下の場合は、６０秒以上の燃焼時間が必要となり、ＵＬ規格９４ＨＢの規格からも試験片が薄くなると燃焼時間が速くなることから、厚みが３．０ｍｍより大幅に薄い１ｍｍ以下、例えば厚み０．５８ｍｍの試験片では、ＵＬ規格９４ＨＢを満足するのは難しいことが分かる。
In the US UL standard, 94HB (Horizontal Combustion Test) defines the following burning rate with a test piece thickness of 3 mm as a boundary.
When the thickness of the test piece is from 3.0 mm to 13 mm: The burning rate at 75 mm between the marked lines of the test piece should not exceed 40 mm per minute.
When the specimen thickness is less than 3.0 mm: The burning rate at 75 mm between the marked lines of the specimen should not exceed 75 mm per minute.
From the above, in the case of a test piece having a thickness of 3.0 mm to 13 mm, a combustion time of 112.5 seconds or more is required for the 75 mm between the marked lines of the test pieces. Time is required, and the burning time increases as the test piece becomes thinner from the standard of UL standard 94HB. Therefore, for a test piece having a thickness of 1 mm or less, for example 0.58 mm, which is significantly thinner than 3.0 mm, the UL standard 94HB It is difficult to satisfy.
従来、薄肉厚みでの難燃効果を得るためには、ハロゲン系難燃剤、リン系難燃剤などの難燃剤やアンチモン化合物のような難燃助剤を用いているが、これらの成分は、材料加工時や燃焼時に発生する有害な変性物質が人体に悪影響を与えることが懸念される事や各種機械物性や耐熱性が低下するなどの問題がある。 Conventionally, flame retardants such as halogen flame retardants and phosphorus flame retardants and flame retardant aids such as antimony compounds have been used to obtain a flame retardant effect with a thin wall thickness. There are problems such as concern that harmful denatured substances generated during processing and combustion may adversely affect the human body, and various mechanical properties and heat resistance are reduced.
例えば、特許文献１「特表２００８−５３０３５１号公報」には、ゴム変性スチレン系樹脂にリン酸エステル系難燃剤を配合したゴム変性スチレン系難燃樹脂組成物が提案されているが、難燃剤を必要とし、樹脂本来の性能を阻害する問題がある。また、特許文献２「特開２０１０−２７５５６５号公報」には、芳香族ポリカーボネート−ポリオルガノシロキサン共重合体を含む芳香族ポリカーボネート樹脂に、ポリテトラフルオロエチレンを配合した樹脂組成物が提案されているが、ポリカーボネート樹脂を変性して難燃性能を発揮するもので、ＨＩＰＳ、ＡＢＳ樹脂などのスチレン系樹脂では実現が難しい。
一方、特許文献３「特許第３９４４２５３号公報」には、熱可塑性樹脂にフッ素樹脂を配合した熱板融着用樹脂組成物が提案されているが、薄肉厚みでの米国ＵＬ規格９４ＨＢ（水平燃焼試験）については考慮されておらず、本発明の目的を達成できるものではない。
For example, Patent Document 1 “Special Table 2008-530351” proposes a rubber-modified styrene-based flame retardant resin composition in which a phosphate-modified flame retardant is blended with a rubber-modified styrene resin. There is a problem of hindering the original performance of the resin. Patent Document 2 “JP 2010-275565 A” proposes a resin composition in which polytetrafluoroethylene is blended with an aromatic polycarbonate resin containing an aromatic polycarbonate-polyorganosiloxane copolymer. However, the polycarbonate resin is modified to exhibit flame retardancy, and it is difficult to realize with a styrene resin such as HIPS and ABS resin.
On the other hand, Patent Document 3 “Patent No. 3944253” proposes a resin composition for hot plate fusion in which a fluororesin is blended with a thermoplastic resin. However, US UL standard 94HB (horizontal combustion test) with a thin thickness is proposed. ) Is not considered, and the object of the present invention cannot be achieved.
本発明は、上記従来の実状に鑑みてなされたものであって、ハロゲン系難燃剤、リン系難燃剤などの難燃剤やアンチモン化合物のような難燃助剤を配合することなく、薄肉厚み（０．５８ｍｍ）における米国ＵＬ規格９４ＨＢに適合する優れた安全性を示し、しかも、外観に優れた成形品を与える熱可塑性樹脂組成物およびその成形品を提供することを課題とする。 The present invention has been made in view of the above-described conventional situation, and has a thin thickness (without flame retardants such as halogen flame retardants and phosphorus flame retardants and flame retardant aids such as antimony compounds). It is an object of the present invention to provide a thermoplastic resin composition exhibiting excellent safety conforming to US UL standard 94HB at 0.58 mm) and giving a molded product having an excellent appearance, and a molded product thereof.
本発明者は、上記課題を解決すべく鋭意検討した結果、特定のグラフト共重合体とビニル共重合体からなる共重合体混合物であって、グラフト共重合体のシアン化ビニル単位の含有量とビニル共重合体のシアン化ビニル単位の含有量の差の絶対値が３．０〜７．０質量％である共重合体混合物に微量のフッ素樹脂を配合することにより、ＵＬ規格９４ＨＢ燃焼時間を長くすることができ、上記課題を解決することができることを見出した。 As a result of intensive studies to solve the above problems, the present inventor is a copolymer mixture composed of a specific graft copolymer and a vinyl copolymer, and the content of vinyl cyanide units in the graft copolymer and By blending a small amount of fluororesin into a copolymer mixture in which the absolute value of the difference in vinyl cyanide unit content of the vinyl copolymer is 3.0 to 7.0% by mass, the UL standard 94HB burning time can be reduced. It has been found that the above problem can be solved.
本発明は、このような知見に基づいて達せられたものであり、以下を要旨とする。 The present invention has been achieved based on such findings, and the gist thereof is as follows.
［１］ ゴム質重合体に、シアン化ビニル化合物と、シアン化ビニル化合物と共重合可能なビニル化合物とをグラフト重合してなるグラフト共重合体（Ａ）と、シアン化ビニル化合物と、シアン化ビニル化合物と共重合可能なビニル化合物とを共重合してなるビニル共重合体（Ｂ）とからなる共重合体混合物に、該共重合体混合物１００質量部に対して０．１〜０．３質量部のフッ素樹脂（Ｃ）を配合してなる熱可塑性樹脂組成物であって、グラフト共重合体（Ａ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＡと、ビニル共重合体（Ｂ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＢの差の絶対値｜ＣＢＡ−ＣＢＢ｜が３．０〜７．０質量％であることを特徴とする熱可塑性樹脂組成物。 [1] A graft copolymer (A) obtained by graft polymerization of a vinyl cyanide compound and a vinyl compound copolymerizable with the vinyl cyanide compound onto the rubber polymer, the vinyl cyanide compound, and cyanide A copolymer mixture comprising a vinyl copolymer (B) obtained by copolymerizing a vinyl compound and a copolymerizable vinyl compound is added to 0.1 to 0.3 parts per 100 parts by mass of the copolymer mixture. the mass of the fluororesin (C) a thermoplastic resin composition obtained by blending a content CB a acetone-soluble fraction of the vinyl cyanide units after methanol washing of the graft copolymer (a), The absolute value of the difference CB B in the content of vinyl cyanide units of acetone-soluble matter after the methanol washing of the vinyl copolymer (B) | CB A −CB B | is 3.0 to 7.0% by mass. Thermoplastic resin characterized by Composition.
［２］ 前記グラフト共重合体（Ａ）が、ゴム質重合体２０〜７５質量部に、シアン化ビニル化合物２３〜３５質量％と、シアン化ビニル化合物と共重合可能なビニル化合物６５〜７７質量％とを含むビニル単量体混合物２５〜８０質量部をグラフト重合してなり、かつ、前記ビニル共重合体（Ｂ）が、シアン化ビニル化合物２０〜３５質量％と、シアン化ビニル化合物と共重合可能なビニル化合物６５〜８０質量％とを含むビニル単量体混合物を共重合してなることを特徴とする［１］に記載の熱可塑性樹脂組成物。 [2] The graft copolymer (A) is 23 to 35 mass% of a vinyl cyanide compound and 65 to 77 mass% of a vinyl compound copolymerizable with the vinyl cyanide compound in 20 to 75 mass parts of a rubbery polymer. 25 to 80 parts by mass of a vinyl monomer mixture containing 25% by weight, and the vinyl copolymer (B) comprises 20 to 35% by mass of a vinyl cyanide compound and a vinyl cyanide compound. The thermoplastic resin composition according to [1], which is obtained by copolymerizing a vinyl monomer mixture containing 65 to 80% by mass of a polymerizable vinyl compound.
［３］ 前記グラフト共重合体（Ａ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＡが２２．０〜３４．０質量％であり、前記ビニル共重合体（Ｂ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＢが２０．０〜３５．０質量％であることを特徴とする［１］または［２］に記載の熱可塑性樹脂組成物。 [3] was 22.0 to 34.0% by weight content of CB A is acetone-soluble fraction of the vinyl cyanide units after methanol washing of the graft copolymer (A), the vinyl copolymer (B the thermoplastic resin according to the content of the acetone-soluble fraction of the vinyl cyanide units after methanol washing CB B is characterized by a 20.0 to 35.0 wt% [1] or [2]) Composition.
