JPS63227647A - Thermoplastic polymer composition - Google Patents
Thermoplastic polymer compositionInfo
- Publication number
- JPS63227647A JPS63227647A JP6179987A JP6179987A JPS63227647A JP S63227647 A JPS63227647 A JP S63227647A JP 6179987 A JP6179987 A JP 6179987A JP 6179987 A JP6179987 A JP 6179987A JP S63227647 A JPS63227647 A JP S63227647A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- compound
- parts
- polymer
- graft copolymer
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 229920001169 thermoplastic Polymers 0.000 title 1
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 69
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 31
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000004711 α-olefin Substances 0.000 claims abstract description 6
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims abstract 2
- 229920005989 resin Polymers 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 52
- 239000011342 resin composition Substances 0.000 claims description 23
- 229920005992 thermoplastic resin Polymers 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 16
- 238000000465 moulding Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 11
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- 150000008360 acrylonitriles Chemical class 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229940114926 stearate Drugs 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004898 kneading 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 150000003505 terpenes 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
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- AXTADRUCVAUCRS-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrole-2,5-dione Chemical compound OCCN1C(=O)C=CC1=O AXTADRUCVAUCRS-UHFFFAOYSA-N 0.000 description 1
- PECLZIRCLUPWGS-UHFFFAOYSA-N 1-(3,5-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC(C)=CC(N2C(C=CC2=O)=O)=C1 PECLZIRCLUPWGS-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- XAHCEMQKWSQGLQ-UHFFFAOYSA-N 1-(4-methoxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(OC)=CC=C1N1C(=O)C=CC1=O XAHCEMQKWSQGLQ-UHFFFAOYSA-N 0.000 description 1
- KCFXNGDHQPMIAQ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrrole-2,5-dione Chemical compound C1=CC(C)=CC=C1N1C(=O)C=CC1=O KCFXNGDHQPMIAQ-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
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GTYRFVGHYNRSKT-UHFFFAOYSA-N 3-benzylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(CC=2C=CC=CC=2)=C1 GTYRFVGHYNRSKT-UHFFFAOYSA-N 0.000 description 1
- MXVZVCCKUVRGQC-UHFFFAOYSA-N 3-hexylpyrrole-2,5-dione Chemical compound CCCCCCC1=CC(=O)NC1=O MXVZVCCKUVRGQC-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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 230000001788 irregular Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 238000011282 treatment Methods 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
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
ａ、産業上の利用分野
本発明は、着色性の改良された耐熱性と成形熱安定性に
優れる熱可塑性樹脂組成物に係り、とくにエチレン−α
−オレフィン系ゴム質重合体の存在下に、芳香族ビニル
化合物とシアン化ビニル化合物を共重合して得られるグ
ラフト共重合体樹脂成分と、メタクリル酸エステル化合
物とα・β−不飽和ジカルボン酸のイミド化合物および
これらと共重合可能なビニル化合物からなる単量体混合
物を重合して得られる共重合体樹脂成分とから成る着色
性の改良された耐熱性と成形熱安定性に優れる熱可塑性
樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a thermoplastic resin composition with improved coloring properties, excellent heat resistance and molding heat stability, and particularly relates to a thermoplastic resin composition having improved colorability and excellent molding heat stability.
- A graft copolymer resin component obtained by copolymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an olefin rubbery polymer, a methacrylic acid ester compound, and an α/β-unsaturated dicarboxylic acid. A thermoplastic resin composition with improved colorability and excellent heat resistance and molding heat stability, consisting of a copolymer resin component obtained by polymerizing a monomer mixture consisting of an imide compound and a vinyl compound copolymerizable with these compounds. relating to things.
ｂ、従来の技術
エチレン−α−オレフィン系ゴム質重合体、例えばエチ
レン−プロピレン系ゴムに芳香族ビニル化合物とシアン
化ビニル化合物を主成分とする単量体混合物をグラフト
共重合して得られるグラフト共重合体（ＡＥＳ樹脂）、
または、該グラフト共重合体（ＡＥＳ樹脂）と芳香族ビ
ニル化合物とシアン化ビニル化合物の共重合体（＾Ｓ樹
脂）とから構成される樹脂組成物（以下単にグラフト共
重合体樹脂と略記する）は成形性、成形外観、耐衝撃性
、耐熱性、機械的強度、耐薬品性などに優れ、かつ射出
成形、押出成形に適した樹脂であり、さらに該ゴム質重
合体の主鎖中に二重結合がないため、耐候性に優れてい
るといった大きな特徴事項がある。しかしながら、その
反面として着色性が劣るという問題を有している。b. Prior art Graft obtained by graft copolymerizing an ethylene-α-olefin rubbery polymer, such as ethylene-propylene rubber, with a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound as main components. copolymer (AES resin),
Alternatively, a resin composition composed of the graft copolymer (AES resin) and a copolymer of an aromatic vinyl compound and a vinyl cyanide compound (^S resin) (hereinafter simply abbreviated as graft copolymer resin) is a resin with excellent moldability, molded appearance, impact resistance, heat resistance, mechanical strength, chemical resistance, etc., and is suitable for injection molding and extrusion molding. Because it has no double bonds, it has excellent weather resistance. However, on the other hand, it has the problem of poor coloring properties.
それ故、このグラフト共重合体樹脂の着色性を改良する
方法として、該グラフト共重合体樹脂にメタクリル酸エ
ステル化合物を主成分とする共重合体を配合する発明が
特開昭５７−１１７５５７号明細書および特開昭６１−
３４０４５号明細書等によって開示されている。Therefore, as a method for improving the colorability of this graft copolymer resin, an invention has been proposed in JP-A-57-117557, in which a copolymer containing a methacrylic acid ester compound as a main component is blended into the graft copolymer resin. Book and Unexamined Japanese Patent Publication 1986-
It is disclosed in the specification of No. 34045 and the like.
ところが、このようなメタクリル酸エステル化合物を主
成分とする共重合体は耐熱性が低いといった欠点がある
。そこで耐熱性が高いことが樹脂の重要な選択基準とな
ることが多い今日では、着色性と耐熱性を同時に満足さ
せる必要があり、そのために、前記メタクリル酸エステ
ル化合物を主成分とした共重合体を耐熱性を有するもの
に改良することが必須となってきた。However, such a copolymer containing a methacrylic acid ester compound as a main component has a drawback of low heat resistance. Nowadays, high heat resistance is often an important selection criterion for resins, and it is necessary to satisfy both colorability and heat resistance at the same time. It has become essential to improve heat resistance.
従来グラフト共重合体樹脂の耐熱性を改良する方法とし
ては、スチレンの一部をα−メチルスチレン、ｐ−メチ
ルスチレン等のスチレン誘導体に代えて共重合する方法
が知られている。Conventionally, as a method for improving the heat resistance of graft copolymer resins, a method is known in which a part of styrene is replaced with a styrene derivative such as α-methylstyrene or p-methylstyrene for copolymerization.
