JP2007119681A - Thermoplastic resin composition and molded product - Google Patents
Thermoplastic resin composition and molded product Download PDFInfo
- Publication number
- JP2007119681A JP2007119681A JP2005316558A JP2005316558A JP2007119681A JP 2007119681 A JP2007119681 A JP 2007119681A JP 2005316558 A JP2005316558 A JP 2005316558A JP 2005316558 A JP2005316558 A JP 2005316558A JP 2007119681 A JP2007119681 A JP 2007119681A
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- JP
- Japan
- Prior art keywords
- parts
- mass
- meth
- monomer
- thermoplastic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 53
- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 80
- -1 acrylic ester Chemical class 0.000 claims abstract description 50
- 229920001577 copolymer Polymers 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 34
- 239000004816 latex Substances 0.000 claims abstract description 34
- 229920000126 latex Polymers 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 31
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 34
- 238000000465 moulding Methods 0.000 abstract description 19
- 229920001971 elastomer Polymers 0.000 description 53
- 239000002245 particle Substances 0.000 description 35
- 238000004519 manufacturing process Methods 0.000 description 32
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010559 graft polymerization reaction Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 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 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 5
- 239000000701 coagulant Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 4
- 239000004797 high-impact polystyrene Substances 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 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 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (1R)-1,3-butanediol Natural products CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 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
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-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
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CTTJWXVQRJUJQW-UHFFFAOYSA-N 2,2-dioctyl-3-sulfobutanedioic acid Chemical compound CCCCCCCCC(C(O)=O)(C(C(O)=O)S(O)(=O)=O)CCCCCCCC CTTJWXVQRJUJQW-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、各種工業材料として利用できる熱可塑性樹脂組成物および成形品に関し、特に耐候性に優れ、耐衝撃性、流動性が良好で、さらに広い成形温度領域で良好な艶消し外観を発現する熱可塑性樹脂組成物とそれを成形した成形品に関する。 The present invention relates to thermoplastic resin compositions and molded articles that can be used as various industrial materials, and in particular, has excellent weather resistance, good impact resistance and fluidity, and exhibits a good matte appearance in a wider molding temperature range. The present invention relates to a thermoplastic resin composition and a molded product obtained by molding the same.
樹脂材料の耐衝撃性を向上させることは、樹脂材料の用途を拡大させるだけでなく成形物の薄肉化や大型化への対応を可能にするなど、工業的な有用性が非常に高いため、樹脂材料の耐衝撃性向上については、これまでに様々な手法が提案されてきた。
このうち、ゴム質重合体と硬質樹脂とを組み合わせることによって、材料の耐衝撃性を高める手法は既に工業化されている。このような材料としては、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂、ハイインパクトポリスチレン（ＨＩＰＳ）樹脂、アクリロニトリル−スチレン−アクリル酸エステル（ＡＳＡ）樹脂、変性ＰＰＥ樹脂およびＭＢＳ樹脂強化ポリ塩化ビニル樹脂等の熱可塑性樹脂組成物が挙げられる。
熱可塑性樹脂組成物の中でも、ゴム質重合体に飽和ゴムであるアルキル（メタ）アクリレートゴム等の成分を用いたＡＳＡ樹脂やアルキル（メタ）アクリレートゴムとポリオルガノシロキサンとの複合ゴム等の成分を用いたＳＡＳ樹脂やエチレン−プロピレン系ゴム成分を用いたＡＥＳ樹脂は良好な耐候性を有するという特徴を有する。
最近、ダッシュボードやインストルメントパネル等の自動車内装用部品や住宅用樹脂化建材等の分野を主体に、光沢が著しく低減された材料、いわゆる艶消し材料に対する需要が高まりつつある。
この様な艶消し化方法としては、架橋硬質重合体を熱可塑性樹脂組成物に配合する方法が提案されている（例えば特許文献１〜特許文献９参照）。
しかしながら、近年の厳しい材料スペックの要求は高まっており、これら先行技術により得られる熱可塑性樹脂では耐衝撃性等が不足し、その使用には制限があった。
Improving the impact resistance of resin materials not only expands the applications of resin materials, but also makes it possible to cope with the reduction in thickness and size of molded products. Various techniques have been proposed so far for improving the impact resistance of resin materials.
Among these, a technique for increasing the impact resistance of a material by combining a rubbery polymer and a hard resin has already been industrialized. Examples of such materials include acrylonitrile-butadiene-styrene (ABS) resin, high impact polystyrene (HIPS) resin, acrylonitrile-styrene-acrylic ester (ASA) resin, modified PPE resin, and MBS resin reinforced polyvinyl chloride resin. A thermoplastic resin composition is mentioned.
Among thermoplastic resin compositions, components such as a composite rubber of an ASA resin or an alkyl (meth) acrylate rubber and a polyorganosiloxane using a component such as an alkyl (meth) acrylate rubber which is a saturated rubber as a rubber polymer. The SAS resin used and the AES resin using the ethylene-propylene rubber component are characterized by having good weather resistance.
Recently, there has been an increasing demand for materials with significantly reduced gloss, so-called matte materials, mainly in the fields of automotive interior parts such as dashboards and instrument panels and resin-based building materials for housing.
As such a matting method, a method of blending a cross-linked hard polymer into a thermoplastic resin composition has been proposed (for example, see Patent Documents 1 to 9).
However, demands for strict material specifications in recent years are increasing, and the thermoplastic resins obtained by these prior arts are insufficient in impact resistance and the use thereof is limited.
また、その様な耐衝撃性の低下を避ける目的で、粒子サイズの大なるゴム状重合体を含む艶消し性の熱可塑性樹脂が提案されている（例えば、特許文献１０〜特許文献１４）。
しかし、これらの方法では耐衝撃性が低下しやすいとの問題は解決できるが、一方で艶消し外観の成形条件に対する依存性が大きくなり、成形品の部位によって光沢差が生じ易く、斑になり易い傾向があった。
Further, for the purpose of avoiding such a decrease in impact resistance, a matte thermoplastic resin containing a rubbery polymer having a large particle size has been proposed (for example, Patent Documents 10 to 14).
However, these methods can solve the problem that the impact resistance tends to decrease, but on the other hand, the dependence of the matte appearance on the molding conditions becomes large, and gloss differences easily occur depending on the part of the molded product, resulting in spots. There was a tendency to be easy.
さらに、この様な艶消し外観の条件依存性や斑の発生が少ない技術として、反応性の官能基を含有する重合体を配合する方法が提案されている（特許文献１５〜特許文献２１）。
しかし、これら技術では、樹脂材料の流動性低下が著しく、成形加工に支障がある場合が多く問題があった。
However, these techniques have a problem in that the flowability of the resin material is remarkably lowered, and there are many problems in molding processing.
本発明は前記課題を解決するためになされたもので、耐候性、耐衝撃性、流動性、そして広い成形加工条件での艶消し性、のいずれもが優れた熱可塑性樹脂組成物および成形品を目的とする。 The present invention has been made to solve the above-mentioned problems, and is a thermoplastic resin composition and a molded product excellent in all of weather resistance, impact resistance, fluidity, and matting property under a wide range of molding conditions. With the goal.
本発明者らは、上記課題を解決するために鋭意検討した結果、酸基含有共重合体ラテックスにより肥大化処理された（メタ）アクリル酸エステル系ゴム状重合体を含むグラフト共重合体と（メタ）アクリル酸エステル系単量体を必須成分とする硬質共重合体とからなる熱可塑性樹脂組成物が上記課題を解決できることを見出し、以下の熱可塑性樹脂組成物および成形品を発明した。
すなわち、本発明の熱可塑性樹脂組成物は、酸基含有共重合体ラテックス（Ｋ）により肥大化処理された（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）に、芳香族ビニル系単量体とシアン化ビニル系単量体を含有するビニル系単量体成分がグラフト重合し、且つ、該ビニル系単量体成分に占めるシアン化ビニル系単量体含有量が２７〜５０質量％であるグラフト共重合体（Ａ）２０質量部〜８０質量部と、（メタ）アクリル酸エステル系単量体を含む硬質共重合体（Ｂ）８０質量部〜２０質量部からなることを特徴とするものである。
本発明の成形品は、上述した熱可塑性樹脂組成物を用いて成形されたものである。
尚、本明細書で「（メタ）アクリル酸」とは「アクリル酸」又は「メタクリル酸」を意味する。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a graft copolymer containing a (meth) acrylic ester rubber-like polymer enlarged by an acid group-containing copolymer latex and ( The inventors have found that a thermoplastic resin composition comprising a hard copolymer containing a meth) acrylate monomer as an essential component can solve the above-mentioned problems, and invented the following thermoplastic resin composition and molded article.
That is, the thermoplastic resin composition of the present invention is obtained by adding an aromatic vinyl-based monomer to a (meth) acrylic acid ester-based rubbery polymer (G) that has been enlarged with an acid group-containing copolymer latex (K). And the vinyl monomer component containing the vinyl cyanide monomer is graft-polymerized, and the vinyl cyanide monomer content in the vinyl monomer component is 27 to 50% by mass It consists of 20 to 80 parts by mass of a certain graft copolymer (A) and 80 to 20 parts by mass of a hard copolymer (B) containing a (meth) acrylate monomer. Is.
The molded product of the present invention is molded using the above-described thermoplastic resin composition.
In the present specification, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”.
本発明の熱可塑性樹脂組成物であれば、耐候性と耐衝撃性、流動性に優れており、特に成形温度などの条件依存性が小さく美麗な艶消し性を発現できる。そして、これらのバランスは従来の熱可塑性樹脂組成物では得られない非常に高いレベルであり、各種工業用材料としての利用価値は極めて高い。 If it is the thermoplastic resin composition of this invention, it is excellent in a weather resistance, impact resistance, and fluidity | liquidity, and it can express beautiful matteness with especially small dependence on conditions, such as molding temperature. These balances are at a very high level that cannot be obtained with conventional thermoplastic resin compositions, and the utility value as various industrial materials is extremely high.