［４］ 前記共重合体混合物が、グラフト共重合体（Ａ）１０〜７０質量％とビニル共重合体（Ｂ）３０〜９０質量％を合計で１００質量％含むことを特徴とする［１］ないし［３］のいずれかに記載の熱可塑性樹脂組成物。 [4] The copolymer mixture contains 10 to 70% by mass of the graft copolymer (A) and 30 to 90% by mass of the vinyl copolymer (B) in total of 100% by mass [1] Thru | or the thermoplastic resin composition in any one of [3].
［５］ ［１］ないし［４］のいずれかに記載の熱可塑性樹脂組成物を成形してなる成形品。 [5] A molded product formed by molding the thermoplastic resin composition according to any one of [1] to [4].
本発明の熱可塑性樹脂組成物によれば、ハロゲン系難燃剤、リン系難燃剤などの難燃剤やアンチモン化合物のような難燃助剤を配合することなく、薄肉厚み（０．５８ｍｍ）における米国ＵＬ規格９４ＨＢに適合する優れた安全性を示し、しかも、外観に優れた成形品が提供される。 According to the thermoplastic resin composition of the present invention, the United States in a thin wall thickness (0.58 mm) without blending flame retardants such as halogen flame retardants and phosphorus flame retardants and flame retardant aids such as antimony compounds. A molded product exhibiting excellent safety conforming to UL standard 94HB and having an excellent appearance is provided.
以下に本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
［熱可塑性樹脂組成物］
本発明の熱可塑性樹脂組成物は、ゴム質重合体に、シアン化ビニル化合物と、シアン化ビニル化合物と共重合可能なビニル化合物（以下「共重合性ビニル化合物」と称す場合がある。）とをグラフト重合してなるグラフト共重合体（Ａ）と、シアン化ビニル化合物と共重合性ビニル化合物とを共重合してなるビニル共重合体（Ｂ）とからなる共重合体混合物に、該共重合体混合物１００質量部に対して０．１〜０．３質量部のフッ素樹脂（Ｃ）を配合してなる熱可塑性樹脂組成物であって、グラフト共重合体（Ａ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＡと、ビニル共重合体（Ｂ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＢの差の絶対値｜ＣＢＡ−ＣＢＢ｜が３．０〜７．０質量％であることを特徴とする。
[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention comprises a rubbery polymer, a vinyl cyanide compound, and a vinyl compound copolymerizable with the vinyl cyanide compound (hereinafter sometimes referred to as “copolymerizable vinyl compound”). To a copolymer mixture comprising a graft copolymer (A) obtained by graft polymerization of a vinyl copolymer (B) obtained by copolymerizing a vinyl cyanide compound and a copolymerizable vinyl compound. A thermoplastic resin composition obtained by blending 0.1 to 0.3 parts by mass of a fluororesin (C) with respect to 100 parts by mass of a polymer mixture, after the graft copolymer (A) is washed with methanol. a content CB a vinyl cyanide units acetone-soluble matter, the absolute value of the difference between the content of CB B acetone-soluble fraction of the vinyl cyanide units after methanol washing of vinyl copolymer (B) | CB a -CB B | is 3.0 Characterized in that it is a 2.0% by weight.
＜グラフト共重合体（Ａ）＞
本発明に係るグラフト共重合体（Ａ）は、ゴム質重合体に、シアン化ビニル化合物および共重合性ビニル化合物をグラフト重合してなるものである。
<Graft copolymer (A)>
The graft copolymer (A) according to the present invention is obtained by graft polymerizing a rubbery polymer with a vinyl cyanide compound and a copolymerizable vinyl compound.
該ゴム質重合体としては、ポリブタジエン、スチレン−ブタジエンゴム、アクリロニトリル−ブタジエンゴム、アクリルゴム、エチレン−プロピレン−非共役ジエン共重合体ゴム（ＥＰＤＭ）等の１種または２種以上を用いることができる。なお、ＥＰＤＭに含有される非共役ジエン成分としては、ジシクロペンタジエン、１，４−ヘキサジエン、１，４−ヘプタジエン、１，５−シクロオクタジエン、６−メチル−１，５−ヘプタジエン、１１−エチル−１，１１−トリデカジエン、５−メチレン−２−ノルボルネン、５−エチリデン−２−ノルボルネン、２，５−ノルボルナジエン、２−メチル−２，５−ノルボルナジエン、メチルテトラヒドロインデン、リモネン等のジオレフィンの１種または２種以上が挙げられる。 As the rubbery polymer, one or more of polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) and the like can be used. . As the non-conjugated diene component contained in EPDM, dicyclopentadiene, 1,4-hexadiene, 1,4-heptadiene, 1,5-cyclooctadiene, 6-methyl-1,5-heptadiene, 11- Diolefins such as ethyl-1,11-tridecadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, methyltetrahydroindene and limonene 1 type or 2 types or more are mentioned.
また、シアン化ビニル化合物としては、例えばアクリロニトリル、メタクリロニトリル等を挙げることができ、これらの１種または２種以上を使用することができる。 Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and one or more of these can be used.
共重合性ビニル化合物としては、芳香族ビニル化合物、芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物が挙げられ、このうち、芳香族ビニル化合物としては、例えば、スチレン、α−メチルスチレン、ｏ−，ｍ−もしくはｐ−メチルスチレン、ビニルキシレン、ｐ−ｔｅｒｔ−ブチルスチレン、エチルスチレン等、好ましくはスチレン、α−メチルスチレンを挙げることができる。これらの芳香族ビニル化合物は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 Examples of copolymerizable vinyl compounds include aromatic vinyl compounds and vinyl compounds that do not contain nitrogen elements other than aromatic vinyl compounds. Among these, examples of aromatic vinyl compounds include styrene, α-methylstyrene, o -, M- or p-methyl styrene, vinyl xylene, p-tert-butyl styrene, ethyl styrene and the like, preferably styrene and α-methyl styrene. These aromatic vinyl compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.
芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物としては、アクリル酸、メタクリル酸等のα，β−不飽和カルボン酸；メチル（メタ）アクリレート（なお、「（メタ）アクリレート」は「アクリレートまたはメタクリレート」を意味する。）、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等のα，β−不飽和カルボン酸エステル類；無水マレイン酸、無水イタコン酸等のα，β−不飽和ジカルボン酸無水物類等を挙げることができる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。 Examples of vinyl compounds containing no nitrogen element other than aromatic vinyl compounds include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl (meth) acrylate (in addition, “(meth) acrylate” is “acrylate or Methacrylate ”.), Α, β-unsaturated carboxylic acid such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. Acid esters; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. These may be used alone or in combination of two or more.
本発明に係るグラフト共重合体（Ａ）としては、具体的にはＡＢＳ（ポリブタジエン−スチレン−アクリロニトリル）樹脂、ＡＳＡ（アクリルゴム−スチレン−アクリロニトリル）樹脂、ＡＥＳ（エチレン−プロピレン−非共役ジエン系ゴム−スチレン−アクリロトリル）樹脂が挙げられる。 Specific examples of the graft copolymer (A) according to the present invention include ABS (polybutadiene-styrene-acrylonitrile) resin, ASA (acrylic rubber-styrene-acrylonitrile) resin, AES (ethylene-propylene-nonconjugated diene rubber). -Styrene-acrylotolyl) resin.
本発明に係るグラフト共重合体（Ａ）は、特にゴム質重合体２０〜７５質量部、好ましくは４０〜７０質量部に、シアン化ビニル化合物２３〜３５質量％および共重合性ビニル化合物６５〜７７質量％を含むビニル単量体混合物２５〜８０質量部、好ましくは３０〜６０質量部をグラフト重合したものが好ましい。 The graft copolymer (A) according to the present invention comprises, in particular, 20 to 75 parts by mass of a rubbery polymer, preferably 40 to 70 parts by mass, 23 to 35% by mass of a vinyl cyanide compound and 65 to 65% of a copolymerizable vinyl compound 65 to 65%. What graft-polymerized 25-80 mass parts of the vinyl monomer mixture containing 77 mass%, Preferably 30-60 mass parts is preferable.
グラフト共重合体（Ａ）において、ゴム質重合体の割合が上記下限より少ないと、得られる熱可塑性樹脂組成物の耐衝撃性が劣る傾向となり、上記上限を超えると共重合体（Ｂ）との相溶性が低下する傾向となるので好ましくない。 In the graft copolymer (A), if the ratio of the rubbery polymer is less than the above lower limit, the resulting thermoplastic resin composition tends to be inferior in impact resistance. If the upper limit is exceeded, the copolymer (B) and This is not preferable because the compatibility tends to decrease.