しかし、かかるメタクリル酸エステル化合物およびスチ
レン誘導体を含む共重合体は耐熱性を改良するために前
記スチレン誘導体量を増加すると成形熱安定性が悪化し
、また、スチレン誘導体の量を減少させると成形熱安定
性の良好な共重合体とはなるが耐熱性が悪化してしまう
。However, in copolymers containing such methacrylic acid ester compounds and styrene derivatives, when the amount of the styrene derivative is increased to improve heat resistance, the molding heat stability deteriorates, and when the amount of the styrene derivative is decreased, the molding heat stability deteriorates. This results in a copolymer with good stability, but the heat resistance deteriorates.
Ｃ０発明が解決しようとする問題点
本発明者等はこうした点に鑑みて鋭意検討した結果、前
記（ａ）エチレン−α−オレフィン系ゴム質重合体の存
在下に芳香族ビニル化合物とシアン化ビニル化合物を主
成分する単量体混合物を共重合して得られるグラフト共
重合体樹脂成分と（Ｒ）メタクリル酸エステル化合物と
α、β−不飽和ジカルボン酸イミド化合物およびこれら
と共重合可能なビニル化合物からなる単量体混合物を重
合して得られる共重合体樹脂成分とを特定の割合で配合
することによって得られた熱可塑性樹脂組成物は着色性
が良好で、耐熱性と成形熱安定性を同時に改良できたも
のであることを認め本発明に至ったものである。Problems to be Solved by the C0 Invention The present inventors have made extensive studies in view of these points, and have found that (a) an aromatic vinyl compound and a cyanide vinyl compound in the presence of the ethylene-α-olefin rubbery polymer. A graft copolymer resin component obtained by copolymerizing a monomer mixture containing the compound as a main component, (R) a methacrylic acid ester compound, an α,β-unsaturated dicarboxylic acid imide compound, and a vinyl compound copolymerizable with these. A thermoplastic resin composition obtained by blending a copolymer resin component obtained by polymerizing a monomer mixture consisting of At the same time, it was recognized that improvements could be made, leading to the present invention.
ｄ８問題点を解決する手段
すなわち、本発明は（Ａ）エチレン−α−オレフィン系
ゴム質重合体５〜６５重量％の存在下に、芳香族ビニル
化合物とシアン化ビニル化合物の合計量９５〜３５重量
％を共重合して得られるグラフト共重合体樹脂成分９５
〜２０重量％と、（Ｂ）メタクリル酸エステル化合物３
５〜９０重量％と、α、β−不飽和ジカルボン酸のイミ
ド化合物５〜５０重量％およびこれらと共重合可能なビ
ニル化合物５〜６０重量％からなる単量体混合物を重合
して得られる共重合体樹脂成分５〜８０重量％、から成
る熱可塑性樹脂組成物である。d8 Means for solving the problem, that is, the present invention provides that (A) the total amount of the aromatic vinyl compound and the vinyl cyanide compound is 95 to 35% in the presence of 5 to 65% by weight of the ethylene-α-olefin rubbery polymer. Graft copolymer resin component obtained by copolymerizing 95% by weight
~20% by weight and (B) methacrylic acid ester compound 3
A copolymer obtained by polymerizing a monomer mixture consisting of 5 to 90% by weight, 5 to 50% by weight of an imide compound of α,β-unsaturated dicarboxylic acid, and 5 to 60% by weight of a vinyl compound copolymerizable with these. It is a thermoplastic resin composition comprising 5 to 80% by weight of a polymer resin component.
ｅ０発明の詳細な説明
構成成分
（Ａ）グラフト共重合体樹脂成分
本発明において用いられるグラフト共重合体樹脂成分と
しては、エチレン−プロピレン共重合体ゴムまたは、エ
チレン−プロピレン−非共役ジエン共重合体ゴムのよう
な、エチレン−α−オレフィン系ゴム質重合体の存在下
に、芳香族ビニル化合物とシアン化ビニル化合物を主成
分とする単量体混合物を共重合して得られるグラフト共
重合体（ＡＥＳ樹脂）、または、該グラフト共重合体と
芳香族ビニル化合物とシアン化ビニル化合物の共重合体
（ＡＳ樹脂）とから成る樹脂組成物が使用される。e0 Detailed Description of the Invention Component (A) Graft Copolymer Resin Component The graft copolymer resin component used in the present invention includes ethylene-propylene copolymer rubber or ethylene-propylene-nonconjugated diene copolymer. A graft copolymer obtained by copolymerizing a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of an ethylene-α-olefin rubbery polymer such as rubber ( AES resin) or a resin composition comprising the graft copolymer, an aromatic vinyl compound, and a cyanide vinyl compound copolymer (AS resin) is used.
前記ゴム質重合体として使用されるエチレン−α・オレ
フィン系ゴムとしては、エチレン−プロピレン共重合体
または、エチレン−プロピレン非共役ジエン共重合体を
使用することが好ましく、とくにプロピレン含量が、２
０〜５５重量％、ムーニー粘度（ＭＬ＋＋４１００℃）
が１５〜５０、ヨウ素価がＯ〜２０であるものが好まし
い。この範囲のゴム質重合体を使用すれば一段と優れた
物性のものが得られる。As the ethylene-α/olefin rubber used as the rubbery polymer, it is preferable to use an ethylene-propylene copolymer or an ethylene-propylene non-conjugated diene copolymer, especially when the propylene content is 2.
0-55% by weight, Mooney viscosity (ML++4100°C)
is preferably 15 to 50, and the iodine value is preferably O to 20. If a rubbery polymer within this range is used, even better physical properties can be obtained.
また、前記単量体として用いられる芳香族ビニル化合物
としては、スチレン、α−メチルスチレン、ｐ−メチル
スチレンなどであり、シアン化ビニル化合物としては、
アクリロニトリル、メタクリロニトリルなどが使用され
る。さらに、必要によりこれらと共重合可能なビニル化
合物、例えば、アクリル酸メチル、メタクリル酸メチル
等のアルキルアクリレート、アルキルメタアクリレート
などを若干量併用することも差し支えない。Further, aromatic vinyl compounds used as the monomer include styrene, α-methylstyrene, p-methylstyrene, etc., and vinyl cyanide compounds include:
Acrylonitrile, methacrylonitrile, etc. are used. Furthermore, if necessary, a small amount of vinyl compounds copolymerizable with these compounds, such as alkyl acrylates and alkyl methacrylates such as methyl acrylate and methyl methacrylate, may be used in combination.
上記グラフト共重合体樹脂成分の製造方法としては前記
ゴム質重合体の存在下に前記芳香族ビニル化合物とシア
ン化ビニル化合物とをラジカル重合してＡＥＳ樹脂を製
造するか、あるいは、前記方法によって製造したＡＥＳ
樹脂の一部を、別途製造した芳香族ビニル化合物とシア
ン化ビニル化合物をラジカル重合して製造したＡＳ樹脂
に代替して混合することによって得られるＡＥＳ樹脂と
ＡＳ樹脂との混合物をグラフト共重合体樹脂成分として
用いることもできる。The graft copolymer resin component may be produced by radical polymerizing the aromatic vinyl compound and vinyl cyanide compound in the presence of the rubbery polymer, or by the method described above. AES
Graft copolymer is a mixture of AES resin and AS resin obtained by substituting and mixing a part of the resin with AS resin produced by radical polymerization of an aromatic vinyl compound and a vinyl cyanide compound produced separately. It can also be used as a resin component.