＜（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）＞
本発明に係るグラフト共重合体（Ａ）を構成する（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）は、（メタ）アクリル酸エステル系単量体単位を有する重合体である。
用いられる（メタ）アクリル酸エステル系単量体としては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ラウリル等のメタクリル酸アルキルエステル、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸−２−エチルヘキシル等のアクリル酸エステルであり、好ましくはアクリル酸ｎ−ブチルおよび／またはアクリル酸−２−エチルヘキシルである。これら（メタ）アクリル酸エステル系単量体においては、炭素数が１〜１２であるアルキル基を有する（メタ）アクリル酸エステル系単量体を必須成分として用いることが好ましい。
また、（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）は、ゴム状重合体１００質量部中に、前述した（メタ）アクリル酸エステル系単量体単位の１種または２種以上を５０質量部以上含むことが好ましい。得られる熱可塑性樹脂組成物の耐衝撃性が優れることから、好ましくは６０質量部以上、より好ましくは７０質量部以上である。
（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）には、上述の（メタ）アクリル酸エステル系単量体単位以外に他の単量体単位を含ませることも可能である。用いることのできる他の単量体としては、例えばスチレン、α−メチルスチレン、ビニルトルエン等の芳香族アルケニル化合物、アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物、メタクリル酸２−ヒドロキシエチルやメタクリル酸グリシジル、メタクリル酸Ｎ、Ｎ−ジメチルアミノエチル等の官能基を有する他の（メタ）アクリル酸エステル、ブタジエンやクロロプレン、イソプレン等のジエン系化合物、アクリルアミドやメタクリルアミド、無水マレイン酸、Ｎ−置換マレイミド等である。これらは目的に応じて１種または２種以上を併用して用いることができる。
本発明においては、（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）を構成する単量体単位に、架橋剤単位とグラフト交叉剤単位のどちらか一方から少なくとも一種以上を含有することが好ましい。この様にすると、得られる熱可塑性樹脂組成物の耐衝撃性と艶消し性とのバランスが良くなる傾向にある。
用いることのできる架橋剤やグラフト交叉剤の例としては、メタクリル酸アリル、シアヌル酸トリアリル、イソシアヌル酸トリアリル等のアリル化合物、ジビニルベンゼン、ジメタクリル酸エチレングリコールジエステル、ジメタクリル酸プロピレングリコールジエステル、ジメタクリル酸１,３−ブチレングリコールジエステル、ジメタクリル酸１,４−ブチレングリコールジエステル等のジ（メタ）アクリル酸エステル化合物が挙げられ、これらのうち２種類以上を併用して用いる。好ましくはグラフト交叉剤としてのアリル化合物と、架橋剤としてのジ（メタ）アクリル酸エステル化合物の組合せであり、より好ましくはグラフト交叉剤としてのメタクリル酸アリルと架橋剤としてのジメタクリル酸１,３−ブチレングリコールジエステルと組合せである。また、含有される多官能性単量体単位は、（メタ）アクリル酸エステル系ゴム状重合体１００質量部中、０.１質量部〜３質量部が好ましく、更に好ましくは０.１質量部〜１質量部である。
（メタ）アクリル酸エステル系単量体を必須成分とする単量体混合物と、二種以上の多官能性単量体とを混合した混合物を、乳化重合することにより、小粒子径の（メタ）アクリル酸エステル系ゴム状重合体（ｇ）を調製できる。小粒子径の（メタ）アクリル酸エステル系ゴム状重合体（ｇ）の質量平均粒子径としては特に限定されないが、酸基含有共重合体ラテックス（Ｋ）による肥大化が進行し易いことから、好ましくは３０ｎｍ〜２５０ｎｍであり、より好ましくは４０ｎｍ〜２００ｎｍ、さらに好ましくは５０ｎｍ〜１５０ｎｍである。２５０ｎｍを越える場合には酸基含有共重合体ラテックス（Ｋ）による肥大化が進行し難くなり、結果として得られる熱可塑性樹脂組成物の艶消し性が悪化するため 好ましくない。
<(Meth) acrylic ester rubbery polymer (G)>
The (meth) acrylate rubber-like polymer (G) constituting the graft copolymer (A) according to the present invention is a polymer having a (meth) acrylate monomer unit.
Examples of (meth) acrylic acid ester monomers used include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid alkyl esters such as lauryl methacrylate, Acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate . In these (meth) acrylic acid ester monomers, it is preferable to use a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms as an essential component.
The (meth) acrylic acid ester-based rubbery polymer (G) contains 50 or more of one or more of the aforementioned (meth) acrylic acid ester-based monomer units in 100 parts by mass of the rubbery polymer. It is preferable to contain at least part by mass. Since the resulting thermoplastic resin composition has excellent impact resistance, it is preferably 60 parts by mass or more, more preferably 70 parts by mass or more.
In addition to the above-mentioned (meth) acrylic acid ester monomer unit, the (meth) acrylic acid ester rubbery polymer (G) can also contain other monomer units. Examples of other monomers that can be used include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, 2-hydroxyethyl methacrylate and methacrylic acid. Other (meth) acrylic acid esters having functional groups such as glycidyl, methacrylate N, N-dimethylaminoethyl, diene compounds such as butadiene, chloroprene, isoprene, acrylamide, methacrylamide, maleic anhydride, N-substituted maleimide Etc. These may be used alone or in combination of two or more according to the purpose.
In the present invention, it is preferable that the monomer unit constituting the (meth) acrylic ester-based rubbery polymer (G) contains at least one or more of either a crosslinking agent unit or a graft crossing agent unit. . If it does in this way, it exists in the tendency for the balance of the impact resistance of the thermoplastic resin composition obtained and mattness to improve.
Examples of crosslinking agents and grafting agents that can be used include allyl compounds such as allyl methacrylate, triallyl cyanurate and triallyl isocyanurate, divinylbenzene, dimethacrylic acid ethylene glycol diester, dimethacrylic acid propylene glycol diester, dimethacrylic acid. Examples include di (meth) acrylic acid ester compounds such as acid 1,3-butylene glycol diester and dimethacrylic acid 1,4-butylene glycol diester, and two or more of these are used in combination. Preferably, it is a combination of an allyl compound as a graft crossing agent and a di (meth) acrylic acid ester compound as a cross-linking agent, more preferably allyl methacrylate as a graft crossing agent and dimethacrylic acid 1,3 as a cross-linking agent. -In combination with butylene glycol diester. The polyfunctional monomer unit contained is preferably 0.1 to 3 parts by mass, more preferably 0.1 parts by mass, in 100 parts by mass of the (meth) acrylic ester rubber-like polymer. -1 part by mass.
By emulsion polymerization of a mixture of a monomer mixture containing a (meth) acrylic acid ester monomer as an essential component and two or more polyfunctional monomers, a small particle diameter (meta ) Acrylic ester rubbery polymer (g) can be prepared. The mass average particle diameter of the (meth) acrylic acid ester-based rubbery polymer (g) having a small particle diameter is not particularly limited, but enlargement due to the acid group-containing copolymer latex (K) is likely to proceed. Preferably they are 30 nm-250 nm, More preferably, they are 40 nm-200 nm, More preferably, they are 50 nm-150 nm. If it exceeds 250 nm, enlargement by the acid group-containing copolymer latex (K) is difficult to proceed, and the matteness of the resulting thermoplastic resin composition is deteriorated, which is not preferable.