また、グラフト共重合体（Ａ）を製造する際に用いるビニル単量体混合物は、ビニル単量体混合物全体を１００質量％として、好ましくはシアン化ビニル化合物２３〜３５質量％、共重合性ビニル化合物６５〜７７質量％、より好ましくはシアン化ビニル化合物２４〜３４質量％と共重合性ビニル化合物６６〜７６質量％、さらに好ましくはシアン化ビニル化合物２６〜３２質量％と共重合性ビニル化合物６８〜７４質量％とからなるものである。ビニル単量体混合物中のシアン化ビニル化合物および共重合性ビニル化合物の割合が上記範囲を外れると、得られる熱可塑性樹脂組成物の成形加工性、耐衝撃性および耐熱性の少なくともいずれかに劣る傾向となり、物性バランスの優れた熱可塑性樹脂組成物を得ることが難しい。 In addition, the vinyl monomer mixture used in producing the graft copolymer (A) is preferably 23 to 35% by mass of a vinyl cyanide compound, preferably 100% by mass of the total vinyl monomer mixture, and copolymerizable vinyl. 65 to 77% by mass of the compound, more preferably 24 to 34% by mass of the vinyl cyanide compound and 66 to 76% by mass of the copolymerizable vinyl compound, further preferably 26 to 32% by mass of the vinyl cyanide compound and 68 of the copolymerizable vinyl compound. It consists of -74 mass%. If the ratio of the vinyl cyanide compound and copolymerizable vinyl compound in the vinyl monomer mixture is outside the above range, the resulting thermoplastic resin composition is inferior to at least one of moldability, impact resistance and heat resistance. It becomes difficult to obtain a thermoplastic resin composition having an excellent balance of physical properties.
また、共重合性ビニル化合物としては、前述の如く、芳香族ビニル化合物と芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物とが挙げられるが、その使用割合は、共重合性ビニル化合物全体を１００質量％として、好ましくは芳香族ビニル化合物５８〜１００質量％、芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物０〜４２質量％、より好ましくは芳香族ビニル化合物６５〜１００質量％、芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物０〜３５質量％、さらに好ましくは芳香族ビニル化合物８０〜１００質量％、芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物０〜２０質量％である。芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物の使用量が多過ぎると成形加工性が劣る傾向にあり、好ましくない。 Examples of the copolymerizable vinyl compound include an aromatic vinyl compound and a vinyl compound containing no nitrogen element other than the aromatic vinyl compound, as described above. 100 mass%, preferably 58-100 mass% aromatic vinyl compound, 0-42 mass% vinyl compound containing no nitrogen element other than aromatic vinyl compound, more preferably 65-100 mass% aromatic vinyl compound, aromatic 0 to 35% by mass of a vinyl compound containing no nitrogen element other than the aromatic vinyl compound, more preferably 80 to 100% by mass of an aromatic vinyl compound, and 0 to 20% by mass of a vinyl compound containing no nitrogen element other than the aromatic vinyl compound. is there. If the amount of the vinyl compound containing no nitrogen element other than the aromatic vinyl compound is too large, the moldability tends to be inferior, which is not preferable.
本発明におけるグラフト共重合体（Ａ）を製造する際のグラフト重合方法については特に制限はなく、塊状重合、溶液重合、塊状懸濁重合、懸濁重合および乳化重合等の一般的な重合方法をいずれも採用することができる。 The graft polymerization method for producing the graft copolymer (A) in the present invention is not particularly limited, and general polymerization methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization and emulsion polymerization are used. Either can be adopted.
上記グラフト重合は、例えば、先ず、乳化重合にて製造されたゴム質重合体を攪拌翼ジャケット付き反応器内に仕込み、次にグラフト重合させるビニル単量体混合物の全量または一部を数回に分けて、一括または連続して滴下し、攪拌しながら４０〜７０℃にて、５〜６０分間放置した後、更に開始剤を添加することにより行うことができる。これにより添加したビニル単量体混合物は、ゴム質重合体に含浸し、ゴム質重合体内にて重合体となって、グラフト共重合体（Ａ）が得られる。 In the graft polymerization, for example, first, a rubbery polymer produced by emulsion polymerization is charged into a reactor equipped with a stirring blade jacket, and then all or part of the vinyl monomer mixture to be graft polymerized is divided into several times. It can be carried out by adding dropwise or separately continuously, leaving the mixture at 40 to 70 ° C. with stirring for 5 to 60 minutes, and further adding an initiator. The vinyl monomer mixture thus added is impregnated into the rubbery polymer, becomes a polymer in the rubbery polymer, and the graft copolymer (A) is obtained.
このようなグラフト重合反応時の蒸留水へのシアン化ビニル化合物の溶解や単量体転化率などの影響から、グラフト共重合体（Ａ）の製造に用いたビニル単量体混合物中のシアン化ビニル化合物の含有量に対して、得られるグラフト共重合体（Ａ）のシアン化ビニル単位の含有量は変化する。 Cyanation in the vinyl monomer mixture used for the production of the graft copolymer (A) due to the effects of dissolution of the vinyl cyanide compound in distilled water and the monomer conversion rate during the graft polymerization reaction. The content of vinyl cyanide units in the resulting graft copolymer (A) varies with the content of vinyl compound.
本発明におけるグラフト共重合体（Ａ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＡは、２２．０〜３４．０質量％、特に２５．０〜３０．０質量％であることが好ましい。このシアン化ビニル単位の含有量ＣＢＡが上記範囲を外れると、得られる熱可塑性樹脂組成物の成形加工性、耐衝撃性および耐熱性の少なくともいずれかに劣る傾向なり、物性バランスの優れた熱可塑性樹脂組成物を得ることが難しい。 Content CB A acetone-soluble fraction of the vinyl cyanide units after methanol washing of the graft copolymer (A) in the present invention, from 22.0 to 34.0% by weight, particularly from 25.0 to 30.0 mass % Is preferred. If the content CB A of the vinyl cyanide units outside the above range, moldability of the thermoplastic resin composition obtained becomes at least tend inferior to any of the impact resistance and heat resistance, the physical property balance excellent thermal It is difficult to obtain a plastic resin composition.
なお、本発明において、グラフト共重合体（Ａ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＡは、グラフト共重合体（Ａ）をメタノール洗浄後にアセトンに溶解させ、アセトン可溶分を濃縮した後、メタノールで再沈殿させ、濾過により沈殿物を採取後、この沈殿物を元素分析にかけ、窒素原子換算することによる求めることができる。 In the present invention, the content CB A acetone-soluble fraction of the vinyl cyanide units after methanol washing of the graft copolymer (A), the graft copolymer (A) is dissolved in acetone washed with methanol, After concentrating the acetone-soluble component, it is reprecipitated with methanol, and after collecting the precipitate by filtration, the precipitate is subjected to elemental analysis and can be determined by converting into nitrogen atoms.
グラフト共重合体（Ａ）は１種を単独で用いてもよく、異なる成分組成のものを２種以上混合して用いてもよい。２種以上のグラフト共重合体を混合して用いる際、これらを混合した状態で、メタノール洗浄後にアセトンに溶解させ、アセトン可溶分を濃縮した後、メタノールで再沈殿させ、濾過により沈殿物を採取後、この沈殿物を元素分析にかけ、窒素原子換算することによりＣＢＡを求めることができる。または、それぞれを単独の状態で、メタノール洗浄後にアセトンに溶解させ、アセトン可溶分を濃縮した後、メタノールで再沈殿させ、濾過により沈殿物を採取後、この沈殿物を元素分析にかけ、窒素原子換算することによる求め、相加平均とした値をＣＢＡとして使用することもできる。 A graft copolymer (A) may be used individually by 1 type, and 2 or more types of different component compositions may be mixed and used for it. When two or more types of graft copolymers are mixed and used, they are mixed and dissolved in acetone after washing with methanol, the acetone-soluble component is concentrated, and then reprecipitated with methanol, and the precipitate is removed by filtration. after collection, over the sediment to elemental analysis, it is possible to obtain the CB a by converting nitrogen atom. Alternatively, each is dissolved in acetone after washing with methanol, and the acetone-soluble component is concentrated, and then reprecipitated with methanol. After collecting the precipitate by filtration, the precipitate is subjected to elemental analysis, and then subjected to nitrogen atoms. A value obtained by conversion and taken as an arithmetic average can also be used as CBA.
＜ビニル共重合体（Ｂ）＞
本発明に係るビニル共重合体（Ｂ）は、シアン化ビニル化合物と共重合性ビニル化合物とを共重合してなるものである。
<Vinyl copolymer (B)>
The vinyl copolymer (B) according to the present invention is obtained by copolymerizing a vinyl cyanide compound and a copolymerizable vinyl compound.
本発明において、ビニル共重合体（Ｂ）を製造する際に用いるシアン化ビニル化合物、共重合性ビニル化合物としては、各々前述のグラフト共重合体（Ａ）を製造する際に用いることができるシアン化ビニル化合物、共重合性ビニル化合物として例示したものが挙げられ、それぞれ、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 In the present invention, as the vinyl cyanide compound and the copolymerizable vinyl compound used for producing the vinyl copolymer (B), cyan which can be used for producing the aforementioned graft copolymer (A), respectively. Examples thereof include those exemplified as the vinyl chloride compound and the copolymerizable vinyl compound, and each may be used alone or in combination of two or more.
