JPH02258816A - Rubber-modified thermoplastic resin and composition thereof - Google Patents
Rubber-modified thermoplastic resin and composition thereofInfo
- Publication number
- JPH02258816A JPH02258816A JP8078989A JP8078989A JPH02258816A JP H02258816 A JPH02258816 A JP H02258816A JP 8078989 A JP8078989 A JP 8078989A JP 8078989 A JP8078989 A JP 8078989A JP H02258816 A JPH02258816 A JP H02258816A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- rubber
- parts
- compound
- 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 24
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 54
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000005060 rubber Substances 0.000 claims abstract description 21
- 150000001993 dienes Chemical class 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 229920001400 block copolymer Polymers 0.000 claims abstract description 14
- 239000011342 resin composition Substances 0.000 claims abstract description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 10
- 150000008360 acrylonitriles Chemical class 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 40
- 229920001577 copolymer Polymers 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 7
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 15
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229920000578 graft copolymer Polymers 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001979 organolithium group Chemical group 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-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
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- FAVWXKQADKRESO-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-1-ene Chemical compound CC=C.CC(=C)C(O)=O FAVWXKQADKRESO-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- NMXSDUSRXRNRLK-UHFFFAOYSA-N 3-methyl-4-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C)=C1C1=CC=CC=C1 NMXSDUSRXRNRLK-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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229920005601 base polymer Polymers 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- FQEKAFQSVPLXON-UHFFFAOYSA-N butyl(trichloro)silane Chemical compound CCCC[Si](Cl)(Cl)Cl FQEKAFQSVPLXON-UHFFFAOYSA-N 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical group N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LGDNMDSHQLWPAK-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound COC(=O)C(C)=C.N#CC=CC=CC1=CC=CC=C1 LGDNMDSHQLWPAK-UHFFFAOYSA-N 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QVKOLZOAOSNSHQ-UHFFFAOYSA-N prop-1-ene;prop-2-enoic acid Chemical compound CC=C.OC(=O)C=C QVKOLZOAOSNSHQ-UHFFFAOYSA-N 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- WDVUXWDZTPZIIE-UHFFFAOYSA-N trichloro(2-trichlorosilylethyl)silane Chemical compound Cl[Si](Cl)(Cl)CC[Si](Cl)(Cl)Cl WDVUXWDZTPZIIE-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
a、産業上の利用分野
本発明は、芳香族ビニル化合物と共役ジエン化合物から
なる特定構造のブロック共重合体の水素添加物の存在下
に、芳香族ビニル化合物およびこれと共重合可能な単量
体化合物をグラフト共重合させて得られる、特定のグラ
フト構造を有し、着色性、ウェルド部の外観などの成形
外観に優れ、低温域での衝撃強度特に落錘衝撃強度およ
び耐薬品性に優れたゴム変性熱可塑性樹脂、および該ゴ
ム変性熱可塑性樹脂と他の共重合体との組成物に関する
。DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention is directed to the production of an aromatic vinyl compound and a conjugated diene compound in the presence of a hydrogenated block copolymer having a specific structure. It has a specific graft structure obtained by graft copolymerization of a monomer compound that can be copolymerized with The present invention relates to a rubber-modified thermoplastic resin with excellent strength and chemical resistance, and a composition of the rubber-modified thermoplastic resin and another copolymer.
b、従来の技術
主鎖に実質的には不飽和結合を含まないエチレン−プロ
ピレン共重合体(EPM)、エチレンーブロビレンージ
エン三元共重合体(f!PDM)などをゴム成分として
用いたスチレン、アクリロニトリルなどとのグラフト共
重合体(ABS樹脂)は、共役ジエン系ゴムを用いたA
BS樹脂に比べ、紫外線、酸素およびオゾンに対する抵
抗性が大きく、格段に耐候性が良いことが知られている
。b. Conventional technology Ethylene-propylene copolymer (EPM), ethylene-propylene-diene terpolymer (f!PDM), etc., which do not substantially contain unsaturated bonds in the main chain, are used as rubber components. A graft copolymer (ABS resin) with styrene, acrylonitrile, etc.
It is known that it has greater resistance to ultraviolet rays, oxygen, and ozone, and has much better weather resistance than BS resin.
しかしABS樹脂には、以下に示す問題がある。However, ABS resin has the following problems.