＜肥大化＞
肥大化剤として用いられる酸基含有共重合体ラテックス（Ｋ）とは、酸基含有単量体単位と（メタ）アクリル酸エステル系単量体単位とを有する共重合体を含有するラテックスである。
酸基含有単量体としては、アクリル酸、メタクリル酸、イタコン酸およびクロトン酸等が挙げられ、（メタ）アクリル酸エステルとしては炭素数が１〜１２のアルキル基を有する（メタ）アクリル酸エステルが好ましい。これについては（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）の製造に用いたものと同様のものが使用できる。ただし、本発明の目的である耐衝撃性と艶消し性、そして成形性に優れた熱可塑性樹脂組成物を得る目的には、酸基含有共重合体のガラス転移温度（Ｔｇ）は低い方が好ましく、アクリル酸エステル系単量体を用いることが好ましい。また、この際アルキル基の炭素数が多いアクリル酸エステル系単量体を用いることが更に好ましい。酸基含有共重合体中の（メタ）アクリル酸エステルの質量割合は、肥大化して得られる（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）の質量平均粒子径を制御しやすいこと、得られる熱可塑性樹脂組成物の艶消し性が優れることから、共重合体中０.１質量部〜３０質量部が好ましく、さらに好ましくは１０質量部〜２５質量部である。また、酸基含有重合体ラテックス中の酸基含有重合体の質量平均粒子径は、小粒子径（メタ）アクリル酸エステル系ゴム状重合体（ｇ）を肥大化させる際のラテックスの安定性が優れ、肥大化して得られる（メタ）アクリル酸エステル系ゴム（Ｇ）の質量平均粒子径を制御しやすいこと、得られる熱可塑性樹脂組成物の艶消し性が優れることから、５０ｎｍ〜２５０ｎｍが好ましい。
本発明の（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）は、小粒子径の（メタ）アクリル酸エステル系ゴム重合体（ｇ）が、前記酸基含有共重合体ラテックス（Ｋ）により肥大化処理されたものである。肥大化処理は、前述のごとく乳化重合で得られた小粒子径（メタ）アクリル酸エステル系ゴム状重合体（ｇ）ラテックス中に、酸基含有共重合体ラテックス（Ｋ）を添加することによって行われ、その肥大化方法については特開昭５０−２５６５５号公報や特開昭５８−６１１０２号公報、特開昭５９−１４９９０２号公報等、既知の方法で行うことができる。
用いる酸基含有共重合体ラテックス（Ｋ）の適正な使用量としては、小粒子径（メタ）アクリル酸エステル系ゴム状重合体（ｇ）の性状や酸基含有共重合体ラテックス（Ｋ）の組成や性状にもよるが、小粒子径（メタ）アクリル酸エステル系ゴム状重合体（ｇ）１００質量部（固形分）に対し、０.１質量部〜１０質量部（固形分）である。好ましくは、０.３質量部〜５質量部である。この量が０.１質量部未満であった場合には、肥大化が進行しないばかりでなく、得られる熱可塑性樹脂組成物の艶消性が悪化し、さらには耐衝撃性が低下する傾向にある。また、１０質量部を越える場合には得られる熱可塑性樹脂組成物の艶消性が再び低下する傾向にある。
よって、本発明の要旨は、酸基含有共重合体ラテックス（Ｋ）で肥大化処理され、この酸基含有共重合体を含む（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）を用いることによって、優れた艶消し外観を有する熱可塑性樹脂組成物を得ることにある。逆に、酸基含有共重合体ラテックス（Ｋ）を用いずに、小粒子径（メタ）アクリル酸エステル系ゴム状重合体（ｇ）のごとく通常の（メタ）アクリル酸エステル系ゴム状重合体をグラフト共重合体のベースに用いた場合には、熱可塑性樹脂組成物の艶消し外観を発現せずに光沢が大きく上昇する。
肥大化処理を行う場合、特開昭５６−１６６２０１号公報に提案されているごとく、無機電解質を少量併用することが肥大化を進行させやすくする点から好ましい。用いる無機電解質はどの様なものでも構わないが、硫酸ナトリウムや塩化ナトリウム、塩化カリウム、炭酸カリウム等、中性ないしアルカリ性の無機電解質が好ましい。無機電解質の使用方法にも限定されず、ゴム状重合体の重合前に予め含ませておいても、肥大化処理前に添加しても一向に差し支えない。また、特開昭５０−２５６５５号公報に提案されている様に、肥大化される小粒子径ゴム状重合体ラテックス（ｇ）のｐＨは７以上になる様に調製することが好ましく、より好ましくは８以上、さらに好ましくは９以上である。ｐＨを調節する方法についてはどの様なものでも構わないが、炭酸ナトリウムや炭酸カリウム、水酸化ナトリウム等のアルカリ性物質を添加する方法が例示される。
肥大化された（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）の質量平均粒子径の範囲は、得られる熱可塑性樹脂組成物の耐衝撃性と艶消し性とのバランスが優れることから、その上限が１０００ｎｍ、好ましくは８００ｎｍ、さらに好ましくは６００ｎｍ、下限は用いた小粒子径（メタ）アクリル酸エステル系ゴム状重合体（ｇ）の粒子径を下回らない範囲で２００ｎｍ、好ましくは２５０ｎｍ、さらに好ましくは３００ｎｍである。また、肥大化処理においては、（メタ）アクリル酸エステル系ゴム（Ｇ）中、肥大化されていない小粒子径の（メタ）アクリル酸エステル系ゴム（ｇ）の存在割合が、１５質量部以下となるよう肥大化することが好ましい。
<Enlargement>
The acid group-containing copolymer latex (K) used as a thickening agent is a latex containing a copolymer having an acid group-containing monomer unit and a (meth) acrylic acid ester monomer unit. .
Examples of the acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, and crotonic acid, and the (meth) acrylic acid ester is a (meth) acrylic acid ester having an alkyl group having 1 to 12 carbon atoms. Is preferred. About this, the thing similar to what was used for manufacture of a (meth) acrylic-ester type rubber-like polymer (G) can be used. However, for the purpose of obtaining a thermoplastic resin composition excellent in impact resistance, matteness and moldability, which is the object of the present invention, the glass transition temperature (Tg) of the acid group-containing copolymer should be lower. It is preferable to use an acrylate monomer. In this case, it is more preferable to use an acrylate monomer having a large number of carbon atoms in the alkyl group. The mass ratio of the (meth) acrylic acid ester in the acid group-containing copolymer is easy to control the mass average particle diameter of the (meth) acrylic acid ester-based rubbery polymer (G) obtained by enlargement. Since the matteness of the resulting thermoplastic resin composition is excellent, the content of the copolymer is preferably 0.1 to 30 parts by mass, and more preferably 10 to 25 parts by mass. The mass average particle diameter of the acid group-containing polymer in the acid group-containing polymer latex is such that the stability of the latex when enlarging the small particle diameter (meth) acrylate rubber polymer (g) is large. 50 nm to 250 nm is preferable because it is easy to control the mass average particle diameter of the (meth) acrylic acid ester rubber (G) obtained by being excellent and enlarged, and the matting property of the resulting thermoplastic resin composition is excellent. .
The (meth) acrylic acid ester rubber polymer (G) of the present invention has a small particle size (meth) acrylic acid ester rubber polymer (g) formed of the acid group-containing copolymer latex (K). It has been enlarged. The enlargement treatment is performed by adding the acid group-containing copolymer latex (K) to the small particle size (meth) acrylate rubber-based polymer (g) latex obtained by emulsion polymerization as described above. As for the enlargement method, known methods such as JP-A-50-25655, JP-A-58-61102 and JP-A-59-149902 can be used.
The appropriate amount of the acid group-containing copolymer latex (K) to be used includes the properties of the small particle size (meth) acrylic ester rubber polymer (g) and the acid group-containing copolymer latex (K). Although it depends on the composition and properties, it is 0.1 part by mass to 10 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the small particle diameter (meth) acrylic ester rubber polymer (g). . Preferably, it is 0.3-5 mass parts. When this amount is less than 0.1 part by mass, not only the enlargement does not proceed, but the matteness of the obtained thermoplastic resin composition deteriorates, and the impact resistance tends to decrease. is there. Moreover, when it exceeds 10 mass parts, it exists in the tendency for the matte property of the thermoplastic resin composition obtained to fall again.
Therefore, the gist of the present invention is to use a (meth) acrylic ester rubber-like polymer (G) which is enlarged with an acid group-containing copolymer latex (K) and contains this acid group-containing copolymer. Is to obtain a thermoplastic resin composition having an excellent matte appearance. On the contrary, a normal (meth) acrylate rubber polymer like a small particle size (meth) acrylate rubber polymer (g) without using an acid group-containing copolymer latex (K). Is used as the base of the graft copolymer, the gloss greatly increases without exhibiting the matte appearance of the thermoplastic resin composition.
When the enlargement treatment is performed, as proposed in JP-A-56-166201, it is preferable to use a small amount of an inorganic electrolyte in terms of facilitating the enlargement. Any inorganic electrolyte may be used, but neutral or alkaline inorganic electrolytes such as sodium sulfate, sodium chloride, potassium chloride, and potassium carbonate are preferable. The method of using the inorganic electrolyte is not limited, and the inorganic electrolyte may be preliminarily contained before the polymerization of the rubbery polymer or may be added before the enlargement treatment. Further, as proposed in JP-A-50-25655, it is preferable to prepare such that the pH of the small particle diameter rubbery polymer latex (g) to be enlarged is 7 or more, more preferably Is 8 or more, more preferably 9 or more. Any method for adjusting the pH may be used, but a method of adding an alkaline substance such as sodium carbonate, potassium carbonate, or sodium hydroxide is exemplified.
The mass average particle diameter range of the enlarged (meth) acrylic ester rubber polymer (G) is excellent in the balance between impact resistance and matting properties of the resulting thermoplastic resin composition. The upper limit is 1000 nm, preferably 800 nm, more preferably 600 nm, and the lower limit is 200 nm, preferably 250 nm, as long as it does not fall below the particle diameter of the small particle size (meth) acrylate rubber polymer (g) used. Preferably it is 300 nm. In the enlargement treatment, the presence ratio of the (meth) acrylate rubber (g) having a small particle size not enlarged in the (meth) acrylate rubber (G) is 15 parts by mass or less. It is preferable to enlarge it.