このビニル共重合体（Ｂ）は、シアン化ビニル化合物と共重合性ビニル化合物とを含むビニル単量体混合物を共重合することにより製造されるが、このビニル単量体混合物中のシアン化ビニル化合物と共重合性ビニル化合物との割合は、ビニル単量体混合物全体を１００質量％として、好ましくはシアン化ビニル化合物２０〜３５質量％、共重合性ビニル化合物６５〜８０質量％、より好ましくはシアン化ビニル化合物２４〜３４質量％と共重合性ビニル化合物６６〜７６質量％、さらに好ましくはシアン化ビニル化合物２６〜３２質量％と共重合性ビニル化合物６８〜７４質量％とからなる。ビニル単量体混合物中のシアン化ビニル化合物および共重合性ビニル化合物の割合が上記範囲を外れると、得られる熱可塑性樹脂組成物の成形加工性、耐衝撃性および耐熱性の少なくともいずれかに劣る傾向となり、物性バランスの優れた熱可塑性樹脂組成物を得ることが難しい。 The vinyl copolymer (B) is produced by copolymerizing a vinyl monomer mixture containing a vinyl cyanide compound and a copolymerizable vinyl compound, and the vinyl cyanide in the vinyl monomer mixture is produced. The ratio of the compound and the copolymerizable vinyl compound is preferably 20 to 35% by mass of the vinyl cyanide compound, 65 to 80% by mass of the copolymerizable vinyl compound, more preferably 100% by mass of the entire vinyl monomer mixture. It comprises 24 to 34% by mass of vinyl cyanide compound and 66 to 76% by mass of copolymerizable vinyl compound, more preferably 26 to 32% by mass of vinyl cyanide compound and 68 to 74% by mass of copolymerizable vinyl compound. If the ratio of the vinyl cyanide compound and copolymerizable vinyl compound in the vinyl monomer mixture is outside the above range, the resulting thermoplastic resin composition is inferior to at least one of moldability, impact resistance and heat resistance. It becomes difficult to obtain a thermoplastic resin composition having an excellent balance of physical properties.
また、共重合性ビニル化合物としては、前述の如く、芳香族ビニル化合物と芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物とが挙げられるが、その使用割合は、共重合性ビニル化合物全体を１００質量％として、好ましくは芳香族ビニル化合物５８〜１００質量％、芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物０〜４２質量％、より好ましくは芳香族ビニル化合物６５〜１００質量％、芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物０〜３５質量％、さらに好ましくは芳香族ビニル化合物８０〜１００質量％、芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物０〜２０質量％である。芳香族ビニル化合物以外の窒素元素を含有しないビニル化合物の使用量が多過ぎると成形加工性が劣る傾向にあり、好ましくない。 Examples of the copolymerizable vinyl compound include an aromatic vinyl compound and a vinyl compound containing no nitrogen element other than the aromatic vinyl compound, as described above. 100 mass%, preferably 58-100 mass% aromatic vinyl compound, 0-42 mass% vinyl compound containing no nitrogen element other than aromatic vinyl compound, more preferably 65-100 mass% aromatic vinyl compound, aromatic 0 to 35% by mass of a vinyl compound containing no nitrogen element other than the aromatic vinyl compound, more preferably 80 to 100% by mass of an aromatic vinyl compound, and 0 to 20% by mass of a vinyl compound containing no nitrogen element other than the aromatic vinyl compound. is there. If the amount of the vinyl compound containing no nitrogen element other than the aromatic vinyl compound is too large, the moldability tends to be inferior, which is not preferable.
ビニル共重合体（Ｂ）は、このようなビニル単量体混合物から、常法に従って、乳化重合、懸濁重合、塊状重合またはこれらの組み合わせからなる共重合反応によって製造することができる。 The vinyl copolymer (B) can be produced from such a vinyl monomer mixture by a copolymerization reaction consisting of emulsion polymerization, suspension polymerization, bulk polymerization, or a combination thereof according to a conventional method.
このような共重合反応時の蒸留水へのシアン化ビニル化合物の溶解や単量体転化率などの影響から、ビニル共重合体（Ｂ）の製造に用いたビニル単量体混合物中のシアン化ビニル化合物の含有量に対して、得られるビニル共重合体（Ｂ）のシアン化ビニル単位の含有量は変化する。 Cyanation in the vinyl monomer mixture used for the production of the vinyl copolymer (B) due to the effects of dissolution of the vinyl cyanide compound in distilled water and the monomer conversion rate during the copolymerization reaction. The content of vinyl cyanide units in the resulting vinyl copolymer (B) varies with respect to the content of the vinyl compound.
本発明におけるビニル共重合体（Ｂ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＢは、２０．０〜３５．０質量％であることが好ましい。このシアン化ビニル単位の含有量ＣＢＢが上記範囲を外れると、得られる熱可塑性樹脂組成物の成形加工性、耐衝撃性および耐熱性の少なくともいずれかに劣る傾向なり、物性バランスの優れた熱可塑性樹脂組成物を得ることが難しい。 Content CB B acetone-soluble fraction of the vinyl cyanide units after methanol washing of vinyl copolymer (B) in the present invention is preferably 20.0 to 35.0 wt%. When the content CB B of the vinyl cyanide units outside the above range, moldability of the thermoplastic resin composition obtained becomes at least tend inferior to any of the impact resistance and heat resistance, the physical property balance excellent thermal It is difficult to obtain a plastic resin composition.
なお、本発明において、ビニル共重合体（Ｂ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＢは、ビニル共重合体（Ｂ）をメタノール洗浄後にアセトンに溶解させ、アセトン可溶分を濃縮した後、メタノールで再沈殿させ、濾過により沈殿物を採取後、この沈殿物を元素分析にかけ、窒素原子換算することによる求めることができる。 In the present invention, the content CB B of the vinyl cyanide unit in the acetone-soluble portion of the vinyl copolymer (B) after washing with methanol is obtained by dissolving the vinyl copolymer (B) in acetone after washing with methanol. After concentrating the acetone-soluble component, it is reprecipitated with methanol, and after collecting the precipitate by filtration, the precipitate is subjected to elemental analysis and can be determined by converting into nitrogen atoms.
なお、ビニル共重合体（Ｂ）の質量平均分子量は、ＧＰＣを用いて測定したポリスチレン換算値で、５０，０００〜３００，０００の範囲が好ましく、さらに好ましくは８５，０００〜２５０，０００の範囲である。ビニル共重合体（Ｂ）の質量平均分子量が上記下限値以上であることにより、得られる成形品の耐衝撃性が良好となり、また、上記上限値以下であることにより、成形加工性が良好となる。 The mass average molecular weight of the vinyl copolymer (B) is a polystyrene converted value measured using GPC, preferably in the range of 50,000 to 300,000, more preferably in the range of 85,000 to 250,000. It is. When the weight average molecular weight of the vinyl copolymer (B) is at least the above lower limit, the resulting molded article has good impact resistance, and when it is at most the above upper limit, the moldability is good. Become.
このビニル共重合体（Ｂ）についても１種を単独で用いてもよく、異なる組成、分子量のものを２種以上混合して用いてもよい。２種以上のビニル共重合体を混合して用いる際、これらを混合した状態で、メタノール洗浄後にアセトンに溶解させ、アセトン可溶分を濃縮した後、メタノールで再沈殿させ、濾過により沈殿物を採取後、この沈殿物を元素分析にかけ、窒素原子換算することによりＣＢＢを求めることができる。または、それぞれを単独の状態で、メタノール洗浄後にアセトンに溶解させ、アセトン可溶分を濃縮した後、メタノールで再沈殿させ、濾過により沈殿物を採取後、この沈殿物を元素分析にかけ、窒素原子換算することによる求め、相加平均とした値をＣＢＢとして使用することもできる。 As for this vinyl copolymer (B), one kind may be used alone, or two or more kinds having different compositions and molecular weights may be mixed and used. When mixing and using two or more kinds of vinyl copolymers, these are mixed and dissolved in acetone after washing with methanol, the acetone-soluble component is concentrated, then reprecipitated with methanol, and the precipitate is removed by filtration. After the collection, this precipitate is subjected to elemental analysis and converted into nitrogen atoms, whereby CB B can be obtained. Alternatively, each is dissolved in acetone after washing with methanol, and the acetone-soluble component is concentrated, and then reprecipitated with methanol. After collecting the precipitate by filtration, the precipitate is subjected to elemental analysis, and then subjected to nitrogen atoms. A value obtained by conversion and taken as an arithmetic average can also be used as CB B.