前記ＡＥＳ樹脂の一部として代替できるＡＳ樹脂の量と
してはグラフト共重合体樹脂成分（Ａ）中のゴム量と、
最終的な熱可塑性樹脂組成物中のゴム質重合体量から必
然的に、決定される。The amount of AS resin that can be substituted as part of the AES resin is the amount of rubber in the graft copolymer resin component (A);
It is necessarily determined from the amount of rubbery polymer in the final thermoplastic resin composition.
グラフト共重合体樹脂成分中のゴム質重合体の含量は一
般に５〜６５重量％が好ましく、特に１０〜５０重量％
とすることが好ましい。また、最終的な熱可塑性樹脂組
成物中のゴム質重合体の含量では一般に７〜３５重量％
、特に１０〜３０重量％とすることが好ましい。The content of the rubbery polymer in the graft copolymer resin component is generally preferably 5 to 65% by weight, particularly 10 to 50% by weight.
It is preferable that In addition, the content of rubbery polymer in the final thermoplastic resin composition is generally 7 to 35% by weight.
, particularly preferably 10 to 30% by weight.
また、グラフト共重合体樹脂成分（（Ａ）成分からゴム
質重合体を除いたもの）中の芳香族ビニル化合物の含量
としては一般に５０〜８５重量％、好ましくは５５〜８
０重量％とするのが良い。The content of aromatic vinyl compound in the graft copolymer resin component (component (A) excluding the rubbery polymer) is generally 50 to 85% by weight, preferably 55 to 8% by weight.
It is preferable to set it to 0% by weight.
さらに、グラフト共重合体樹脂成分中のビニルシアン化
合物の含量としては一般に１５〜５０重量％、好ましく
は２０〜４５重量％とするのが良い。Furthermore, the content of the vinyl cyanide compound in the graft copolymer resin component is generally 15 to 50% by weight, preferably 20 to 45% by weight.
そしてグラフト共重合体樹脂成分中のマトリックス樹脂
（溶剤可溶分）の極限粘度〔η〕 （メチルエチルケト
ン、３０℃）は、一般に０．２５〜１、特に０．３〜０
．８の範囲のものが好ましい。The intrinsic viscosity [η] (methyl ethyl ketone, 30°C) of the matrix resin (solvent soluble content) in the graft copolymer resin component is generally 0.25 to 1, particularly 0.3 to 0.
．． A range of 8 is preferred.
前記ＡＥＳ樹脂および＾Ｓ樹脂を製造するラジカル重合
方法としては各種の方法、例えば、乳化重合法、塊状重
合法、懸濁重合法、溶液重合法などが適用できる。Various methods such as emulsion polymerization, bulk polymerization, suspension polymerization, and solution polymerization can be used as the radical polymerization method for producing the AES resin and ^S resin.
また前記重合法によって使用される重合開始剤、分子量
調節剤、乳化剤、分散安定剤、溶媒などの重合用薬剤に
ついては一般に知られている重合用薬剤を使用すること
ができる。Furthermore, generally known polymerization agents such as polymerization initiators, molecular weight regulators, emulsifiers, dispersion stabilizers, and solvents used in the polymerization method can be used.
これら重合用薬剤を具体的に示せば、重合開始剤として
は、乳化重合の場合グラフト反応に用いるラジカル重合
開始剤としては、クメンハイドロパーオキシド、ジイソ
プロピルベンゼンハイドロパーオキシド、パラメンタン
ハイドロパーオキシド等で代表される有機ハイドロパー
オキシド類と含糖ピロリン酸処方、スルホキシレート処
方等で代表される還元剤との組み合せによるレドックス
系あるいは過硫酸塩、アゾビスイソブチロニトリル、ベ
ンゾイルペルオキシドなどの過酸化物が使用される。Specifically, these polymerization agents include cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, etc. as radical polymerization initiators used in emulsion polymerization and graft reactions. Redox systems or peroxidation of persulfates, azobisisobutyronitrile, benzoyl peroxide, etc. by combining representative organic hydroperoxides with reducing agents such as sugar-containing pyrophosphate formulations and sulfoxylate formulations. things are used.
また溶液、塊状重合、懸濁重合では、例えばケトンパー
オキサイド、ジアルキルパーオキサイド、ジアシルパー
オキサイド、パーオキシエステル、ハイドロパーオキサ
イドなどの有機過酸化物が使用される。In solution, bulk polymerization, and suspension polymerization, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and hydroperoxide are used.
分子量調節剤としては好ましくはノルマルオクチルメル
カプタン、ノルマルドデシルメルカプタン、ターシャリ
−ドデシルメルカプタン、メルカプトエタノール等のメ
ルカプタン頻タービノーレン、ジペンテン、ｔ−テルピ
ネンおよび少量の他の環状テルペン類よりなるテルペン
類、及びクロロホルム、四塩化炭素等のハロゲン化炭化
水素等を使用することができる。Preferred molecular weight modifiers include mercaptans such as normal octyl mercaptan, normal dodecyl mercaptan, tertiary dodecyl mercaptan, and mercaptoethanol, and terpenes such as terbinolene, dipentene, t-terpinene, and small amounts of other cyclic terpenes, as well as chloroform and terpenes. Halogenated hydrocarbons such as carbon chloride can be used.
乳化剤としては好ましくはロジン酸カリウム、ロジン酸
ナトリウム等のロジン酸塩、オレイン酸カリウム、ラウ
リン酸カリウム、ラウリン酸ナトリウム、ステアリン酸
ナトリウム、ステアリン酸カリウム等の脂肪酸のナトリ
ウム、カリウム塩およびラウリル硫酸ナトリウム等の脂
肪族アルコールの硫酸エステル塩、さらにドデシルベン
ゼンスルホン酸ナトリウム等のアルキルアリルスルホン
酸塩等である。Preferred emulsifiers include rosinate salts such as potassium rosinate and sodium rosinate, sodium and potassium salts of fatty acids such as potassium oleate, potassium laurate, sodium laurate, sodium stearate, and potassium stearate, and sodium lauryl sulfate. sulfate ester salts of aliphatic alcohols, and alkylaryl sulfonates such as sodium dodecylbenzenesulfonate.
分散安定剤としては、第３リン酸カルシウムとドデシル
ベンゼンスルホン酸ナトリウム等のアルキルアリルスル
ホン酸塩との組合せたもの、またはポリビニルアルコー
ル等が用いられる。As the dispersion stabilizer, a combination of tertiary calcium phosphate and an alkylaryl sulfonate such as sodium dodecylbenzenesulfonate, polyvinyl alcohol, or the like is used.
溶剤としては、トルエン、エチルベンゼン、メチルエチ
ルケトンなどがある。Examples of the solvent include toluene, ethylbenzene, and methyl ethyl ketone.
前記重合法における重合条件としては、乳化重合の場合
一般に５〜９０℃、好ましくは５０〜８５℃の温度で、
また他の重合法では一般に５０〜１８０℃、好ましくは
８０〜１５０℃の温度で、一般に１〜１５時間、好まし
くは２〜１０時間程時間台を行なうことにより得られる
。In the case of emulsion polymerization, the polymerization conditions in the above polymerization method are generally at a temperature of 5 to 90°C, preferably 50 to 85°C,
In other polymerization methods, the polymerization is generally carried out at a temperature of 50 to 180 DEG C., preferably 80 to 150 DEG C., for a period of generally 1 to 15 hours, preferably 2 to 10 hours.