＜グラフト共重合体（Ａ）＞
本発明のグラフト共重合体（Ａ）は、前述した酸基含有共重合体ラテックス（Ｋ）により肥大化された（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）に、芳香族ビニル系単量体とシアン化ビニル系単量体、更に必要に応じて共重合可能な他の単量体からなるビニル系単量体をグラフト重合することによって得ることができる。
グラフト重合に用いる芳香族ビニル系単量体としては、例えばスチレン、α−メチルスチレン、ｐ−メチルスチレン等のビニルトルエン類、ｐ−クロルスチレン等のハロゲン化スチレン類、ｐ−ｔ−ブチルスチレン、ジメチルスチレン、ビニルナフタレン類等が使用でき、樹脂の原料としてはスチレンまたはα−メチルスチレンが好ましい。
グラフト重合に用いる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、シアン化ビニリデン等が使用できるが、樹脂の原料としてはアクリロニトリルが好適である。
また、目的に応じて他の単量体を用いることは特に制限されない。用いることのできる単量体としては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸−ｎ−ブチル、アクリル酸−２−エチルヘキシル、アクリル酸−ｎ−ヘキシル、タクリル酸メチル、メタクリル酸エチル等の不飽和カルボン酸エステル系単量体や、無水マレイン酸、無水イタコン酸、無水シトラコン酸等の不飽和ジカルボン酸無水物、マレイミド、Ｎ−メチルマレイミド、Ｎ−ブチルマレイミド、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等の不飽和ジカルボン酸のイミド化合物等が使用できる。これらは、一種単独でも二種以上を併用することもできる。
単量体の使用割合は、芳香族ビニル系単量体／シアン化ビニル系単量体／その他単量体（質量比）＝５０〜８０／２７〜５０／０〜４０、好ましくは５０〜７０／３０〜４０／０〜２０である。
グラフト重合されるビニル系単量体成分中のシアン化ビニル系単量体の使用割合が上記の範囲を外れると、成形条件によって光沢が容易に変化し、艶消しの効果が十分に発揮できない。
グラフト共重合体（Ａ）は、肥大化された（メタ）アクリル酸エステル系ゴム状重合体に単量体成分を乳化グラフト重合させたものであることが好ましく、更に（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）１０質量部〜８０質量部と単量体成分９０質量部〜２０質量部（ゴム状重合体と単量体成分の合計量が１００質量部）となる様にグラフト共重合させることが好ましい。このような質量割合で乳化グラフト重合すると、最終的に得られる熱可塑性樹脂組成物の耐衝撃性と流動性、艶消し性が優れる。単量体成分の量が１０質量部未満の場合は、最終的に得られる熱可塑性樹脂組成物の耐衝撃性が低下する傾向にあり、８０質量部を超えると再び耐衝撃性が低下しさらに艶消し性が悪化する傾向にある。さらに好ましくは、グラフト共重合体（Ａ）中、ゴム状重合体（Ｇ）が３０〜７０質量部で、単量体成分は７０〜３０質量部である。このような場合、最終的に得られる熱可塑性樹脂組成物は、耐衝撃性と成形性、艶消し性を高いレベルでバランス良く発現するため好ましい。
（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）やグラフト共重合体（Ａ）を製造する際の乳化重合は、乳化剤を使用してラジカル重合技術により行うことができる。また、グラフト重合する単量体中には、グラフト率やグラフト成分の分子量を制御するための各種連鎖移動剤を添加することができる。
グラフト重合に用いる乳化剤としては、特に制限はないが、乳化重合時のラテックスの安定性が優れ、重合率を高めることができるため、サルコシン酸ナトリウム、脂肪酸カリウム、脂肪酸ナトリウム、アルケニルコハク酸ジカリウム、ロジン酸石鹸等の各種カルボン酸塩、アルキル硫酸エステル、アルキルベンゼンスルホン酸ナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸エステルナトリウムなどの中から選ばれたアニオン系乳化剤が好ましく用いられる。これらは目的に応じて使い分けられ、もちろん小粒子（メタ）アクリル酸エステル系ゴム状重合体（ｇ）の調製に用いた乳化剤をそのまま利用し、乳化グラフト重合時に追添加しなくても良い。
重合に用いるラジカル重合開始剤としては、特に限定されないが、過酸化物、アゾ系開始剤または酸化剤・還元剤を組み合わせたレドックス系開始剤を用いることができる。この中でレドックス系開始剤が好ましく、特に硫酸第一鉄・ピロリン酸ナトリウム・ブドウ糖・ヒドロパーオキサイドや、硫酸第一鉄・エチレンジアミン四酢酸二ナトリウム塩・ロンガリット・ヒドロパーオキサイドを組み合わせたレドックス系開始剤が好ましい。
乳化グラフト重合で得られたグラフト共重合体（Ａ）ラテックスは、ついで、凝固剤を溶解させた熱水中に投入され、凝析、固化される。凝固剤としては、硫酸、塩酸、リン酸、硝酸等の無機酸や、塩化カルシウム、酢酸カルシウム、硫酸アルミニウム等の金属塩等を用いることができる。凝固剤の選定は重合で用いた乳化剤と対にして選定される。すなわち、脂肪酸石鹸やロジン酸石鹸等のカルボン酸石鹸のみが使用されていた場合にはどの様な凝固剤を用いても回収可能であるが、アルキルベンゼンスルホン酸ナトリウムの様な酸性領域でも安定な乳化力を示す乳化剤が含まれている場合には上記無機酸では不十分であり、金属塩を用いる必要がある。次いで、上述のように凝固剤を使用して固化させたグラフト共重合体（Ａ）を、水または温水中に再分散させてスラリー状とし、グラフト共重合体（Ａ）中に残存する乳化剤残渣を水中に溶出させ、洗浄する。洗浄後、スラリーを脱水機等で脱水し、得られた固体を気流乾燥機等で乾燥すると、グラフト共重合体（Ａ）が粉体または粒子状で得られる。
<Graft copolymer (A)>
The graft copolymer (A) of the present invention is obtained by adding an aromatic vinyl-based monomer to the (meth) acrylic ester rubber-like polymer (G) enlarged by the acid group-containing copolymer latex (K) described above. It can be obtained by graft polymerization of a monomer and a vinyl cyanide monomer and, if necessary, a vinyl monomer comprising another monomer copolymerizable.
Examples of the aromatic vinyl monomer used for graft polymerization include vinyl toluenes such as styrene, α-methyl styrene and p-methyl styrene, halogenated styrenes such as p-chloro styrene, pt-butyl styrene, Dimethyl styrene, vinyl naphthalenes and the like can be used, and styrene or α-methyl styrene is preferable as a raw material for the resin.
Acrylonitrile, methacrylonitrile, vinylidene cyanide and the like can be used as the vinyl cyanide monomer used for the graft polymerization, but acrylonitrile is preferred as the resin raw material.
Moreover, it does not restrict | limit especially using another monomer according to the objective. Examples of the monomer that can be used include methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, acrylic acid-n-hexyl, methyl tacrylate, methyl methacrylate, and the like. Unsaturated carboxylic acid ester monomers, unsaturated dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- An imide compound of an unsaturated dicarboxylic acid such as cyclohexylmaleimide can be used. These can be used alone or in combination of two or more.
The use ratio of the monomer is aromatic vinyl monomer / vinyl cyanide monomer / other monomer (mass ratio) = 50-80 / 27-50 / 0-40, preferably 50-70. / 30-40 / 0-20.
If the proportion of vinyl cyanide monomer used in the vinyl monomer component to be grafted is out of the above range, the gloss easily changes depending on the molding conditions, and the matte effect cannot be fully exhibited.
The graft copolymer (A) is preferably obtained by emulsion graft polymerization of a monomer component to an enlarged (meth) acrylic ester rubber-like polymer, and further a (meth) acrylic ester-based polymer. Graft copolymer (G) 10 parts by weight to 80 parts by weight and monomer component 90 parts by weight to 20 parts by weight (total amount of rubbery polymer and monomer component 100 parts by weight) It is preferable to polymerize. When emulsion graft polymerization is carried out at such a mass ratio, the finally obtained thermoplastic resin composition has excellent impact resistance, fluidity and matte properties. When the amount of the monomer component is less than 10 parts by mass, the impact resistance of the finally obtained thermoplastic resin composition tends to decrease, and when it exceeds 80 parts by mass, the impact resistance decreases again. The matte property tends to deteriorate. More preferably, in the graft copolymer (A), the rubber-like polymer (G) is 30 to 70 parts by mass, and the monomer component is 70 to 30 parts by mass. In such a case, the thermoplastic resin composition finally obtained is preferable because the impact resistance, the moldability, and the matteness are expressed at a high level with a good balance.
Emulsion polymerization in producing the (meth) acrylic ester rubber-like polymer (G) and the graft copolymer (A) can be performed by a radical polymerization technique using an emulsifier. Moreover, various chain transfer agents for controlling the graft ratio and the molecular weight of the graft component can be added to the monomer to be graft polymerized.
The emulsifier used for the graft polymerization is not particularly limited. However, since the stability of the latex during emulsion polymerization is excellent and the polymerization rate can be increased, sodium sarcosine, fatty acid potassium, fatty acid sodium, alkenyl succinate dipotassium, rosin An anionic emulsifier selected from various carboxylates such as acid soaps, alkyl sulfates, sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is preferably used. These are properly used according to the purpose, and of course, the emulsifier used for the preparation of the small particle (meth) acrylate rubber-based polymer (g) may be used as it is, and may not be added at the time of emulsion graft polymerization.
Although it does not specifically limit as a radical polymerization initiator used for superposition | polymerization, The redox initiator which combined the peroxide, the azo initiator, or the oxidizing agent and the reducing agent can be used. Of these, redox initiators are preferred, especially redox initiators that combine ferrous sulfate, sodium pyrophosphate, glucose, hydroperoxide, ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, hydroperoxide. Agents are preferred.
The graft copolymer (A) latex obtained by emulsion graft polymerization is then charged into hot water in which a coagulant is dissolved, and coagulated and solidified. As the coagulant, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and metal salts such as calcium chloride, calcium acetate and aluminum sulfate can be used. The coagulant is selected in combination with the emulsifier used in the polymerization. That is, when only carboxylic acid soaps such as fatty acid soaps and rosin acid soaps are used, they can be recovered using any coagulant, but stable emulsification is possible even in acidic regions such as sodium alkylbenzene sulfonate. When an emulsifier exhibiting power is contained, the above inorganic acid is insufficient, and a metal salt must be used. Next, the graft copolymer (A) solidified using a coagulant as described above is re-dispersed in water or warm water to form a slurry, and an emulsifier residue remaining in the graft copolymer (A) Elute in water and wash. After washing, the slurry is dehydrated with a dehydrator or the like, and the obtained solid is dried with an air dryer or the like, whereby the graft copolymer (A) is obtained in the form of powder or particles.