＜共重合体混合物＞
本発明に係る共重合体混合物は、グラフト共重合体（Ａ）とビニル共重合体（Ｂ）とからなるものであるが、これらの合計量１００質量部において、各々、次のような割合で含有されることが好ましい。
グラフト共重合体（Ａ）：１０〜７０質量部、特に１５〜４０質量部
ビニル共重合体（Ｂ）：３０〜９０質量部、特に６０〜８５質量部
さらに、該共重合体混合物中におけるゴム含有量は、好ましくは５〜２０質量％、より好ましくは６〜１６質量％、さらに好ましくは８〜１４質量％である。ゴム含有量がこの範囲であると、燃焼性に優れる傾向にある。
<Copolymer mixture>
The copolymer mixture according to the present invention is composed of the graft copolymer (A) and the vinyl copolymer (B), and in the total amount of 100 parts by mass, respectively, in the following proportions: It is preferable to contain.
Graft copolymer (A): 10 to 70 parts by weight, especially 15 to 40 parts by weight Vinyl copolymer (B): 30 to 90 parts by weight, particularly 60 to 85 parts by weight Further, rubber in the copolymer mixture The content is preferably 5 to 20% by mass, more preferably 6 to 16% by mass, and still more preferably 8 to 14% by mass. When the rubber content is within this range, the combustibility tends to be excellent.
グラフト共重合体（Ａ）の配合量が上記下限よりも少ないと、得られる樹脂組成物が耐衝撃性に劣る傾向となり、上記上限を超えると、耐熱性に劣る傾向となる。また、ビニル共重合体（Ｂ）の配合量が上記下限より少ないと、得られる樹脂組成物が流動性、燃焼性に劣る傾向となり、上記上限を超えると耐衝撃性に劣る傾向となる。 If the amount of the graft copolymer (A) is less than the lower limit, the resulting resin composition tends to be inferior in impact resistance, and if it exceeds the upper limit, the heat resistance tends to be inferior. Moreover, when there are few compounding quantities of a vinyl copolymer (B) than the said minimum, the resin composition obtained will tend to be inferior to fluidity | liquidity and combustibility, and when it exceeds the said upper limit, it will be inferior to impact resistance.
また、本発明に係る共重合体混合物において、この共重合体混合物中のグラフト共重合体（Ａ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＡと、ビニル共重合体（Ｂ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＢとの差の絶対値｜ＣＢＡ−ＣＢＢ｜は３．０〜７．０質量％であり、好ましくはこの値は５．０〜７．０質量％である。
｜ＣＢＡ−ＣＢＢ｜が上記範囲内であることにより、フッ素樹脂（Ｃ）との併用で、米国ＵＬ規格９４ＨＢに適合する優れた安全性を得ることが可能となる。
Further, in the copolymer mixture of the present invention, the content of CB A acetone-soluble fraction of the vinyl cyanide units after methanol washing of the graft copolymer of the copolymer mixture (A), vinyl copolymerization the absolute value of the difference between the content CB B acetone-soluble fraction of the vinyl cyanide units after methanol washing coalescence (B) | CB a -CB B | is 3.0 to 7.0 wt%, preferably This value is 5.0 to 7.0% by mass.
When | CB A −CB B | is within the above range, it is possible to obtain excellent safety conforming to US UL standard 94HB in combination with the fluororesin (C).
なお、前述の如く、グラフト共重合体（Ａ）、ビニル共重合体（Ｂ）はそれぞれ１種を単独で用いてもよく、２種以上を混合して用いてもよい。これらを２種以上用いる場合、共重合体混合物中のグラフト共重合体（Ａ）、ビニル共重合体（Ｂ）のいずれの組み合わせにおいても、｜ＣＢＡ−ＣＢＢ｜が上記範囲となるようにする。 In addition, as above-mentioned, a graft copolymer (A) and a vinyl copolymer (B) may be used individually by 1 type, respectively, and may mix and use 2 or more types, respectively. When two or more of these are used, in any combination of the graft copolymer (A) and the vinyl copolymer (B) in the copolymer mixture, | CB A -CB B | is in the above range. To do.
＜フッ素樹脂（Ｃ）＞
本発明で用いるフッ素樹脂（Ｃ）としては、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、テトラフルオロエチレン、テトラフルオロエチレン・エチレン共重合体、ポリビリニデンフルオライド、ポリビニルフルオライド、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体等の分子中にフッ素原子を含む樹脂が挙げられる。
これらの中でもポリテトラフルオロエチレン、テトラフルオロエチレン・エチレン共重合体、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体が好ましく、特にポリテトラフルオロエチレンが好ましい。
<Fluororesin (C)>
Examples of the fluororesin (C) used in the present invention include polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, and tetrafluoroethylene. -Resins containing fluorine atoms in the molecule such as hexafluoropropylene copolymer and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer.
Among these, polytetrafluoroethylene, tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer are preferable, and polytetrafluoroethylene is particularly preferable.
なお、フッ素樹脂の市販の製品としては、例えば、旭硝子（株）製の「Ｆｌｕｏｎ（登録商標） ＰＴＦＥ ＣＤ１シリーズ」のファインパウダー（粉末状）や「Ｆｌｕｏｎ（登録商標） ＰＴＦＥ ＡＤシリーズ」のディスパージョン（液体状）、ダイキン工業（株）製の「ポリフロン Ｆシリーズ」の粉末状、「ポリフロン Ｄシリーズ」の液体状のものを挙げることができる。 Examples of commercially available fluororesin products include “Fluon (registered trademark) PTFE CD1 series” fine powder (powder) manufactured by Asahi Glass Co., Ltd. and “Fluon (registered trademark) PTFE AD series” dispersion. (Liquid), Daikin Industries, Ltd. “Polyflon F series” powder, and “Polyflon D series” liquid.
フッ素樹脂としては、ファインパウダー粉末状（パウダー）、液体状（ラテックス）のどちらの形態でも使用することができ、この場合、それぞれフッ素樹脂成分として所定量を配合すればよい。 The fluororesin can be used in either fine powder powder form (powder) or liquid form (latex). In this case, a predetermined amount may be blended as the fluororesin component.
フッ素樹脂の分子量については特に制限は無いが、数平均分子量（Ｍｎ）は７０万以上、好ましくは１００万以上のものが、米国ＵＬ規格９４ＨＢ性能を安定化させることから好適である。なお、分子量は標準比重から算出することができる。 Although there is no restriction | limiting in particular about the molecular weight of a fluororesin, A number average molecular weight (Mn) is 700,000 or more, Preferably a thing of 1 million or more is suitable in order to stabilize US UL specification 94HB performance. The molecular weight can be calculated from the standard specific gravity.
本発明において、フッ素樹脂は、さらに、芳香族ビニル、シアン化ビニル、メタクリル酸エステル、アクリル酸エステルなどの一種類や複数の単量体とフッ素樹脂とを共重合もしくは単量体の重合物とを混合させたものを使用しても良い。このうち、共重合の場合、例えば、フッ素樹脂の重合物に、単量体を添加しながら乳化重合する方法がある。また、共重合体とフッ素樹脂との混合物の場合、その混合方法としては、ラテックスとラテックスのブレンド、ラテックスとパウダーのブレンド、ビーズとラテックスのブレンド、ビーズとパウダーのブレンドなどが挙げられるが、より好ましくは、ラテックス同士のブレンドである。 In the present invention, the fluororesin further includes a copolymer of a monomer or a polymer of a monomer and a fluoropolymer with one or more monomers such as aromatic vinyl, vinyl cyanide, methacrylic acid ester, and acrylic acid ester. You may use what mixed these. Among these, in the case of copolymerization, for example, there is a method of emulsion polymerization while adding a monomer to a polymer of a fluororesin. In the case of a mixture of a copolymer and a fluororesin, examples of the mixing method include latex and latex blend, latex and powder blend, bead and latex blend, and bead and powder blend. Preferably, it is a blend of latexes.
このようなフッ素樹脂の具体例としては、例えば、市販品の三菱レイヨン（株）社製「メタブレンＡ−３０００」、「メタブレンＡ−３８００」などを挙げることができる。
このようなフッ素樹脂とラテックス同士のブレンドされたフッ素樹脂を用いることにより、米国ＵＬ規格９４ＨＢ性能を発揮させつつ、分散性や外観についても良好となる。
Specific examples of such a fluororesin include, for example, commercially available products “Metbrene A-3000” and “Metbrene A-3800” manufactured by Mitsubishi Rayon Co., Ltd.
By using such a fluororesin blended with a fluororesin and latex, the dispersibility and appearance are improved while exhibiting the US UL standard 94HB performance.
本発明の熱可塑性樹脂組成物は、フッ素樹脂（Ｃ）を上記のグラフト共重合体（Ａ）とビニル共重合体（Ｂ）との共重合体混合物１００質量部に対して０．１〜０．３質量部、好ましくは０．１〜０．２質量部含有する。フッ素樹脂（Ｃ）の含有量が上記下限以上であることにより米国ＵＬ規格９４ＨＢに適合する優れた安全性を得ることが可能となり、フッ素樹脂（Ｃ）の含有量が上記上限以下であることにより良好な成形品外観を得ることができる。 In the thermoplastic resin composition of the present invention, the fluororesin (C) is added in an amount of 0.1 to 0 with respect to 100 parts by mass of the copolymer mixture of the graft copolymer (A) and the vinyl copolymer (B). .3 parts by mass, preferably 0.1 to 0.2 parts by mass. When the content of the fluororesin (C) is not less than the above lower limit, it becomes possible to obtain excellent safety conforming to the US UL standard 94HB, and the content of the fluororesin (C) is not more than the above upper limit. A good molded product appearance can be obtained.