（Ｂ）共重合体樹脂成分
前記グラフト共重合体樹脂成分と組合わせて用いられる
共重合体樹脂成分（Ｂ）としては、メタクリル酸エステ
ル化合物３５〜９０重量％、α、β−不飽和ジカルボン
酸のイミド化合物５〜５０重量％およびこれらと共重合
可能な、ビニル化合物５〜６０重量％からなる単量体を
重合して得られるものが使用され、前記単量体の一構成
成分として用いられるメタクリル酸エステル化合物とし
ては、例えばメチルメタクリレート、エチルメタクリレ
ート、プロピルメタクリレート、ヒドロキシメチルメタ
クリレート、ヒドロキシエチルメタクＪ）レート、グリ
シジルメタクリレートなどがある。これらの中でもメチ
ルメタクリレートを使用することが好ましく、共重合体
樹脂成分（Ｂ）中に３５〜９０重量％、好ましくは、４
０〜８５重量％の範囲とする必要がある。この範囲より
少い場合は着色性は改良できず、また、この範囲より多
い場合は耐衝撃性が悪くなる。(B) Copolymer resin component The copolymer resin component (B) used in combination with the above-mentioned graft copolymer resin component includes 35 to 90% by weight of a methacrylic acid ester compound, α,β-unsaturated dicarboxylic acid A monomer consisting of 5 to 50% by weight of an imide compound and 5 to 60% by weight of a vinyl compound copolymerizable with these is used, and is used as a constituent component of the monomer. Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, propyl methacrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, and glycidyl methacrylate. Among these, it is preferable to use methyl methacrylate, and the copolymer resin component (B) contains 35 to 90% by weight, preferably 4
It is necessary to set it as the range of 0-85 weight%. If the amount is less than this range, the colorability cannot be improved, and if it is more than this range, the impact resistance will deteriorate.
前記共重合体樹脂成分の一構成成分として使用されるα
、β−不飽和ジカルボン酸のイミド化合物としては次式
％式％
（式中Ｒ１、Ｒ２、Ｒ３は水素、アルキル基、アルケニ
ル基、シクロアルキル基、フェニル基、フェニレン基、
アルキレン基などを示す。）で表わし得る。その具体的
な化合物の例としては、マレイミド、Ｎ−メチルマレイ
ミド、Ｎ−ブチルマレイミド、Ｎ−シクロへキシルマレ
イミド、Ｎ−フェニルマレイミド、Ｎ−（ｐ−メチルフ
ェニル）マレイミド、Ｎ−（ｐ−ヒドロキシフェニル）
マレイミド、Ｎ−（３，５−ジメチルフェニル）マレイ
ミド、Ｎ−（ｐ−メトキシフェニル）マレイミド、Ｎ−
ベンジルマレイミド、Ｎ−（１−１−フチル）−マレイ
ミド、Ｎ−ヒドロキシエチルマレイミドなどがある。こ
れらは１種または２種以上で使用される。これら化合物
の中で好ましい化合物としては、Ｎ−フェニルマレイミ
ド、Ｎ−シクロへキシルマレイミドであり、特に好まし
くは成形外観上、Ｎ−シクロへキシルマレイミドである
。α used as a component of the copolymer resin component
, as an imide compound of β-unsaturated dicarboxylic acid, the following formula % formula % (wherein R1, R2, R3 are hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, a phenylene group,
Indicates an alkylene group, etc. ). Specific examples of the compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(p-methylphenyl)maleimide, N-(p-hydroxy phenyl)
Maleimide, N-(3,5-dimethylphenyl)maleimide, N-(p-methoxyphenyl)maleimide, N-
Examples include benzylmaleimide, N-(1-1-phthyl)-maleimide, and N-hydroxyethylmaleimide. These may be used alone or in combination of two or more. Preferred among these compounds are N-phenylmaleimide and N-cyclohexylmaleimide, with N-cyclohexylmaleimide being particularly preferred in terms of molded appearance.
該α、β−不飽和ジカルボン酸のイミド化合物は共重合
体樹脂成分中に５〜５０重量％、好ましくは５〜４０重
量％の範囲内で含有させることが必要であり、この範囲
より少ないと、耐熱性の改良はできず、また多いと耐衝
撃性が悪くなる。The imide compound of α,β-unsaturated dicarboxylic acid needs to be contained in the copolymer resin component in an amount of 5 to 50% by weight, preferably 5 to 40% by weight, and if it is less than this range, , heat resistance cannot be improved, and if too much, impact resistance deteriorates.
また、これら単量体と共重合可能なビニル化合物として
は、芳香族ビニル化合物、シアン化ビニル化合物、アク
リル酸エステル化合物等がある。Furthermore, examples of vinyl compounds that can be copolymerized with these monomers include aromatic vinyl compounds, vinyl cyanide compounds, and acrylic acid ester compounds.
前記共重合可能なビニル化合物中、芳香族ビニル化合物
の含有量は２０〜８０重量％が好ましく、さらに好まし
くは３０〜７０重量％であり、シアン化ビニル化合物の
含有量は好ましくは２０〜８０重量％、さらに好ましく
は３０〜７０重量％である。芳香族ビニル化合物の存在
により成形加工性、色調が向上し、シアン化ビニル化合
物の存在により衝撃強度が向上する。In the copolymerizable vinyl compound, the content of the aromatic vinyl compound is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and the content of the vinyl cyanide compound is preferably 20 to 80% by weight. %, more preferably 30 to 70% by weight. The presence of aromatic vinyl compounds improves moldability and color tone, and the presence of vinyl cyanide compounds improves impact strength.
前記芳香族ビニル化合物としては、スチレンが好ましく
、または、前記シアン化ビニル化合物としてはアクリロ
ニトリルが好ましい。これらビニル化合物は共重合体樹
脂成分中に５〜６０重量％、好ましくは１０〜５５重量
％の範囲内とする必要があり、この範囲より少いと耐衝
撃性が低く、多いと着色性と耐熱性を同時に改良するこ
とは困難である。The aromatic vinyl compound is preferably styrene, and the vinyl cyanide compound is preferably acrylonitrile. These vinyl compounds need to be contained in the copolymer resin component in an amount of 5 to 60% by weight, preferably 10 to 55% by weight.If it is less than this range, the impact resistance will be low, and if it is more than this, the coloring property and heat resistance will be low. It is difficult to improve both properties at the same time.
上記共重合体樹脂成分の製造方法としては、前記グラフ
ト共重合体樹脂成分の製造方法と同様な重合法、すなわ
ち乳化重合法、懸濁重合法、塊状重合法などが適用され
、これらいずれの方法を用いても良い。As the method for producing the copolymer resin component, the same polymerization methods as the method for producing the graft copolymer resin component, such as emulsion polymerization, suspension polymerization, and bulk polymerization, are applicable, and any of these methods may be used. You may also use
また、前記重合法によって使用される重合開始剤、分子
量調節剤、乳化剤、分散安定剤、溶媒などの重合用薬剤
については一般に知られている重合用薬剤を使用するこ
とができる。Furthermore, generally known polymerization agents can be used as polymerization agents such as polymerization initiators, molecular weight regulators, emulsifiers, dispersion stabilizers, and solvents used in the polymerization method.