＜硬質共重合体（Ｂ）＞
本発明において、使用される（メタ）アクリル酸エステル系単量体を必須成分とする硬質共重合体（Ｂ）は、（メタ）アクリル系エステル系単量体を２０〜１００質量部含有していることが好ましく、さらに好ましくは、４０〜１００質量部、さらに好ましくは８０〜１００質量部である。
用いられる（メタ）アクリル酸エステル系単量体としては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ラウリル等のメタクリル酸アルキルエステル、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸−２−エチルヘキシル等のアクリル酸エステルであり、好ましくはアクリル酸ｎ−ブチルおよび／またはアクリル酸−２−エチルヘキシルである。これら（メタ）アクリル酸エステル系単量体においては、炭素数が１〜１２であるアルキル基を有する（メタ）アクリル酸エステル系単量体を必須成分として用いることが好ましい。
硬質共重合体（Ｂ）としては、メタクリル酸メチル等のメタクリル酸エステル系単量体の重合成分、或いはメタクリル酸エステル系単量体とアクリル酸メチル等のアクリル酸エステル系単量体および／又は共重合可能なその他の単量体との共重合成分が好ましいが、メタクリル酸エステルとアクリル酸エステルの各単量体の質量比率は１００／０〜５０／５０が好ましく、さらには９９／１〜８０／２０の範囲であることが好ましい。アクリル酸エステルがこの範囲よりも多くなると得られる熱可塑性樹脂組成物の熱安定性および耐熱性が損なわれる傾向にある。
なお、共重合可能なその他の単量体成分としては、シアン化ビニル系単量体、芳香族ビニル系単量体、マレイミド化合物が挙げられる。
シアン化ビニル系単量体としては、アクリロニトリル、メタクリルニトリル等が挙げられ、特にアクリロニトリルが好ましい。
また、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、ｐ−メチルスチレン、ブロムスチレン等が挙げられる。特にスチレン、α−メチルスチレンが好ましい。
マレイミド化合物としては、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等が挙げられる。
また、場合により官能基により変性された単量体を含んでもよく、例えば、不飽和カルボン酸として、アクリル酸、メタクリル酸、イタコン酸、フマル酸等が挙げられる。これらは、それぞれ１種を単独で、或いは２種以上を混合して用いることができる。その使用割合は単量体混合物中１００質量部に対して３０質量部以下、特に１０質量部以下であることが好ましい。
硬質共重合体（Ｂ）を配合することにより、耐候性および艶消し性、耐熱性や流動性等の特性を改善することができるが、硬質共重合体（Ｂ）の配合量がグラフト共重合体（Ａ）と硬質共重合体（Ｂ）との合計１００質量部に対して８０質量部を超えるとゴム強化樹脂中のゴム含有量が低減することにより、耐衝撃強度が低下する。このため、硬質共重合体（Ｂ）の配合量は、グラフト共重合体（Ａ）と硬質共重合体（Ｂ）との合計１００質量部中に２０〜８０質量部、好ましくは３０〜７０質量部、より好ましくは４０〜６０質量部とする。
なお、硬質共重合体（Ｂ）は、１種を単独で用いても良く、異なる組成、分子量のものを２種以上混合して用いても良い。
<Hard copolymer (B)>
In this invention, the hard copolymer (B) which has the (meth) acrylic acid ester monomer used as an essential component contains 20-100 mass parts of (meth) acrylic ester monomers. Preferably, it is 40-100 mass parts, More preferably, it is 80-100 mass parts.
Examples of (meth) acrylic acid ester monomers used include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid alkyl esters such as lauryl methacrylate, Acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate . In these (meth) acrylic acid ester monomers, it is preferable to use a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms as an essential component.
As the hard copolymer (B), a polymerization component of a methacrylic acid ester monomer such as methyl methacrylate, or an acrylic acid ester monomer such as a methacrylic acid ester monomer and methyl acrylate and / or A copolymerization component with other copolymerizable monomers is preferable, but the mass ratio of each monomer of methacrylic acid ester and acrylic acid ester is preferably 100/0 to 50/50, more preferably 99/1 to A range of 80/20 is preferred. When the amount of acrylic ester exceeds this range, the thermal stability and heat resistance of the resulting thermoplastic resin composition tend to be impaired.
Examples of other monomer components that can be copolymerized include vinyl cyanide monomers, aromatic vinyl monomers, and maleimide compounds.
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, and bromostyrene. In particular, styrene and α-methylstyrene are preferable.
Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide and the like.
Moreover, the monomer modified | denatured by the functional group by the case may be included, for example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid etc. are mentioned as unsaturated carboxylic acid. These can be used individually by 1 type or in mixture of 2 or more types. The use ratio is preferably 30 parts by mass or less, particularly 10 parts by mass or less, with respect to 100 parts by mass in the monomer mixture.
By blending the hard copolymer (B), it is possible to improve the properties such as weather resistance, matte property, heat resistance and fluidity, but the blending amount of the hard copolymer (B) is graft copolymer weight. When it exceeds 80 parts by mass with respect to 100 parts by mass in total of the coalesced (A) and the hard copolymer (B), the rubber content in the rubber-reinforced resin is reduced, so that the impact strength is lowered. For this reason, the compounding quantity of a hard copolymer (B) is 20-80 mass parts in a total of 100 mass parts of a graft copolymer (A) and a hard copolymer (B), Preferably it is 30-70 mass. Parts, more preferably 40-60 parts by mass.
In addition, a hard copolymer (B) may be used individually by 1 type, and may mix and use 2 or more types of a different composition and molecular weight.
＜熱可塑性樹脂組成物＞
本発明の良好な艶消し表面を与える熱可塑性樹脂組成物及びその樹脂成形品は、（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）に、グラフト重合されるビニル系単量体成分全体に占めるシアン化ビニル系単量体含有量が２７〜５０質量％、好ましくは３０〜４０質量％であることが必須であり、この範囲で極めて良好な艶消し性を付与でき、幅広い成形条件においても安定した艶消し外観の熱可塑性樹脂組成物及びその樹脂成形品を得ることが可能となった。
本発明の熱可塑性樹脂組成物は、グラフト共重合体（Ａ）と硬質共重合体（Ｂ）の混合比率は、グラフト共重合体（Ａ）を２０〜８０質量部配合し、好ましくは３０〜７０質量部、更に好ましくは４０〜６０質量部である。２０質量部未満では艶消し効果が小さくなり、衝撃性も低下する。また、８０質量部を超えると、成形性が悪くなる。
また、本発明の熱可塑性樹脂組成物には、本効果を損なわない範囲で他の熱可塑性樹脂（Ｃ）や、炭酸カルシウムやタルク等の無機充填材を配合し、成形品の改質や成形性の改良を行うことができる。
他の熱可塑性樹脂（Ｃ）としては、ポリカーボネート樹脂、ポリブチレンテレフタレート（ＰＢＴ樹脂）、ポリエチレンテレフタレート（ＰＥＴ樹脂）、ポリ塩化ビニル、ポリスチレン、変性ポリフェニレンエーテル（変性ＰＰＥ樹脂）、ポリアミドからなる群から選ばれる少なくとも１種以上であることが好ましい。
本発明の熱可塑性樹脂組成物は、グラフト共重合体（Ａ）と硬質共重合体（Ｂ）とをＶ型ブレンダやヘンシェルミキサで混合し、その混合物を溶融混練することで製造される。その溶融混練では、押出機または、バンバリーミキサ、加熱ニーダ、ロール等の混練機等を用いることができる。
得られた熱可塑性樹脂組成物は、そのまま成形品の製造原料に供することができる。また、必要に応じて、この熱可塑性樹脂組成物に、顔料や染料等の着色剤、熱安定剤、光安定剤、補強剤、充填材、難燃剤、発泡剤、滑剤、可塑剤、帯電防止剤、加工助剤等を配合することができる。
<Thermoplastic resin composition>
The thermoplastic resin composition that gives a good matte surface of the present invention and the resin molded product thereof are applied to the entire vinyl monomer component that is graft-polymerized to the (meth) acrylate rubber polymer (G). It is essential that the vinyl cyanide monomer content occupies 27 to 50% by mass, preferably 30 to 40% by mass. In this range, extremely good matting properties can be imparted, and even under a wide range of molding conditions. It has become possible to obtain a thermoplastic resin composition having a stable matte appearance and a resin molded product thereof.
In the thermoplastic resin composition of the present invention, the mixing ratio of the graft copolymer (A) to the hard copolymer (B) is 20 to 80 parts by mass of the graft copolymer (A), preferably 30 to 30 parts. It is 70 mass parts, More preferably, it is 40-60 mass parts. If it is less than 20 parts by mass, the matting effect is reduced and the impact property is also lowered. Moreover, when it exceeds 80 mass parts, a moldability will worsen.
In addition, the thermoplastic resin composition of the present invention is blended with other thermoplastic resins (C) and inorganic fillers such as calcium carbonate and talc as long as the effects are not impaired, and reforming and molding of molded products. The improvement of the property can be performed.
The other thermoplastic resin (C) is selected from the group consisting of polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, modified polyphenylene ether (modified PPE resin), and polyamide. It is preferable that it is at least 1 or more types.
The thermoplastic resin composition of the present invention is produced by mixing the graft copolymer (A) and the hard copolymer (B) with a V-type blender or a Henschel mixer, and melt-kneading the mixture. In the melt-kneading, an extruder or a kneader such as a Banbury mixer, a heating kneader, or a roll can be used.
The obtained thermoplastic resin composition can be used as it is as a raw material for producing molded products. If necessary, this thermoplastic resin composition may be added to a colorant such as a pigment or dye, a heat stabilizer, a light stabilizer, a reinforcing agent, a filler, a flame retardant, a foaming agent, a lubricant, a plasticizer, or an antistatic agent. Agents, processing aids, etc. can be blended.
＜成形品＞
本発明の成形品は、上述した熱可塑性樹脂組成物を、射出成形法、押出成形法、共押出成形法、異型押出成形法、ブロー成形法、圧縮成形法、カレンダ成形法、インフレーション成形法等の各種成形方法によって成形されたものである。
また場合によっては、他の樹脂や金属等に被覆して使用することも可能である。ここで、被覆されることのできる他の樹脂としては特に限定されないが、前述の他の熱可塑性樹脂（Ｃ）や、ＡＢＳ樹脂やハイインパクトポリスチレン樹脂（ＨＩＰＳ）等のゴム変性熱可塑性樹脂、フェノール樹脂やメラミン樹脂などの熱硬化性樹脂等が広く使用できる。
<Molded product>
The molded article of the present invention is obtained by using the above-described thermoplastic resin composition by injection molding, extrusion molding, coextrusion molding, profile extrusion molding, blow molding, compression molding, calendar molding, inflation molding, etc. These are molded by various molding methods.
In some cases, it may be used by coating with other resin or metal. Here, the other resin that can be coated is not particularly limited, but other thermoplastic resins (C) described above, rubber-modified thermoplastic resins such as ABS resin and high impact polystyrene resin (HIPS), phenol, and the like. Thermosetting resins such as resins and melamine resins can be widely used.
以下、実施例及び比較例により本発明をさらに具体的に説明するが、本発明はその要旨を越えない限り、以下の例に限定されるものではない。なお、以下の例中の％および部数は明記しない限りは質量基準とする。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to the following examples, unless the summary is exceeded. In the following examples,% and parts are based on mass unless otherwise specified.