＜他の添加剤＞
本発明の熱可塑性樹脂組成物には、更に上記の諸成分の他に、その物性を損なわない範囲において、樹脂組成物の製造時（混合時）、成形時に用いられる通常の他の添加剤、例えば、滑剤、顔料、染料、耐熱剤、酸化劣化防止剤、紫外線吸収剤、耐候剤、離型剤、可塑剤、帯電防止剤、着色剤（カーボンブラック、酸化チタン、顔料、染料など）、炭素繊維、ガラス繊維、充填剤（タルクやウォラストナイト、炭酸カルシウム、シリカなど）、抗菌剤、防カビ剤、シリコ−ンオイル、カップリング剤などの１種または２種以上を配合することができる。
<Other additives>
In the thermoplastic resin composition of the present invention, in addition to the above-mentioned components, other additives usually used at the time of molding (mixing) and molding of the resin composition, as long as the physical properties are not impaired, For example, lubricants, pigments, dyes, heat-resistant agents, antioxidants, UV absorbers, weathering agents, release agents, plasticizers, antistatic agents, colorants (carbon black, titanium oxide, pigments, dyes, etc.), carbon One type or two or more types of fibers, glass fibers, fillers (talc, wollastonite, calcium carbonate, silica, etc.), antibacterial agents, fungicides, silicone oils, coupling agents, and the like can be blended.
また、本発明の目的を損なわない程度に、例えば前記共重合体混合物１００質量部に対して１０質量部以下の範囲であれば、前記グラフト共重合体（Ａ）、ビニル共重合体（Ｂ）およびフッ素樹脂（Ｃ）以外の樹脂およびゴムやエラストマー等が含まれていてもよい。 In addition, the graft copolymer (A) and the vinyl copolymer (B) are within a range of 10 parts by mass or less with respect to 100 parts by mass of the copolymer mixture so as not to impair the object of the present invention. Further, a resin other than the fluororesin (C), rubber, elastomer, and the like may be included.
含有し得るその他の樹脂としては、ＨＩＰＳ樹脂などのゴム強化スチレン系樹脂、その他に、ＡＳ樹脂、ポリスチレン樹脂、ポリカーボネート樹脂、ナイロン樹脂、メタクリル樹脂、ポリ塩化ビニル樹脂、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、ポリフェニレンエーテル樹脂などが挙げられる。また、これらを２種類以上ブレンドしたものでも良く、さらに、相溶化剤や官能基などにより変性された上記樹脂を配合してもよい。 Examples of other resins that can be contained include rubber-reinforced styrene resins such as HIPS resin, AS resin, polystyrene resin, polycarbonate resin, nylon resin, methacrylic resin, polyvinyl chloride resin, polybutylene terephthalate resin, polyethylene terephthalate resin. And polyphenylene ether resin. Moreover, what blended these 2 or more types may be sufficient, and you may mix | blend the said resin modified | denatured with the compatibilizing agent, the functional group, etc. further.
ただし、ハロゲン系難燃剤、リン系難燃剤などの難燃剤やアンチモン化合物のような難燃助剤を配合することなく薄肉厚み（０．５８ｍｍ）における米国ＵＬ規格９４ＨＢに適合する優れた安全性を示し、しかも、外観に優れた成形品を提供するという本発明の効果を得るために、本発明の熱可塑性樹脂組成物は、ハロゲン系難燃剤、リン系難燃剤などの難燃剤やアンチモン化合物のような難燃助剤を実質的に含有しないことが重要である。ここで「実質的に含有しない」とは、熱可塑性樹脂組成物中の含有量として３０００質量ｐｐｍ以下であることをいう。 However, excellent safety conforming to US UL standard 94HB at a thin wall thickness (0.58 mm) without blending flame retardants such as halogen flame retardants, phosphorus flame retardants, and flame retardant aids such as antimony compounds. In addition, in order to obtain the effect of the present invention to provide a molded article having an excellent appearance, the thermoplastic resin composition of the present invention includes a flame retardant such as a halogen-based flame retardant and a phosphorus-based flame retardant, and an antimony compound. It is important that such a flame retardant aid is not substantially contained. Here, “substantially does not contain” means that the content in the thermoplastic resin composition is 3000 ppm by mass or less.
＜製造方法＞
本発明の熱可塑性樹脂組成物を製造する方法には特に制限はなく、本発明の熱可塑性樹脂組成物は、通常行われている方法および装置を使用して製造することができる。一般的に使用されている方法は、溶融混合法であり、その際に用いる装置の例としては、一軸押出機、二軸押出機、バンバリーミキサー、ローラー、ニーダー等を挙げることができる。熱可塑性樹脂組成物の製造は、回分式または連続式のいずれで行ってもよく、また、各成分の混合順序にも特に制限はなく、全ての成分が十分に均一に混合されればよい。
<Manufacturing method>
There is no restriction | limiting in particular in the method to manufacture the thermoplastic resin composition of this invention, The thermoplastic resin composition of this invention can be manufactured using the method and apparatus currently performed normally. A generally used method is a melt mixing method, and examples of the apparatus used at that time include a single screw extruder, a twin screw extruder, a Banbury mixer, a roller, and a kneader. The production of the thermoplastic resin composition may be carried out either batchwise or continuously, and there is no particular limitation on the mixing order of the components, and it is sufficient that all the components are mixed sufficiently uniformly.
［成形品］
本発明の成形品は、上述した本発明の熱可塑性樹脂組成物を成形してなるものであり、その成形方法としては、射出成形、シート押出成形、真空成形、圧空成形、異形押出成形、発泡成形、ブロー成形など、熱可塑性樹脂組成物に汎用の成形方法をいずれも適用することができる。
[Molding]
The molded product of the present invention is formed by molding the above-described thermoplastic resin composition of the present invention, and the molding method includes injection molding, sheet extrusion molding, vacuum molding, pressure molding, profile extrusion molding, foaming. Any general-purpose molding method can be applied to the thermoplastic resin composition such as molding and blow molding.
本発明の熱可塑性樹脂組成物を成形して得られる成形品の用途としては特に制限はないが、その優れた安全性と優れた外観により、ＯＡ・家電分野、電気・電子分野、自動車分野、建材分野等の各種用途に有用である。 Although there is no restriction | limiting in particular as a use of the molded article obtained by shape | molding the thermoplastic resin composition of this invention, Due to the outstanding safety | security and the outstanding external appearance, OA / home appliance field, the electric / electronic field, the automotive field, Useful for various applications in the field of building materials.
以下、製造例、実施例および比較例を挙げて本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
以下において、得られた樹脂組成物の各種物性ないし特性の評価方法は次の通りである。 In the following, evaluation methods for various physical properties and characteristics of the obtained resin composition are as follows.
（１）燃焼時間：ＵＬ９４ ＨＢ規格の試験方法に従って、厚み０．５８ｍｍで試験を実施し、試験片の標線間（７５ｍｍ）の燃焼時間（秒）を計測した。 (1) Burning time: According to the test method of UL94 HB standard, the test was conducted with a thickness of 0.58 mm, and the burning time (seconds) between the marked lines (75 mm) of the test pieces was measured.
（２）ＨＢ判定：ＵＬ９４ ＨＢ規格の試験方法に従って、厚み０．５８ｍｍで試験を実施し、ＵＬ９４ＨＢに適合するか否かを判定し（ＨＢ規格では６０秒以上必要）、ＵＬ９４ＨＢに適合するものを○とし、適合しない物を×と表記した。 (2) HB determination: According to the test method of UL94 HB standard, the test is conducted at a thickness of 0.58 mm to determine whether it conforms to UL94HB (60 seconds or more is required in the HB standard). ○ was marked as non-conforming.
（３）外観：２ｍｍ厚み、１００ｍｍ×１００ｍｍ（縦×横）の板状の成形品を成形し、表面外観を目視にて観察し、良好なものを○、劣るものを×として判定した。 (3) Appearance: A plate-shaped molded product having a thickness of 2 mm and a size of 100 mm × 100 mm (length × width) was molded, and the surface appearance was visually observed.