具体的に示せば、重合開始剤としては
熱可塑性樹旨組 物の製造
本発明の熱可塑性樹脂組成物を製造するためには前記グ
ラフト共重合体樹脂成分（八）と共重合体樹脂成分（Ｂ
）の配合割合を重量比で９５：５〜２０ ： ８０、好
ましくは９０ ： １０〜３０ ： ７０、さらに好ま
しくは８５ Ｆ １５〜４０ ： ６０とする必要があ
る。したがって、この範囲を越えて、グラフト共重合体
樹脂成分が多い場合には、本発明の特徴の１つである着
色性が殆ど改良されない。一方、この範囲よりもグラフ
ト共重合体樹脂成分が少ないと耐衝撃性が低くなり好ま
しくない。Specifically, as a polymerization initiator, the above-mentioned graft copolymer resin component (8) and copolymer resin component (8) are used to produce the thermoplastic resin composition of the present invention. B
) should be in a weight ratio of 95:5 to 20:80, preferably 90:10 to 30:70, and more preferably 85F15 to 40:60. Therefore, if the amount of the graft copolymer resin component exceeds this range, the colorability, which is one of the characteristics of the present invention, will hardly be improved. On the other hand, if the graft copolymer resin component is less than this range, the impact resistance will be low, which is not preferable.
グラフト共重合体樹脂成分と共重合体樹脂成分との混合
物は、重合終了後の、反応混合物である溶液−溶液また
は、溶液−ラテックス等の状態のままで、両者を混合し
た後、樹脂組成物の回収操作を行っても良いし、あるい
は、樹脂回収操作後の粉体−粉体、粉体−ペレット１、
ペレット−ペレット等の形態で両者を混合して本発明の
熱可塑性樹脂組成物を製造しても良い。The mixture of the graft copolymer resin component and the copolymer resin component is mixed in a state such as a solution-solution or solution-latex, which is a reaction mixture after completion of polymerization, and then mixed into a resin composition. Alternatively, after the resin recovery operation, powder-powder, powder-pellet 1,
The thermoplastic resin composition of the present invention may be manufactured by mixing both in the form of pellets or the like.
前記グラフト共重合体成分（Ａ）と共重合体樹脂成分（
Ｂ）との混錬り方法としては、各種押出機、バンバリー
ミキサ−、ニーダ−、ロールなどが使用される。好まし
い混錬方法としては押出機を用いる方法である。The graft copolymer component (A) and the copolymer resin component (
For kneading with B), various extruders, Banbury mixers, kneaders, rolls, etc. are used. A preferred kneading method is a method using an extruder.
混合温度は混合するグラフト共重合体樹脂成分（Ａ）と
共重合体樹脂成分（Ｂ）の融点以上の温度が必要であり
、一般に１５０〜３００℃、特に２００〜２８０°Ｃの
温度であることが好ましい。The mixing temperature must be higher than the melting point of the graft copolymer resin component (A) and copolymer resin component (B) to be mixed, and should generally be 150 to 300°C, particularly 200 to 280°C. is preferred.
本発明の熱可塑性樹脂組成物の使用に際して、ガラス繊
維、炭素繊維、金属繊維、ガラスピーズ、アラベスト、
ウォラスナイト、炭酸カルシウム、タルク、硫酸バリウ
ムなどの充填剤を、単独または併用して用いることがで
きる。これらの充填剤のうちガラス繊維、炭素繊維の形
状としては、６〜６０μｍの繊維径と３０μｍ以上の繊
維長を有するものが好ましい。When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass peas, arabest,
Fillers such as wallasnite, calcium carbonate, talc, and barium sulfate can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.
これらの充填剤は、熱可塑性樹脂組成物１００重量部に
対して５〜１５重量部含有していることが好ましい。It is preferable that these fillers are contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the thermoplastic resin composition.
また公知の難燃剤、酸化防止剤、可塑剤、着色剤、滑剤
などの添加物を添加して用いることもできる。Additionally, known additives such as flame retardants, antioxidants, plasticizers, colorants, and lubricants may be added.
好ましい難燃剤および酸化防止剤は燐系化合物である。Preferred flame retardants and antioxidants are phosphorus compounds.
さらに要求される性能に応じて他の重合体、例えば、ポ
リエチレン、ポリプロピレン、ＢＲ，、ＮＢＲ。Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, BR, NBR.
ＳＢＲ、５−Ｂ−Ｓブロック共重合体、水添５−Ｂ−３
、ポリスチレン、ＨＩＰＳ、 ＡＢＳ樹脂、ポリスル
ホン、ポリエーテルスルホン、ＮＢＳ 、メタクリル酸
メチル−スチレン共重合体、５４−Ｓブロソ共重合体ポ
リイミド、ｐｐｓ 、ポリエーテルエーテルケトン、フ
ッ化ビニリデン重合体などを適宜ブレンドすることもで
きる。SBR, 5-B-S block copolymer, hydrogenated 5-B-3
, polystyrene, HIPS, ABS resin, polysulfone, polyethersulfone, NBS, methyl methacrylate-styrene copolymer, 54-S broso copolymer polyimide, pps, polyetheretherketone, vinylidene fluoride polymer, etc., as appropriate. You can also.
本発明の熱可塑性樹脂組成物は、一般に射出成形、シー
ト押出、真空成形、異形成形、発泡成形などによって各
種成形品に成形される。The thermoplastic resin composition of the present invention is generally molded into various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like.
上記成形法によって得られた各種成形品は、その優れた
性質を利用して、自動車の外装、内装部材および電気・
電子機器関連の各種部品やハウジングなどに使用するこ
とができる。The various molded products obtained by the above molding method take advantage of their excellent properties to be used in automobile exteriors, interior parts, electrical equipment, etc.
It can be used for various parts and housings related to electronic devices.
ｆ、実施例
以下、実施例により本発明をさらに詳細に説明するが、
これらはいずれも例示的なものであって本発明の内容を
限定するものではない。f. Examples The present invention will be explained in more detail by Examples below.
All of these are illustrative and do not limit the content of the present invention.
以下の各側において、部および％はそれぞれ重量部およ
び重量％を示す。In each side below, parts and percentages refer to parts and percentages by weight, respectively.
なお、実施例に使用したグラフト共重合体樹脂成分およ
び共重合体樹脂成分は以下の方法により製造した。Incidentally, the graft copolymer resin component and the copolymer resin component used in the examples were manufactured by the following method.