［製造例１］ 小粒子径（メタ）アクリル酸エステル系ゴム状重合体（ｇ−１）の製造
攪拌装置および温度制御ジャケット付き１０リットルのステンレス製オートクレーブに、脱イオン水（以後、単に水と略記）４００部、アルケニルコハク酸ジカリウム（花王（株）製ラテムルＡＳＫ）１.０部、硫酸ナトリウム０.３部、アクリル酸ｎ−ブチル９７部、アクリロニトリル３部、シアヌル酸トリアリル０.８部、ジメタクリル酸１,３−ブチレングリコールエステル０.３部を攪拌下で仕込み、反応器内を窒素置換後、内容物を昇温した。
内温５５℃にて、過硫酸カリウム０.２部、水５部からなる水溶液を添加し重合を開始せしめた。重合発熱が確認されたらジャケット温度を５０℃とし、重合発熱が確認されなくなるまで重合を継続した。重合開始から３時間後に冷却し、固形分が１９.９％、質量平均粒子径が７５ｎｍおよびｐＨが８.６である小粒子径アクリル酸エステル系ゴム状重合体（ｇ−１）ラテックスを得た。
[Production Example 1] Production of small particle size (meth) acrylic ester rubber polymer (g-1) To a 10 liter stainless steel autoclave with a stirrer and a temperature control jacket, deionized water (hereinafter simply referred to as water and Abbreviation) 400 parts, dipotassium alkenyl succinate (Latemul ASK manufactured by Kao Corporation) 1.0 part, 0.3 part of sodium sulfate, 97 parts of n-butyl acrylate, 3 parts of acrylonitrile, 0.8 part of triallyl cyanurate, Dimethacrylic acid 1,3-butylene glycol ester (0.3 parts) was charged with stirring, and the contents in the reactor were heated after the atmosphere in the reactor was replaced with nitrogen.
At an internal temperature of 55 ° C., an aqueous solution comprising 0.2 part of potassium persulfate and 5 parts of water was added to initiate polymerization. When a polymerization exotherm was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until no polymerization exotherm was confirmed. The mixture was cooled 3 hours after the start of polymerization to obtain a small particle size acrylic ester rubbery polymer (g-1) latex having a solid content of 19.9%, a mass average particle size of 75 nm and a pH of 8.6. It was.
［製造例２］ 小粒子径アクリル酸エステル系ゴム状重合体（ｇ−２）の製造
製造例１記載例において、ジメタクリル酸１,３−ブチレングリコールエステルを使用しない以外は同様の方法で重合を行い、固形分が１９.９％、質量平均粒子径が８０ｎｍおよびｐＨが８.４である小粒子径アクリル酸エステル系ゴム状重合体（ｇ−２）ラテックスを得た。
[Production Example 2] Production of small particle size acrylic ester rubbery polymer (g-2) Polymerization was carried out in the same manner as in Production Example 1 except that 1,3-butylene glycol ester of dimethacrylic acid was not used. A small particle size acrylic ester rubbery polymer (g-2) latex having a solid content of 19.9%, a mass average particle size of 80 nm and a pH of 8.4 was obtained.
［製造例３］ 小粒子径アクリル酸エステル系ゴム状重合体（ｇ−３）の製造
製造例１記載例において、シアヌル酸トリアリルを使用しない以外は同様の方法で重合を行い、固形分が２０.０％、質量平均粒子径が７５ｎｍおよびｐＨが８.５である小粒子径アクリル酸エステル系ゴム状重合体（ｇ−３）ラテックスを得た。
[Production Example 3] Production of small particle size acrylic ester rubbery polymer (g-3) In Production Example 1, the polymerization was conducted in the same manner except that triallyl cyanurate was not used, and the solid content was 20 A small particle size acrylic ester rubbery polymer (g-3) latex having 0.0%, a mass average particle size of 75 nm and a pH of 8.5 was obtained.
［製造例４］ 酸基含有共重合体ラテックス（Ｋ）の調製
試薬注入容器、冷却管、ジャケット加熱機および攪拌装置を備えた反応器内に、ナトリウム２.５部、ナトリウムホルムアルデヒドスルホキシレート二水和物０.３部、水２００部、オレイン酸カリウム２.２部、ジオクチルスルホコハク酸３.６部、硫酸第一鉄七水塩０.００３部、エチレンジアミン四酢酸二ナトリウム０.００９部を窒素フロー下で仕込み、６０℃に昇温した。
６０℃になった時点から、アクリル酸ｎ−ブチル８１.５部、メタクリル酸１８.５部、クメンヒドロパーオキシド０.５部からなる混合物を１２０分かけて連続的に滴下した。滴下終了後さらに、２時間６０℃のまま熟成を行い、固形分が３３.０％、重合転化率が９９％および質量平均粒子径が１４５ｎｍである酸基含有共重合体ラテックス（Ｋ）を得た。
[Production Example 4] Preparation of acid group-containing copolymer latex (K) In a reactor equipped with a reagent injection vessel, a condenser, a jacket heater and a stirrer, 2.5 parts of sodium, sodium formaldehyde sulfoxylate 0.3 parts of hydrate, 200 parts of water, 2.2 parts of potassium oleate, 3.6 parts of dioctylsulfosuccinic acid, 0.003 part of ferrous sulfate heptahydrate, 0.0009 part of disodium ethylenediaminetetraacetate The mixture was charged under a nitrogen flow and heated to 60 ° C.
When the temperature reached 60 ° C., a mixture comprising 81.5 parts of n-butyl acrylate, 18.5 parts of methacrylic acid and 0.5 part of cumene hydroperoxide was continuously added dropwise over 120 minutes. After completion of the dropwise addition, the mixture was aged for 2 hours at 60 ° C. to obtain an acid group-containing copolymer latex (K) having a solid content of 33.0%, a polymerization conversion rate of 99%, and a mass average particle diameter of 145 nm. It was.
［製造例５］ （メタ）アクリル酸エステル系ゴム状重合体（Ｇ）の製造
製造例１〜製造例３で製造したアクリル酸エステル系ゴム状重合体（ｇ−１）〜（ｇ−３）、酸基含有共重合体ラテックス（Ｋ）を用い、アクリル酸エステル系ゴム状重合体（ｇ）の内温６５℃かつ攪拌下にて、表１に示す所定量を一括で添加し、その温度を保ちながら３０分間攪拌を継続し肥大化されたアクリル酸エステル系ゴム状重合体（Ｇ−１ａ）〜（Ｇ−１ｃ）、（Ｇ−２）、（Ｇ−３）ラテックスを得た。またこの際、肥大化処理する前に１％水酸化ナトリウム水溶液にてアクリル酸エステル系ゴム状重合体（Ｇ）のｐＨを９〜１０の間に調節した。
[Production Example 5] Production of (meth) acrylic acid ester rubbery polymer (G) The acrylic acid ester rubbery polymers (g-1) to (g-3) produced in Production Example 1 to Production Example 3. Using the acid group-containing copolymer latex (K), a predetermined amount shown in Table 1 was added all at once at an internal temperature of 65 ° C. and stirring of the acrylic ester rubbery polymer (g), and the temperature Acrylic ester rubber polymers (G-1a) to (G-1c) to (G-2), (G-3) and (G-3) latex were obtained by continuing stirring for 30 minutes while maintaining the viscosity. At this time, the pH of the acrylic ester rubbery polymer (G) was adjusted to 9 to 10 with a 1% aqueous sodium hydroxide solution before the enlargement treatment.
［製造例６］ 大粒子径アクリル酸エステル系ゴム状重合体（Ｚ−１）の製造
製造例１記載の例において、用いるアルケニルコハク酸ジカリウムの量を０.２部とし、重合終了後にさらに０.８部を追添加する以外は同様にして重合を行い、固形分が１９.４％、質量平均粒子径が３７０ｎｍおよびｐＨが８.７である大粒子径なアクリル酸エステル系ゴム状重合体（Ｚ−１）ラテックスを得た。
[Production Example 6] Production of large particle size acrylic ester rubbery polymer (Z-1) In the example described in Production Example 1, the amount of dipotassium alkenyl succinate used was set to 0.2 part, and further 0 after the completion of polymerization. Polymerization was carried out in the same manner except that 0.8 part was added, and a large particle size acrylate rubber polymer having a solid content of 19.4%, a mass average particle size of 370 nm and a pH of 8.7. (Z-1) Latex was obtained.
複合ゴム状重合体の平均粒子径は、MATEC APPLIED SCIENCES社製サブミクロン粒度分布測定器ＣＨＤＦ−２０００を用いて測定した。 The average particle size of the composite rubbery polymer was measured using a submicron particle size distribution analyzer CHDF-2000 manufactured by MATEC APPLIED SCIENCES.
［製造例７］ グラフト共重合体（Ａ−１）の製造
試薬注入容器、冷却管、ジャケット加熱機および攪拌装置を備えた反応器に、 アクリル酸エステル系ゴム状重合体（Ｇ−１ａ）ラテックス（固形分として）５０部、水（アクリル酸エステル系ゴム状重合体ラテックス中の水も含む）１７０部、ロンガリット０.１５部、アルケニルコハク酸ジカリウム０.５部を入れ、攪拌しつつ窒素気流下で内温を７５℃に昇温した。
次いで、アクリロニトリル４部、スチレン９部、ｔ−ブチルハイドロパーオキサイド０.０８部の混合液を１時間にわたって滴下し重合した。滴下終了後、温度７５℃の状態を１時間保持した後、硫酸第一鉄七水塩０.００１部、エチレンジアミン四酢酸二ナトリウム塩０.００３部、ロンガリット０.１５部、イオン交換水１０部からなる水溶液を添加し、次いで、アクリロニトリル１１部、スチレン２６部、ｔ−ブチルハイドロパーオキサイド０.２部からなる混合物を１.５時間にわたって滴下し、その間内温が８０℃を越えない様に重合せしめた。
滴下終了後、温度８０℃の状態を３０分間保持した後冷却し、グラフト共重合体（Ａ−１）ラテックスを得た。次いで１.２％硫酸水溶液１５０部を７５℃に加熱し、攪拌下この中へこのグラフト共重合体（Ａ−１）ラテックス１００部を徐々に滴下し凝固し、さらに９０℃に昇温して５分間保持した。次いで析出物を脱水、洗浄、乾燥し、アセトン不溶分７２％、還元粘度が０.７６ｄｌ／ｇである白色粉末状のグラフト共重合体（Ａ−１）を得た。
[Production Example 7] Production of graft copolymer (A-1) Acrylic ester-based rubbery polymer (G-1a) latex in a reactor equipped with a reagent injection container, a condenser tube, a jacket heater and a stirrer (As solid content) 50 parts, 170 parts of water (including water in the acrylic ester rubbery polymer latex), 0.15 part of Rongalite, 0.5 part of dipotassium alkenyl succinate, and nitrogen stream with stirring The internal temperature was raised to 75 ° C. below.