＜製造例１：グラフト共重合体（Ａ）の製造＞
蒸留水１７０質量部に、ジエン系ゴム（ポリブタジエン、ゲル含有量：９５％、平均粒子径：３０００Å）５０質量部と、スチレン７３質量％およびアクリロニトリル２７質量％のビニル単量体混合物５０質量部と、不均化ロジン酸カリウム１質量部、水酸化ナトリウム０．０１質量部、ピロリン酸ナトリウム０．４５質量部、硫酸第１鉄０．０１質量部、デキストローズ０．５７質量部、ｔ−ドデシルメルカプタン０．０８質量部およびクメンハイドロパーオキサイド１．０質量部とを仕込み、６０℃から反応を開始し、途中で７５℃まで昇温し、２時間半後に乳化グラフト重合を完結させた。
反応生成物のラテックスを硫酸水溶液で凝固、水洗した後、乾燥してグラフト共重合体（Ａ）を得た。なお、単量体転化率は９６％、ゴム含有量は６０．５質量％であった。
<Production Example 1: Production of Graft Copolymer (A)>
To 170 parts by weight of distilled water, 50 parts by weight of a diene rubber (polybutadiene, gel content: 95%, average particle size: 3000 kg), 50 parts by weight of a vinyl monomer mixture of 73% by weight of styrene and 27% by weight of acrylonitrile , 1 part by weight of disproportionated potassium rosinate, 0.01 parts by weight of sodium hydroxide, 0.45 parts by weight of sodium pyrophosphate, 0.01 parts by weight of ferrous sulfate, 0.57 parts by weight of dextrose, t-dodecyl Mercaptan (0.08 parts by mass) and cumene hydroperoxide (1.0 parts by mass) were charged, the reaction was started at 60 ° C., the temperature was raised to 75 ° C., and emulsion graft polymerization was completed after 2 and a half hours.
The latex of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a graft copolymer (A). The monomer conversion was 96% and the rubber content was 60.5% by mass.
グラフト共重合体（Ａ）をメタノールで洗浄後、アセトンに溶解させた後、このアセトン可溶分を濃縮し、メタノールで再沈殿させ、濾過により沈殿物を採取した。この沈殿物を乾燥させた後、元素分析装置として、Ｙａｎａｃｏ製ＭＴ−６を使用して、窒素原子換算によるシアン化ビニル単位の含有量を、グラフト共重合体（Ａ）のシアン化ビニル単位の含有量とした。
このグラフト共重合体（Ａ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は２６．５質量％であった。
After the graft copolymer (A) was washed with methanol and dissolved in acetone, the acetone-soluble component was concentrated, reprecipitated with methanol, and the precipitate was collected by filtration. After drying this precipitate, using Yanaco MT-6 as an elemental analyzer, the content of vinyl cyanide units in terms of nitrogen atoms was determined as the amount of vinyl cyanide units in the graft copolymer (A). It was set as content.
The content of the vinyl cyanide unit of the acetone-soluble component after the methanol washing of the graft copolymer (A) was 26.5% by mass.
＜製造例２：ビニル共重合体（Ｂ−１）の製造＞
蒸留水１２０質量部に、アルキルベンゼンスルホン酸ナトリウム０．００３質量部と、スチレン７９．０質量％およびアクリロニトリル２１．０質量％のビニル単量体混合物１００質量部と、ｔ−ドデシルメルカプタン０．３５質量部、過酸化ベンゾイル０．１５質量部およびリン酸カルシウム０．５質量部とを添加して、１１０℃で１０時間懸濁重合し、ビニル共重合体（Ｂ−１）を得た。
このビニル共重合体（Ｂ−１）の質量平均分子量Ｍｗは１７５，０００で、単量体転化率は９８％であった。
<Production Example 2: Production of vinyl copolymer (B-1)>
To 120 parts by weight of distilled water, 0.003 part by weight of sodium alkylbenzenesulfonate, 100 parts by weight of a vinyl monomer mixture of 79.0% by weight of styrene and 21.0% by weight of acrylonitrile, and 0.35 part by weight of t-dodecyl mercaptan Part, 0.15 parts by mass of benzoyl peroxide and 0.5 parts by mass of calcium phosphate were added, and suspension polymerization was carried out at 110 ° C. for 10 hours to obtain a vinyl copolymer (B-1).
This vinyl copolymer (B-1) had a mass average molecular weight Mw of 175,000 and a monomer conversion rate of 98%.
ビニル共重合体（Ｂ−１）をメタノールで洗浄後、アセトンに溶解した後、このアセトン可溶分を濃縮し、メタノールで再沈殿させ、濾過により沈殿物を採取した。この沈殿物を乾燥させた後、元素分析装置として、Ｙａｎａｃｏ製ＭＴ−６を使用して、窒素原子換算によるシアン化ビニル単位の含有量を、ビニル共重合体（Ｂ−１）のシアン化ビニル単位の含有量とした。
このビニル共重合体（Ｂ−１）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は２０．０質量％であった。
The vinyl copolymer (B-1) was washed with methanol and then dissolved in acetone. Then, the acetone-soluble component was concentrated, reprecipitated with methanol, and the precipitate was collected by filtration. After this precipitate was dried, MT-6 manufactured by Yanaco was used as an elemental analyzer, and the content of vinyl cyanide units in terms of nitrogen atoms was determined using the vinyl cyanide of vinyl copolymer (B-1). The content of the unit.
Content of the vinyl cyanide unit of the acetone soluble part after methanol washing of this vinyl copolymer (B-1) was 20.0 mass%.
＜製造例３：ビニル共重合体（Ｂ−２）の製造＞
ビニル単量体混合物として、スチレン６７．０質量％とアクリロニトリル３３．０質量％のビニル単量体混合物を用い、ｔ−ドデシルメルカプタンの量を０．４質量部とした以外は製造例２と同条件で懸濁重合を行い、ビニル共重合体（Ｂ−２）を得た。
このビニル共重合体（Ｂ−２）の質量平均分子量Ｍｗは８９，０００で、単量体転化率は９７％であり、メタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は３２．３質量％であった。
<Production Example 3: Production of vinyl copolymer (B-2)>
As a vinyl monomer mixture, a vinyl monomer mixture of 67.0% by mass of styrene and 33.0% by mass of acrylonitrile was used, and the amount of t-dodecyl mercaptan was changed to 0.4 parts by mass. Suspension polymerization was performed under the conditions to obtain a vinyl copolymer (B-2).
This vinyl copolymer (B-2) has a mass average molecular weight Mw of 89,000, a monomer conversion rate of 97%, and an acetone-soluble vinyl cyanide unit content after washing with methanol of 32%. It was 3 mass%.
＜製造例４：ビニル共重合体（Ｂ−３）の製造＞
ビニル単量体混合物として、スチレン７６．５質量％とアクリロニトリル２３．５質量％のビニル単量体混合物を用い、ｔ−ドデシルメルカプタンの量を０．５質量部とした以外は製造例２と同条件で懸濁重合を行い、ビニル共重合体（Ｂ−３）を得た。
このビニル共重合体（Ｂ−３）の質量平均分子量Ｍｗは１４１，０００で、単量体転化率は９８％であり、メタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は２２．５質量％であった。
<Production Example 4: Production of Vinyl Copolymer (B-3)>
As a vinyl monomer mixture, a vinyl monomer mixture of 76.5% by mass of styrene and 23.5% by mass of acrylonitrile was used, and the amount of t-dodecyl mercaptan was changed to 0.5 parts by mass. Suspension polymerization was performed under the conditions to obtain a vinyl copolymer (B-3).
The vinyl copolymer (B-3) has a mass average molecular weight Mw of 141,000, a monomer conversion rate of 98%, and an acetone-soluble vinyl cyanide unit content after washing with methanol of 22%. It was 5% by mass.
＜製造例５：ビニル共重合体（Ｂ−４）の製造＞
ビニル単量体混合物として、スチレン６９．０質量％とアクリロニトリル３１．０質量％のビニル単量体混合物を用い、ｔ−ドデシルメルカプタンの量を０．３質量部とした以外は製造例２と同条件で懸濁重合を行い、ビニル共重合体（Ｂ−４）を得た。
このビニル共重合体（Ｂ−４）の質量平均分子量Ｍｗは２１５，０００で、単量体転化率は９７％であり、メタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は３０．１質量％であった。
<Production Example 5: Production of vinyl copolymer (B-4)>
As a vinyl monomer mixture, a vinyl monomer mixture of 69.0% by mass of styrene and 31.0% by mass of acrylonitrile was used, and the amount of t-dodecyl mercaptan was changed to 0.3 parts by mass. Suspension polymerization was performed under the conditions to obtain a vinyl copolymer (B-4).
This vinyl copolymer (B-4) has a mass average molecular weight Mw of 215,000, a monomer conversion rate of 97%, and an acetone-soluble vinyl cyanide unit content after washing with methanol of 30%. It was 1 mass%.
＜製造例６：ビニル共重合体（Ｂ−５）の製造＞
ビニル単量体混合物として、スチレン７５．０質量％とアクリロニトリル２５．０質量％のビニル単量体混合物を用い、ｔ−ドデシルメルカプタンの量を０．５質量部とした以外は製造例２と同条件で懸濁重合を行い、ビニル共重合体（Ｂ−５）を得た。
このビニル共重合体（Ｂ−５）の質量平均分子量Ｍｗは８８，０００で、単量体転化率は９７％であり、メタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は２４．１質量％であった。
<Production Example 6: Production of vinyl copolymer (B-5)>
As a vinyl monomer mixture, the same as in Production Example 2 except that a vinyl monomer mixture of 75.0% by mass of styrene and 25.0% by mass of acrylonitrile was used and the amount of t-dodecyl mercaptan was changed to 0.5 parts by mass. Suspension polymerization was performed under the conditions to obtain a vinyl copolymer (B-5).