グラフト計重ム １８ （八）の１゛１〈へＥＳ樹脂
〉
リボン型攪拌翼を備えた内容積５０Ａのステンレス製オ
ートクレーブに予め均一の溶液状態にしたヨウ素価１５
、ムーニー粘度４２、ジエン成分として５−エチリデン
−２−ノルボルネンを含むＥｒ’ＤＭ （日本合成ゴム
■製 ＪＳＲＥＰ２２） ３５重量部、スチレン４５．
５重量部、トルエン１８０重量部、ターシャリ−ドデシ
ルメルカプタン０．０５重量部を仕込み攪拌しながら昇
温し、５０℃にてアクリロニトリル１９．５重量部、ベ
ンゾイルパーオキサイド０．５重量部、ジクミルパーオ
キサイド０．１重量部を添加し、さらに昇温し、８０℃
に達した後は、８０℃一定に制御しながら攪拌回転数１
１００ｒｐにて、重合反応を行なわせる。反応開始後６
時間目から１時間を要して１２０℃まで昇温し、さらに
２時間反応を行なって終了した。重合率は９７％であっ
た。Graft weighing device 18 (8)-1゛1〈ES resin〉 Iodine value 15 was made into a uniform solution state in advance in a stainless steel autoclave with an internal volume of 50 A equipped with a ribbon-type stirring blade.
, Mooney viscosity 42, Er'DM containing 5-ethylidene-2-norbornene as a diene component (JSREP22 manufactured by Japan Synthetic Rubber ■) 35 parts by weight, styrene 45.
5 parts by weight of acrylonitrile, 180 parts by weight of toluene, and 0.05 parts by weight of tertiary dodecyl mercaptan were charged, heated while stirring, and heated to 50°C. Add 0.1 part by weight of oxide and further raise the temperature to 80℃
After reaching the temperature, increase the stirring speed to 1 while controlling the temperature at a constant 80℃.
The polymerization reaction is carried out at 100 rpm. 6 after the start of the reaction
The temperature was raised to 120° C. over a period of 1 hour, and the reaction was continued for an additional 2 hours to complete the reaction. The polymerization rate was 97%.
１００℃まで冷却した後、２，２′ −メチレン−ビス
（４−メチル−６−ｔ−ブチルフェノール）０．２重量
部を添加した後、反応混合物をオートクレーブより抜き
出し、水蒸気蒸留により大部分の未反応単量体と溶媒を
留去し、細かく粉砕した後、４０璽■φベント押出機（
２２０°Ｃ〉７００ ｍ１ｇ真空）にて実質的に揮発分
を留去するとともに重合体をペレットとして回収した。After cooling to 100°C and adding 0.2 parts by weight of 2,2'-methylene-bis(4-methyl-6-t-butylphenol), the reaction mixture was taken out of the autoclave and most of the unused material was removed by steam distillation. After distilling off the reaction monomer and solvent and finely pulverizing, a 40 mm diameter vented extruder (
The volatiles were substantially distilled off at 220° C. (vacuum 700 ml) and the polymer was recovered as pellets.
〈へＳ樹脂〉
共重合体樹脂 分（Ｂ）の製造
く重合体陽１〉
リボン型攪拌翼を備えた内容積５０１のステンレス製オ
ートクレーブに予め均一溶液したメチルメタクリレート
５５重量部１、Ｎ−シクロへキシルマレイミド２０重量
部、スチレン１８重量部、アクリロニトリル７重量部、
トルエン３０重量部、ターシャリ−ドデシルメルカプタ
ン０．３重量部を仕込み、攪拌しながら昇温し、５０℃
にてジクミルパーオキサイド０．１重量部を添加した。<S resin> Copolymer resin Production of component (B) Polymer positive 1> 55 parts by weight of methyl methacrylate 1, N-cyclo, which was uniformly dissolved in advance in a stainless steel autoclave with an internal volume of 50 cm equipped with a ribbon-type stirring blade 20 parts by weight of hexylmaleimide, 18 parts by weight of styrene, 7 parts by weight of acrylonitrile,
30 parts by weight of toluene and 0.3 parts by weight of tertiary dodecyl mercaptan were added, and the temperature was raised to 50°C while stirring.
0.1 part by weight of dicumyl peroxide was added.
さらに昇温しで１２０℃に達した後は、１２０℃一定に
制御しながら攪拌回転数１１００ｒｐにて、５時間反応
を行った。重合収率は９０％であった。以後の処理は前
記ＡＥＳ樹脂の製造と同様の方法で行ない、重合体を得
た。After the temperature was further increased to 120°C, the reaction was carried out for 5 hours at a stirring rotation speed of 1100 rpm while controlling the temperature to be constant at 120°C. The polymerization yield was 90%. The subsequent treatments were performed in the same manner as in the production of the AES resin to obtain a polymer.
く重合体階２〉
攪拌機付ステンレス反応器内部を窒素で元分置換した後
、窒素気流中でイオン交換水２００重量部、ドデシルベ
ンゼンスルホン酸ナトリウム２重量部を添加して、攪拌
しながらメチルメタクリレート７５重量部、Ｎ−シクロ
ヘキシルマレイミド１０重量部、ステンレス１０重量部
、アクリロニトリル５重量部、ターシャリ−ドデシルメ
ルカプタン０．２重量部、ホルムアルデヒドスルホン酸
ナトリウム三水塩０．４重量部、エチレンジアミンテト
ラ酢酸ナトリウム０．２重量部、硫酸第１鉄０．００５
重量部およびクメンヒドロパーオキサイド０．３重量部
を加える。攪拌を続けながら、７０℃で４時間重合反応
を行なった。この時の重合収率は９６％であった。塩化
カルシウム水溶液を用いて凝固した後、脱水乾燥を行な
い重合体を得た。Polymer stage 2> After replacing the inside of a stainless steel reactor with a stirrer with nitrogen, 200 parts by weight of ion-exchanged water and 2 parts by weight of sodium dodecylbenzenesulfonate were added in a nitrogen stream, and methyl methacrylate was added with stirring. 75 parts by weight, 10 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of stainless steel, 5 parts by weight of acrylonitrile, 0.2 parts by weight of tertiary dodecyl mercaptan, 0.4 parts by weight of sodium formaldehyde sulfonate trihydrate, 0 parts by weight of sodium ethylenediaminetetraacetate .2 parts by weight, ferrous sulfate 0.005
parts by weight and 0.3 parts by weight of cumene hydroperoxide. The polymerization reaction was carried out at 70° C. for 4 hours while stirring was continued. The polymerization yield at this time was 96%. After coagulating using an aqueous calcium chloride solution, dehydration and drying were performed to obtain a polymer.
〈重合体Ｎａ３．）
メチルメタクリレート４５重量部とＮ−シクロヘキシル
マレイミド１０重量部、スチレン３０重量部、アクリソ
ニトリル１５重量部とした以外は、上記〈重合体隘２〉
と同様の方法で重合体を得た。<Polymer Na3. ) 45 parts by weight of methyl methacrylate, 10 parts by weight of N-cyclohexylmaleimide, 30 parts by weight of styrene, and 15 parts by weight of acrisonitrile, except for the above <Polymer number 2>
A polymer was obtained in the same manner as above.
く重合体階４〉
メチルメタクリレート５０重量部とＮ−シクロヘキシル
マレイミド３５重量部、スチレン１０重量部、アクリロ
ニトリル５部、とした以外は上記く重合体隘２〉と同様
の方法で重合体を得た。Polymer Level 4 A polymer was obtained in the same manner as in Polymer Level 2 above, except that 50 parts by weight of methyl methacrylate, 35 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of styrene, and 5 parts of acrylonitrile were used. .