Subsequently, a mixed liquid of 4 parts of acrylonitrile, 9 parts of styrene, and 0.08 part of t-butyl hydroperoxide was dropped over 1 hour to polymerize. After completion of the dropwise addition, the temperature was maintained at 75 ° C. for 1 hour, then 0.001 part of ferrous sulfate heptahydrate, 0.003 part of disodium ethylenediaminetetraacetate, 0.15 part of Rongalite, 10 parts of ion-exchanged water Then, a mixture of 11 parts of acrylonitrile, 26 parts of styrene and 0.2 part of t-butyl hydroperoxide is added dropwise over 1.5 hours, so that the internal temperature does not exceed 80 ° C. Polymerized.
After completion of dropping, the temperature was maintained at 80 ° C. for 30 minutes and then cooled to obtain a graft copolymer (A-1) latex. Next, 150 parts of a 1.2% aqueous sulfuric acid solution was heated to 75 ° C., and 100 parts of the graft copolymer (A-1) latex was gradually dropped into the solution while stirring to solidify. Hold for 5 minutes. Next, the precipitate was dehydrated, washed and dried to obtain a graft copolymer (A-1) in the form of a white powder having an acetone insoluble content of 72% and a reduced viscosity of 0.76 dl / g.
［製造例８〜１６］ グラフト共重合体（Ａ−２）〜（Ａ−１０）の製造
製造例７記載の例において、用いるアクリル酸エステル系ゴム状重合体（Ｇ−１ａ）を（Ｇ−１ｂ）、（Ｇ−１ｃ）、（Ｇ−２）、（Ｇ−３）に変更し、またグラフト組成比を表２のように変更した以外は同様にして重合を行い、グラフト共重合体（Ａ−２）〜（Ａ−１０）を得た。その製造結果を表２に示した。
[Production Examples 8 to 16] Production of Graft Copolymers (A-2) to (A-10) In the example described in Production Example 7, the acrylate rubber polymer (G-1a) to be used is (G- 1b), (G-1c), (G-2), (G-3), and the polymerization was carried out in the same manner except that the graft composition ratio was changed as shown in Table 2, and the graft copolymer ( A-2) to (A-10) were obtained. The production results are shown in Table 2.
［製造例１７］ グラフト共重合体（Ａ−１１）の製造
製造例７記載の例において、用いるアクリル酸エステル系ゴム状重合体（Ｇ−１ａ）を酸基含有共重合体（Ｋ）によって肥大化されていない（Ｚ−１）に変更した以外は同様にして重合を行い、アセトン不溶分６９％、還元粘度が０.７７ｄｌ／ｇである粉末状のグラフト共重合体（Ａ−１１）を得た。
[Production Example 17] Production of graft copolymer (A-11) In the example described in Production Example 7, the acrylic ester rubbery polymer (G-1a) used is enlarged by the acid group-containing copolymer (K). Polymerization was carried out in the same manner except that (Z-1) was not converted to a powdery graft copolymer (A-11) having an acetone insoluble content of 69% and a reduced viscosity of 0.77 dl / g. Obtained.
・アセトン不溶分は、次のようにして求めた。
グラフト共重合体２.５ｇを８０ｍｌのアセトンに添加し、６５〜７０℃にて３時間還流し、得られた懸濁アセトン溶液を１４０００ｒｐｍにて３０分間遠心分離して、沈殿成分と上澄み溶液（アセトン溶液）をそれぞれ分取した。そして、沈殿成分を十分に乾燥させてその質量（Ｙ（ｇ））を測定した。そして、次式よりアセトン不溶分を算出した。
アセトン不溶分（％）＝（Ｙ／２.５）×１００
・還元粘度は次のようにして求めた。
アセトン可溶成分０.２ｇを１００ｃｃのＮ,Ｎ−ジメチルホルムアミドに溶解させた溶液の溶液粘度を自動粘度計（サン電子工業（株）製）を用いて２５℃で測定し、同条件で測定した溶媒粘度よりアセトン可溶分の還元粘度を求めた。
-Acetone-insoluble matter was determined as follows.
The graft copolymer (2.5 g) was added to 80 ml of acetone and refluxed at 65 to 70 ° C. for 3 hours. The obtained suspension acetone solution was centrifuged at 14000 rpm for 30 minutes to obtain a precipitate component and a supernatant solution ( Acetone solution) was collected. And the precipitation component was fully dried and the mass (Y (g)) was measured. And acetone insoluble matter was computed from following Formula.
Acetone insoluble content (%) = (Y / 2.5) × 100
-The reduced viscosity was determined as follows.
The solution viscosity of a solution obtained by dissolving 0.2 g of acetone-soluble component in 100 cc of N, N-dimethylformamide was measured at 25 ° C. using an automatic viscometer (manufactured by Sun Electronics Co., Ltd.), and measured under the same conditions. The reduced viscosity of the acetone-soluble component was determined from the solvent viscosity.
［製造例１８］ 硬質共重合体（Ｂ−１）
アクリロニトリル８部、スチレン２２部、メタクリル酸メチル７０部よりなり、 Ｎ,Ｎ−ジメチルホルムアミド溶液から２５℃で測定した還元粘度が０.３９ｄｌ／ｇであるアクリロニトリル−スチレン−メタクリル酸メチル三元共重合体（Ｂ−１）を公知の懸濁重合により製造した。
[Production Example 18] Rigid copolymer (B-1)
Acrylonitrile-styrene-methyl methacrylate ternary copolymer consisting of 8 parts of acrylonitrile, 22 parts of styrene and 70 parts of methyl methacrylate, and having a reduced viscosity of 0.39 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. The union (B-1) was produced by a known suspension polymerization.
［製造例１９］ 硬質共重合体（Ｂ−２）
メタクリル酸メチル９０部およびアクリル酸メチル１０部からなり、Ｎ,Ｎ−ジメチルホルムアミド溶液から２５℃で測定した還元粘度が０.２８ｄｌ／ｇであるアクリル樹脂（Ｂ−２）を公知の懸濁重合により製造した。
[Production Example 19] Rigid copolymer (B-2)
A known suspension polymerization of acrylic resin (B-2) comprising 90 parts of methyl methacrylate and 10 parts of methyl acrylate and having a reduced viscosity of 0.28 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. Manufactured by.
［製造例２０］ 硬質共重合体（Ｂ−３）
メタクリル酸メチル９９部およびアクリル酸メチル１部からなり、Ｎ,Ｎ−ジメチルホルムアミド溶液から２５℃で測定した還元粘度が０.２５ｄｌ／ｇであるアクリル樹脂（Ｂ−３）を公知の懸濁重合により製造した。
［製造例２１］ 硬質共重合体（Ｂ−４）
アクリロニトリル２７部およびスチレン７３部よりなり、Ｎ,Ｎ−ジメチルホルムアミド溶液から２５℃で測定した還元粘度が０.６１ｄｌ／ｇであるアクリロニトリル−スチレン共重合体（Ｂ−４）を公知の懸濁重合により製造した。
［製造例２２］ 硬質共重合体（Ｂ−５）
アクリロニトリル３９部およびスチレン６１部よりなり、Ｎ,Ｎ−ジメチルホルムアミド溶液から２５℃で測定した還元粘度が０.７５ｄｌ／ｇであるアクリロニトリル−スチレン共重合体（Ｂ−５）を公知の懸濁重合により製造した。
[Production Example 20] Rigid copolymer (B-3)
Known suspension polymerization of acrylic resin (B-3) comprising 99 parts of methyl methacrylate and 1 part of methyl acrylate and having a reduced viscosity of 0.25 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution Manufactured by.
[Production Example 21] Rigid copolymer (B-4)
A known suspension polymerization of acrylonitrile-styrene copolymer (B-4) comprising 27 parts of acrylonitrile and 73 parts of styrene and having a reduced viscosity of 0.61 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. Manufactured by.
[Production Example 22] Hard copolymer (B-5)
A known suspension polymerization of acrylonitrile-styrene copolymer (B-5) comprising 39 parts of acrylonitrile and 61 parts of styrene and having a reduced viscosity of 0.75 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. Manufactured by.