This vinyl copolymer (B-5) has a mass average molecular weight Mw of 88,000, a monomer conversion rate of 97%, and an acetone-soluble vinyl cyanide unit content after washing with methanol of 24%. It was 1 mass%.
＜製造例７：ビニル共重合体（Ｂ−６）の製造＞
ビニル単量体混合物として、スチレン７３．０質量％とアクリロニトリル２７．０質量％のビニル単量体混合物を用い、ｔ−ドデシルメルカプタンの量を０．４質量部とした以外は製造例２と同条件で懸濁重合を行い、ビニル共重合体（Ｂ−６）を得た。
このビニル共重合体（Ｂ−６）の質量平均分子量Ｍｗは１１５，０００で、単量体転化率は９７％であり、メタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は２５．７質量％であった。
<Production Example 7: Production of vinyl copolymer (B-6)>
As a vinyl monomer mixture, a vinyl monomer mixture of 73.0% by mass of styrene and 27.0% by mass of acrylonitrile was used, and the amount of t-dodecyl mercaptan was changed to 0.4 parts by mass. Suspension polymerization was performed under the conditions to obtain a vinyl copolymer (B-6).
This vinyl copolymer (B-6) has a mass average molecular weight Mw of 115,000, a monomer conversion of 97%, and an acetone-soluble vinyl cyanide unit content after washing with methanol of 25%. 0.7% by mass.
＜製造例８：ビニル共重合体（Ｂ−７）の製造＞
ビニル単量体混合物として、スチレン７２．０質量％とアクリロニトリル２８．０質量％のビニル単量体混合物を用い、ｔ−ドデシルメルカプタンの量を０．３質量部とした以外は製造例２と同条件で懸濁重合を行い、ビニル共重合体（Ｂ−７）を得た。
このビニル共重合体（Ｂ−７）の質量平均分子量Ｍｗは１０５，０００で、単量体転化率は９８％であり、メタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は２７．１質量％であった。
<Production Example 8: Production of vinyl copolymer (B-7)>
As a vinyl monomer mixture, a vinyl monomer mixture of 72.0% by mass of styrene and 28.0% by mass of acrylonitrile was used, and the amount of t-dodecyl mercaptan was changed to 0.3 part by mass. Suspension polymerization was performed under the conditions to obtain a vinyl copolymer (B-7).
This vinyl copolymer (B-7) has a mass average molecular weight Mw of 105,000, a monomer conversion rate of 98%, and an acetone-soluble vinyl cyanide unit content after washing with methanol of 27%. It was 1 mass%.
＜製造例９：ビニル共重合体（Ｂ−８）の製造＞
ビニル単量体混合物として、スチレン６５．０質量％とアクリロニトリル３５．０質量％のビニル単量体混合物を用い、ｔ−ドデシルメルカプタンの量を０．４質量部とした以外は製造例２と同条件で懸濁重合を行い、ビニル共重合体（Ｂ−８）を得た。
このビニル共重合体（Ｂ−８）の質量平均分子量Ｍｗは８１，０００で、単量体転化率は９８％であり、メタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量は３４．０質量％であった。
<Production Example 9: Production of vinyl copolymer (B-8)>
As a vinyl monomer mixture, a vinyl monomer mixture of 65.0% by mass of styrene and 35.0% by mass of acrylonitrile was used, and the amount of t-dodecyl mercaptan was changed to 0.4 parts by mass. Suspension polymerization was performed under the conditions to obtain a vinyl copolymer (B-8).
This vinyl copolymer (B-8) has a mass average molecular weight Mw of 81,000, a monomer conversion of 98%, and an acetone-soluble vinyl cyanide unit content after washing with methanol of 34%. It was 0.0 mass%.
［実施例１〜５、比較例１〜６］
上記各製造例で得られた各重合体とフッ素樹脂と滑剤を表１，２に示す割合で配合し、ヘンシェルミキサーで混合した後、押出機で混練してペレット化した。
得られた樹脂組成物のペレットを用いて、前述の各評価（１）〜（３）を行い、結果を表１，２に示した。
なお、フッ素樹脂としては旭硝子（株）製「Ｆｌｕｏｎ（登録商標）ＰＴＦＥファインパウダーＣＤ−１」（数平均分子量３００万）を用い、滑剤としては日油（株）社製ＥＢＳ−ＷＡＸ「アルフローＨ−５０Ｓ」を用いた。
[Examples 1-5, Comparative Examples 1-6]
Each polymer obtained in each of the above production examples, a fluororesin, and a lubricant were blended in the ratios shown in Tables 1 and 2, mixed with a Henschel mixer, and then kneaded with an extruder to be pelletized.
Each of the evaluations (1) to (3) described above was performed using the obtained pellets of the resin composition, and the results are shown in Tables 1 and 2.
In addition, “Fluon (registered trademark) PTFE fine powder CD-1” (number average molecular weight 3 million) manufactured by Asahi Glass Co., Ltd. is used as the fluororesin, and EBS-WAX “Alflow H” manufactured by NOF Corporation is used as the lubricant. −50S ”was used.
＜考察＞
実施例１〜５のように、本発明の熱可塑性樹脂組成物によれば、ハロゲン系難燃剤、リン系難燃剤などの難燃剤やアンチモン化合物のような難燃助剤を配合することなく、薄肉厚み（０．５８ｍｍ）における米国ＵＬ規格９４ＨＢに適合する優れた安全性を示し、しかも、外観に優れた熱可塑性樹脂成形品が提供される。
<Discussion>
As in Examples 1 to 5, according to the thermoplastic resin composition of the present invention, without blending a flame retardant such as a halogen-based flame retardant, a phosphorus-based flame retardant, or a flame retardant aid such as an antimony compound, A thermoplastic resin molded article exhibiting excellent safety conforming to US UL standard 94HB at a thin wall thickness (0.58 mm) and having an excellent appearance is provided.
一方、比較例１〜４は、シアン化ビニル単位の含有量差の絶対値｜ＣＢＡ−ＣＢＢ｜が、３．０〜７．０質量％を外れているので燃焼時間が短く、米国ＵＬ規格９４ＨＢに適合しない。比較例５は、フッ素樹脂の添加量が本発明の範囲より少ないため、燃焼時間が短く、米国ＵＬ規格９４ＨＢに適合せず、比較例６は多いために外観が悪い。 On the other hand, in Comparative Examples 1 to 4, the absolute value of the difference in content of vinyl cyanide units | CB A −CB B | Does not conform to standard 94HB. In Comparative Example 5, the addition amount of the fluororesin is less than the range of the present invention, so the combustion time is short, and it does not conform to US UL standard 94HB.
本発明の熱可塑性樹脂組成物を成形してなる成形品は、薄肉化に対応でき、特に、薄肉でのＨＢ性能を十分に発揮することができ、さらに外観にも優れていることから、その用途として、例えば、電気・電子関連の用途では、ノートパソコン、携帯電話、プリンター、テレビ、オーディオなどのＯＡ機器や家電製品の外装材など、市場のニーズに合わせて多彩な用途に使用することができ、その工業的有用性は非常に高い上に、環境負荷の低減にも有効である。 Since the molded product formed by molding the thermoplastic resin composition of the present invention can cope with thinning, in particular, it can fully exhibit HB performance with a thin wall, and further has an excellent appearance. As applications, for example, in electrical and electronic applications, it can be used for a variety of applications in accordance with market needs, such as notebook computers, mobile phones, printers, televisions, audio equipment and other office automation equipment, and exterior materials for home appliances. In addition to its very high industrial utility, it is also effective in reducing environmental impact.
Claims (5)
グラフト共重合体（Ａ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＡと、ビニル共重合体（Ｂ）のメタノール洗浄後のアセトン可溶分のシアン化ビニル単位の含有量ＣＢＢの差の絶対値｜ＣＢＡ−ＣＢＢ｜が３．０〜７．０質量％であることを特徴とする熱可塑性樹脂組成物。 Graft copolymer (A) formed by graft polymerization of vinyl cyanide compound and vinyl compound copolymerizable with vinyl cyanide compound on rubber polymer, vinyl cyanide compound, vinyl cyanide compound, In a copolymer mixture comprising a vinyl copolymer (B) obtained by copolymerizing a copolymerizable vinyl compound, 0.1 to 0.3 parts by mass of 100 parts by mass of the copolymer mixture A thermoplastic resin composition comprising a fluorine resin (C),
A content CB A acetone-soluble fraction of the vinyl cyanide units after methanol washing of the graft copolymer (A), acetone-soluble matter of the vinyl cyanide units after methanol washing of vinyl copolymer (B) A thermoplastic resin composition characterized in that the absolute value | CB A -CB B | of the difference in the content CB B is 3.0 to 7.0% by mass.
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