〈重合体隘５〉
メチルメタクリレート５５重量部とＮ−フェニルマレイ
ミド２０重量部、スチレン１８重量部、アクリロニトリ
ル７重量部、トルエン３０重量部、ターシャリ−ドデシ
ルメルカプタン０．２重量部を仕込み昇温し、１４０℃
に達した後１４０℃一定に制御した以外は上記〈重合体
Ｉｌ＆ｌｌ＞と同様の方法で重合体を得た。<Polymer size 5> 55 parts by weight of methyl methacrylate, 20 parts by weight of N-phenylmaleimide, 18 parts by weight of styrene, 7 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.2 parts by weight of tertiary dodecyl mercaptan were charged, and the temperature was raised. 140℃
A polymer was obtained in the same manner as in the above <Polymer Il&ll> except that the temperature was controlled to be constant at 140°C after reaching the temperature.
く重合体隘６〉
メチルメタクリレート５５重量部、Ｎ−シクロへキシル
マレイミド３重量部、アクリロニトリル１３重量部、ス
チレン２９重量部とした以外は、上記〈重合体隘１〉と
同様の方法で重合体を得た。Polymer number 6> Polymer was prepared in the same manner as in the above <Polymer number 1> except that 55 parts by weight of methyl methacrylate, 3 parts by weight of N-cyclohexylmaleimide, 13 parts by weight of acrylonitrile, and 29 parts by weight of styrene were used. I got it.
く重合体隘７〉
メチルメタクリレート２５重量部、Ｎ−シクロへキシル
マレイミド２０重量部、スチレン４０重量部、アクロニ
トリル１５重量部、とした以外は上記く重合体隘２〉と
同様の方法で重合体を得た。Polymer Number 7> Polymer was prepared in the same manner as in Polymer Number 2 above, except that 25 parts by weight of methyl methacrylate, 20 parts by weight of N-cyclohexylmaleimide, 40 parts by weight of styrene, and 15 parts by weight of acronitrile were used. Obtained union.
く重合体１１ｋＬ８）
メチルメタクリレート８０重量部、Ｎ−シクロへキシル
マレイミド２０重量部とした以外は、上記〈重合体Ｎａ
２＞ と同様の方法で重合体を得た。Polymer 11kL8) The above <Polymer Na
A polymer was obtained in the same manner as in 2>.
く重合体９〉
メチルメタクリレート２５重量部、Ｎ−シクロへキシル
マレイミド６０重量部、スチレン１０重量部、アクリロ
ニトリル５重量部とした以外は、上記く重合体１１１１
１２〉 と同様の方法で重合体を得た。Polymer 9> Polymer 1111 as above except that 25 parts by weight of methyl methacrylate, 60 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of styrene, and 5 parts by weight of acrylonitrile were used.
A polymer was obtained in the same manner as in 12>.
く重合体１０〉
メチルメタクリレート５５重量部、α−メチルスチレン
３０重量部、スチレン１０重量部、アクリロニトリル５
重量部とした以外は、上記く重合体２）と同様の方法で
重合体を得た。Polymer 10> 55 parts by weight of methyl methacrylate, 30 parts by weight of α-methylstyrene, 10 parts by weight of styrene, 5 parts by weight of acrylonitrile
A polymer was obtained in the same manner as in Polymer 2) above, except that the parts by weight were changed.
く重合体１１＞
メチルメタクリレート５５重量部、スチレン２５重量部
、アクリロニトリル２０重量部とした以外は、上記〈重
合体トｈ２〉と同様の方法で重合体を得た。Polymer 11> A polymer was obtained in the same manner as in <Polymer h2> above, except that 55 parts by weight of methyl methacrylate, 25 parts by weight of styrene, and 20 parts by weight of acrylonitrile were used.
実施例
上記の方法で得たへＥＳ樹脂へＳ樹脂ペレットと共重合
体（Ｂ）のベレットを表−１に示す組成により配合して
４９ｍｍφ押出機（２５０℃）にて、溶融混錬して表−
１の如き熱可塑性樹脂組成物を得た。Example S resin pellets and copolymer (B) pellets were blended into the ES resin obtained by the above method according to the composition shown in Table 1, and melted and kneaded in a 49 mmφ extruder (250°C). Table -
A thermoplastic resin composition such as No. 1 was obtained.
該熱可塑性樹脂組成物を用いて９０ＴＯＮ射出成形機（
２５０°Ｃ）にて試験片を成形しその物性を測定した。A 90TON injection molding machine (
A test piece was molded at 250°C) and its physical properties were measured.
また得られた熱可塑性樹脂組成物を下記配合量にて配合
して、押出機を通して着色ベレットを得た。それをさら
に成形して色調評価プレートを得た。また、黒色配合物
の着色性については、色差計にて、明度を測定し、マン
セル色数値（値が大きい合着色性は悪い）で表わした。Further, the obtained thermoplastic resin composition was blended in the following amount and passed through an extruder to obtain a colored pellet. It was further molded to obtain a color tone evaluation plate. Regarding the colorability of the black formulation, the brightness was measured using a color difference meter and expressed as a Munsell color value (the larger the value, the worse the colorability).
他の着色配合については、彩度を目視で判定した。For other coloring formulations, saturation was determined visually.
黒色配合 樹脂 １００カーボンブラン
ク ０．５
ステアリン酸Ｃａ Ｏ，３
赤色配合 樹脂 １００ベンガラ
１．０
ステアリン酸Ｃａ Ｏ，５
青色配合 樹脂 １００群青
１．０
ステアリン酸Ｃａ Ｏ，５
また、耐候性については、サンシャインウエザオメータ
ーで１０００時間照射した後でアイゾツト衝撃値を測定
した。結果を表−１に示す。Black blended resin 100 carbon blank 0.5 Ca stearate O,3 Red blended resin 100 red iron
1.0 Ca stearate O,5 Blue blend resin 100 Ultramarine
1.0 Ca O,5 stearate Regarding weather resistance, Izod impact value was measured after 1000 hours of irradiation with a sunshine weatherometer. The results are shown in Table-1.
表−１の物性は次の方法によって測定された。The physical properties shown in Table 1 were measured by the following method.