［実施例１〜実施例９、比較例１〜比較例６］ 熱可塑性樹脂組成物の製造
上記製造したグラフト共重合体（Ａ−１）〜（Ａ−１１）、ビニル系共重合体（Ｂ１）〜（Ｂ−５）を、表４に示す割合で配合し、さらにエチレンビスステアリルアミド０.４部、光安定剤（旭電化工業（株）製「アデカスタブＬＡ−６３Ｐ」０.２部、紫外線吸収剤（旭電化工業（株）製、「アデカスタブＬＡ−３６」）０.２部、着色剤として酸化チタン（石原産業（株）製「ＣＲ６０−２」）３部とを添加した後、ヘンシェルミキサを用いて混合し、この混合物をバレル温度２３０℃に加熱した脱気式二軸押出機（池貝鉄工（株）製「ＰＣＭ−３０」）で賦形し、ペレットを作製した。
得られたペレットを、中央機器（株）製４０ｍｍφ単軸押出機を用い、バレル温度１９０℃および２５０℃、冷却ロール温度５５℃で、幅６０ｍｍＴダイから樹脂をシート状に吐出させ、巻き取り速度を調節することによって厚み約１.０ｍｍに調節した幅２００ｍｍのシートを押出成形した。
[Example 1 to Example 9, Comparative Example 1 to Comparative Example 6] Production of thermoplastic resin composition Graft copolymers (A-1) to (A-11) produced above, vinyl copolymer (B1) ) To (B-5) in the proportions shown in Table 4, and 0.4 parts of ethylene bisstearylamide, 0.2 parts of light stabilizer (Adeka Stub LA-63P manufactured by Asahi Denka Kogyo Co., Ltd.), After adding 0.2 part of an ultraviolet absorber (Asahi Denka Kogyo Co., Ltd., “Adeka Stub LA-36”) and 3 parts of titanium oxide (“CR60-2” manufactured by Ishihara Sangyo Co., Ltd.) as a colorant, The mixture was mixed using a Henschel mixer, and the mixture was shaped with a degassing twin-screw extruder ("PCM-30" manufactured by Ikekai Tekko Co., Ltd.) heated to a barrel temperature of 230 ° C to produce pellets.
Using the 40 mmφ single screw extruder manufactured by Chuo Kikai Co., Ltd., the pellets obtained were discharged at a barrel temperature of 190 ° C. and 250 ° C., a cooling roll temperature of 55 ° C. in a sheet form from a 60 mm wide die, and the winding speed A sheet having a width of 200 mm, which was adjusted to a thickness of about 1.0 mm, was extruded.
実施例および比較例で得られた熱可塑性樹脂組成物を下記の評価試験によって評価した。なお、評価の結果を表４に示す。
(i)シャルピー衝撃強度
ＩＳＯ １７９に準拠した方法により行い、ノッチあり試片を用い、２３℃雰囲気下で１２時間以上試験片を放置した後に測定を行った。
(ii)メルトボリュームレート（流動性）
ＩＳＯ １１３３に準拠する方法で、バレル温度２２０℃、加重９８Ｎの条件で測定した。
(iii)成形光沢度、その温度依存性
光沢度は入射光６０°の反射率として測定した。
バレル温度１９０℃と２５０℃条件下おける成形シートの温度依存性は以下の式（１）にて求めた。
[光沢差(％)]＝(２５０℃成形品の光沢度)−(１９０℃成形品の光沢度) ・・・式（１）
（iv）成形外観
目視判定より、その艶消し性、フィッシュアイやダイラインの発生状態、表面のきめの細かさを判定し、問題なく良好なシートと認められたものを○、問題が多く実用に耐えないものを×、その中間を△と評価した。
(v)耐候性（加速暴露試験）
上記の白着色シートを、サンシャインウェザーメーター（スガ試験機（株）製）でブラックパネル温度６３℃、サイクル条件６０分（降雨：１２分）にて１,０００時間処理した。色差計で測定した暴露後試験片と未暴露試験片との色の違いを変色度ΔＥで評価した。
The thermoplastic resin compositions obtained in the examples and comparative examples were evaluated by the following evaluation tests. The evaluation results are shown in Table 4.
(i) Charpy impact strength Measurement was carried out by a method according to ISO 179, using a notched specimen and leaving the specimen for 12 hours or more in a 23 ° C. atmosphere.
(ii) Melt volume rate (fluidity)
Measurement was performed under the conditions of a barrel temperature of 220 ° C. and a load of 98 N by a method based on ISO 1133.
(iii) Molding Glossiness and Temperature Dependence The glossiness was measured as a reflectance of incident light of 60 °.
The temperature dependence of the molded sheet under the barrel temperature conditions of 190 ° C. and 250 ° C. was determined by the following equation (1).
[Gloss difference (%)] = (Glossiness of molded product at 250 ° C.) − (Glossiness of molded product at 190 ° C.) Formula (1)
(Iv) Molding appearance Judgment of matteness, appearance of fish eyes and die lines, and fineness of the surface are judged by visual judgment. Those which could not be tolerated were evaluated as x, and the middle was evaluated as Δ.
(v) Weather resistance (accelerated exposure test)
The white colored sheet was treated with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 1,000 hours at a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall: 12 minutes). The difference in color between the exposed test piece and the unexposed test piece measured with a color difference meter was evaluated by the degree of color change ΔE.
実施例および比較例より、次のことが明らかとなった。
実施例１〜９の熱可塑性樹脂組成物は、シャルピー衝撃強度とメルトボリュームレートが共に高く、成形温度１９０℃と２５０℃において良好な艶消し性を、そしてさらにサンシャインウェザーメーターによる耐候性試験では変色は小さいものであった。このような樹脂組成物は工業的価値が高い。
比較例１〜３の熱可塑性樹脂組成物は、グラフト共重合体（Ａ）中のシアン化ビニル系単量体の含有量が範囲を外れているため、１９０℃における艶消し性は比較的良好なものの、２５０℃において光沢が著しく向上し艶消しが不十分であり、この様に成形温度によって艶消し外観が変化する樹脂組成物は工業的利用価値が低い。
比較例４の熱可塑性樹脂組成物は、酸基含有共重合体ラテックス（Ｋ）を適用しない（メタ）アクリル酸エステル系ゴム状重合体（Ｇ）を含むグラフト共重合体（Ａ−１１）を用いたために、成形温度１９０℃および２５０℃のいずれの条件においても艶消し性が得られていない。この様な樹脂組成物は工業的利用価値が低い。
比較例５〜６の熱可塑性樹脂組成物は、硬質重合体に（メタ）アクリル酸エステル系単量体を含まないため、サンシャインウェザーメーターによる耐候性試験での変色が大きいものであった。このような樹脂組成物は工業的価値が低い。
From the examples and comparative examples, the following became clear.
The thermoplastic resin compositions of Examples 1 to 9 have both high Charpy impact strength and melt volume rate, good mattness at molding temperatures of 190 ° C. and 250 ° C., and further discoloration in a weather resistance test using a sunshine weather meter. Was small. Such a resin composition has high industrial value.
The thermoplastic resin compositions of Comparative Examples 1 to 3 have relatively good matte properties at 190 ° C. because the content of the vinyl cyanide monomer in the graft copolymer (A) is outside the range. However, the gloss is remarkably improved at 250 ° C. and the matte is insufficient, and thus the resin composition whose matte appearance changes depending on the molding temperature has low industrial utility value.
The thermoplastic resin composition of Comparative Example 4 is a graft copolymer (A-11) containing a (meth) acrylic ester rubber polymer (G) to which the acid group-containing copolymer latex (K) is not applied. Since it was used, the matte property was not obtained in any of the molding temperatures of 190 ° C and 250 ° C. Such a resin composition has low industrial utility value.
Since the thermoplastic resin compositions of Comparative Examples 5 to 6 did not contain a (meth) acrylic acid ester monomer in the hard polymer, the color change in the weather resistance test using a sunshine weather meter was large. Such a resin composition has low industrial value.
本発明の成形品は様々な用途で使用され、例えば、工業的用途として、車両部品、特に無塗装で使用される各種外装・内装部品、壁材、窓枠等の建材部品、食器、玩具、掃除機ハウジング、テレビジョンハウジング、エアコンハウジング等の家電部品、インテリア部材、船舶部材および通信機器ハウジング、ノートパソコンハウジング、ＰＤＡハウジング、液晶プロジェクターハウジング等の電機機器ハウジングに好適である。 The molded article of the present invention is used in various applications. For example, as industrial applications, vehicle parts, especially various exterior / interior parts used without painting, wall materials, building material parts such as window frames, tableware, toys, It is suitable for electric appliance housings such as household appliance parts such as vacuum cleaner housings, television housings, air conditioner housings, interior members, marine members and communication equipment housings, notebook personal computer housings, PDA housings, liquid crystal projector housings and the like.
Claims (2)
（メタ）アクリル酸エステル系単量体を含む硬質共重合体（Ｂ）８０質量部〜２０質量部からなることを特徴とする熱可塑性樹脂組成物。 The (meth) acrylic ester rubber-like polymer (G) enlarged by the acid group-containing copolymer latex (K) contains an aromatic vinyl monomer and a vinyl cyanide monomer. Graft copolymer of vinyl monomer component and graft copolymer (A) having a vinyl cyanide monomer content in the vinyl monomer component of 27 to 50% by mass is 20 parts by mass to 80 parts by mass,
A thermoplastic resin composition comprising 80 to 20 parts by mass of a hard copolymer (B) containing a (meth) acrylic acid ester monomer.
A molded article comprising the thermoplastic resin composition according to claim 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711096A (en) * | 1993-04-28 | 1995-01-13 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| JPH09216987A (en) * | 1996-02-09 | 1997-08-19 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin composition |
| JP2000186124A (en) * | 1998-12-22 | 2000-07-04 | Kanegafuchi Chem Ind Co Ltd | Graft copolymer and resin composition |
| JP2003049042A (en) * | 2001-08-09 | 2003-02-21 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition excellent in matting property and molded article using the same |
| JP2004346237A (en) * | 2003-05-23 | 2004-12-09 | Umg Abs Ltd | Thermoplastic resin composition and molded product |
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2005
- 2005-10-31 JP JP2005316558A patent/JP4907949B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711096A (en) * | 1993-04-28 | 1995-01-13 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| JPH09216987A (en) * | 1996-02-09 | 1997-08-19 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin composition |
| JP2000186124A (en) * | 1998-12-22 | 2000-07-04 | Kanegafuchi Chem Ind Co Ltd | Graft copolymer and resin composition |
| JP2003049042A (en) * | 2001-08-09 | 2003-02-21 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition excellent in matting property and molded article using the same |
| JP2004346237A (en) * | 2003-05-23 | 2004-12-09 | Umg Abs Ltd | Thermoplastic resin composition and molded product |
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