ＭＦＩＩ ： 八ＳＴＭ Ｄ−１２３８２４０
’Ｃ１０ｋｇ／ｃＩＡアイゾツト衝撃強度： ＡＳＴＭ
Ｄ−２５６−５６（断面１／４ Ｘ １／２インチ、
ノツチ付）耐候性：サンシャインウェザオメーター条件
ブラックパネル温度 ６３°Ｃ
降雨サイクル １８分７１２０分アイゾツト衝
撃強度−ＡＳＴＭ Ｄ−２５６−５６（断面１／８ Ｘ
ｉ／２インチ、ノツチなし）■樹脂：スチレンーアクリ
ロニトリル共重合体三井東圧社製 ＬＩＴＡＣ−Ａ Ｉ
２０ＰＣＡＢＳ樹脂二日本合成ゴム■製 ＪＳＲＡＢＳ
１０成形熱安定、性：３．５ｏｚ射出成形機２６０℃
×１５分滞留後の成形品表
面のシルバーストリークの有無
実施例１〜６の配合による熱可塑性樹脂組成物では、比
較例９に示すＡＢＳ樹脂単独のものと同程度の黒さおよ
び彩度のものが得られている。MFII: 8 STM D-1238240
'C10kg/cIA Izot impact strength: ASTM
D-256-56 (cross section 1/4 x 1/2 inch,
(with notch) Weather resistance: Sunshine Weatherometer conditions Black panel temperature 63°C Rainfall cycle 18 minutes 7120 minutes Izot impact strength - ASTM D-256-56 (cross section 1/8
i/2 inch, no notch) ■Resin: Styrene-acrylonitrile copolymer manufactured by Mitsui Toatsu Co., Ltd. LITAC-A I
20PCABS resin made by Nippon Synthetic Rubber JSRABS
10 Molding heat stability, property: 3.5oz injection molding machine 260℃
× Presence of silver streaks on the surface of the molded product after residence for 15 minutes The thermoplastic resin compositions with the formulations of Examples 1 to 6 had the same blackness and chroma as the ABS resin alone shown in Comparative Example 9. is obtained.
比較例１は、α、β不飽和ジカルボン酸のイミド化合物
が少ないため耐熱性を改良することができない。また、
比較例−２は、メチルメタアクリレートの量が少ないた
め着色性が悪く、比較例−３は、メタクリル酸エステル
化合物とα、β−不飽和ジカルボン酸のイミド化合物以
外のビニルモノマーを使用しないため衝撃強度が低い。In Comparative Example 1, the heat resistance cannot be improved because the imide compound of α,β unsaturated dicarboxylic acid is small. Also,
Comparative Example 2 had poor coloring properties due to the small amount of methyl methacrylate, and Comparative Example 3 had no impact because it did not use vinyl monomers other than the methacrylic acid ester compound and the imide compound of α,β-unsaturated dicarboxylic acid. The strength is low.
さらに、比較例−４は、α、β−不飽和ジカルボン酸の
イミド化合物量が多く、メタクリル酸エステル化合物が
少ないため、衝撃強度と着色性が悪い。また、比較例５
．６の熱可塑性樹脂組成物ではα、β−不飽和ジカルボ
ン酸のイミド化合物を使用しなければ着色性は良好であ
るが、耐熱性と成形熱安定性が低い。Furthermore, Comparative Example 4 has a large amount of an imide compound of α,β-unsaturated dicarboxylic acid and a small amount of a methacrylic acid ester compound, and therefore has poor impact strength and colorability. Also, Comparative Example 5
．． The thermoplastic resin composition of No. 6 has good colorability unless an imide compound of an α,β-unsaturated dicarboxylic acid is used, but its heat resistance and molding thermal stability are low.
ｇ０発明の効果
本発明の熱可塑性樹脂組成物は前記実施例などにて明ら
かにした如く、着色性と耐熱性と成形熱安定性のバラン
スに優れた熱可塑性樹脂組成物であり、このように優れ
た材質である本発明の熱可塑性樹脂組成物は射出成形、
押出成形などによって各種成形品として成形され、自動
車の外装、内装部材および電気・電子機器関連の各種部
品やハウジングなどに使用することができ、工業的に極
めて有用なものである。g0 Effects of the Invention The thermoplastic resin composition of the present invention is a thermoplastic resin composition with an excellent balance of colorability, heat resistance, and molding heat stability, as clarified in the above examples. The thermoplastic resin composition of the present invention, which is an excellent material, can be used for injection molding,
It is formed into various molded products by extrusion molding and the like, and can be used for the exterior and interior parts of automobiles, and various parts and housings related to electrical and electronic devices, making it extremely useful industrially.
Claims (1)
５重量％の存在下に、芳香族ビニル化合物とシアン化ビ
ニル化合物の合計量９５〜３５重量％を共重合して得ら
れるグラフト共重合体樹脂成分９５〜２０重量％と、 （Ｂ）メタクリル酸エステル化合物３０〜９０重量％、
α，β−不飽和ジカルボン酸のイミド化合物５〜５０重
量％およびこれらと共重合可能なビニル化合物５〜６０
重量％からなる単量体混合物を重合して得られる共重合
体樹脂成分（Ｂ）５〜８０重量％、から成る熱可塑性樹
脂組成物。[Claims] (A) Ethylene-α-olefin rubbery polymers 5 to 6
95 to 20% by weight of a graft copolymer resin component obtained by copolymerizing a total amount of 95 to 35% by weight of an aromatic vinyl compound and a vinyl cyanide compound in the presence of 5% by weight, and (B) methacrylic acid. ester compound 30-90% by weight,
5 to 50% by weight of an imide compound of α,β-unsaturated dicarboxylic acid and 5 to 60% of a vinyl compound copolymerizable with these
A thermoplastic resin composition comprising 5 to 80% by weight of a copolymer resin component (B) obtained by polymerizing a monomer mixture comprising 5% to 80% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62061799A JPH0813920B2 (en) | 1987-03-17 | 1987-03-17 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62061799A JPH0813920B2 (en) | 1987-03-17 | 1987-03-17 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63227647A true JPS63227647A (en) | 1988-09-21 |
| JPH0813920B2 JPH0813920B2 (en) | 1996-02-14 |
Family
ID=13181508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62061799A Expired - Lifetime JPH0813920B2 (en) | 1987-03-17 | 1987-03-17 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813920B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05320473A (en) * | 1992-05-18 | 1993-12-03 | Toray Ind Inc | Thermoplastic resin composition |
| JP2006045465A (en) * | 2004-08-09 | 2006-02-16 | Umg Abs Ltd | Thermoplastic resin composition and molded article |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191239A (en) * | 1983-09-12 | 1986-05-09 | アトランテイツク・リツチフイ−ルド・カンパニ− | Polymer alloy |
| JPS61101547A (en) * | 1984-10-25 | 1986-05-20 | Sumitomo Naugatuck Co Ltd | Resin composition |
| JPS61174248A (en) * | 1985-01-28 | 1986-08-05 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| JPS61204255A (en) * | 1985-03-06 | 1986-09-10 | アトランテイツク・リツチフイールド・カンパニー | Polymer composition, formed composition and manufacture |
-
1987
- 1987-03-17 JP JP62061799A patent/JPH0813920B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191239A (en) * | 1983-09-12 | 1986-05-09 | アトランテイツク・リツチフイ−ルド・カンパニ− | Polymer alloy |
| JPS61101547A (en) * | 1984-10-25 | 1986-05-20 | Sumitomo Naugatuck Co Ltd | Resin composition |
| JPS61174248A (en) * | 1985-01-28 | 1986-08-05 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| JPS61204255A (en) * | 1985-03-06 | 1986-09-10 | アトランテイツク・リツチフイールド・カンパニー | Polymer composition, formed composition and manufacture |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05320473A (en) * | 1992-05-18 | 1993-12-03 | Toray Ind Inc | Thermoplastic resin composition |
| JP2006045465A (en) * | 2004-08-09 | 2006-02-16 | Umg Abs Ltd | Thermoplastic resin composition and molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0813920B2 (en) | 1996-02-14 |
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