(1)着色性に劣る。ABS樹脂に代表されるゴム変性
樹脂は、均一系樹脂に比べ、着色性に劣るとされている
0発明者らが検討したところでは、同じゴム変性樹脂の
中でも、ABS樹脂はABS樹脂と比べ、とくに彩やか
な色、濃い色において鮮明さと深みが不足し、同じ程度
の色の濃さに着色するためには、着色材が多量に必要で
あった。(1) Poor colorability. Rubber-modified resins, such as ABS resins, are said to have poorer coloring properties than homogeneous resins. According to the inventors' research, even among the same rubber-modified resins, ABS resins have lower coloring properties than ABS resins. In particular, vivid colors and deep colors lack clarity and depth, and a large amount of coloring agent is required to achieve the same level of color intensity.
(2)ウェルド部の外観が劣る。ABS樹脂は、その耐
候性が優れていることから、車輌用途の外装材として使
用されているが、ウェルド部の外観が悪く、成形不良品
と見なされることがあり、ウェルド部が目立たないよう
に金型を修正したり、ABS樹脂の流動性を出して対処
するために、滑材を大量に添加したりする必要があった
。(2) The appearance of the weld portion is poor. ABS resin is used as an exterior material for vehicles due to its excellent weather resistance, but the appearance of the welded part is poor and it is sometimes considered to be a defective product, so it is necessary to make the welded part less noticeable. It was necessary to modify the mold and add a large amount of lubricant to improve the fluidity of the ABS resin.
(3)低温での耐衝撃性に劣る。 ABS樹脂と比べ
耐寒性とくに低温における耐衝撃性に劣っている。この
ため耐候性に優れるという大きな長所があるにも拘らず
、その使用範囲は著しく制限されている。低温での耐衝
撃性を改良するために、ABS樹脂をポリマーブレンド
するなどの試みがなされているが、ABS樹脂の耐候性
を保持したまま、低温での耐衝撃性を改良することは困
難であった。(3) Poor impact resistance at low temperatures. It is inferior to ABS resin in cold resistance, especially impact resistance at low temperatures. For this reason, although it has the great advantage of being excellent in weather resistance, its range of use is extremely limited. Attempts have been made to improve the impact resistance at low temperatures by blending ABS resin with polymers, but it is difficult to improve the impact resistance at low temperatures while maintaining the weather resistance of ABS resin. there were.
(4)耐灯油性、耐ガソリン性に劣る。ABS樹脂は、
耐候性に優れていることから、自動車外装部品などへ使
用されているが、耐灯油性、耐ガソリン性が劣る。その
改良方法として、ABS樹脂中のゴム量を低減させるな
どの対策が必要であり、その結果強度が低下し、使用部
位、使用方法などに制約を生ずる場合があった。(4) Poor kerosene resistance and gasoline resistance. ABS resin is
Due to its excellent weather resistance, it is used for automobile exterior parts, but it has poor kerosene and gasoline resistance. As a method for improving this, it is necessary to take measures such as reducing the amount of rubber in the ABS resin, which results in a decrease in strength, which sometimes creates restrictions on the parts where it can be used, how it can be used, etc.
C0発明が解決しようとする課題
こうした点に関し、鋭意検討した結果、本発明者らは、
芳香族ビニル化合物と共役ジエン化合物からなる特定構
造のブロック共重合体であって、かつその水素添加物か
らなるゴム質重合体の存在下に、芳香族ビニル化合物お
よびこれと共重合可能な単量体化合物をグラフト共重合
させ、特定のグラフト構造を付与することで、着色性、
ウェルド部の外観、低温耐衝撃性および耐薬品性に著し
く優れた耐候性樹脂を得ることに成功し、本発明に到っ
たものである。Problems to be Solved by the C0 Invention As a result of intensive study regarding these points, the present inventors have
A block copolymer with a specific structure consisting of an aromatic vinyl compound and a conjugated diene compound, in the presence of a rubbery polymer consisting of a hydrogenated product thereof, an aromatic vinyl compound and a monomer copolymerizable therewith. By graft copolymerizing body compounds and imparting a specific graft structure, coloring properties,
The present invention was achieved by successfully obtaining a weather-resistant resin that has excellent weld part appearance, low-temperature impact resistance, and chemical resistance.
60課題を解決するための手段
本発明は、芳香族ビニル化合物と共役ジエン化合物から
なるブロック共重合体で、その重合体の数平均分子量が
5.000〜1.ooo、000、重量平均分子量(M
−)と数平均分子量(Mn)の比(Mw/Mn)が10
以下、かつジエン部のビニル結合含有量が10〜90%
であり、ジエン重合体部分を水素添加して該重合体のオ
レフィン性不飽和結合の少なくとも70%が水素添加さ
れた水添ジエン系重合体−(i)5〜80重量部の存在
下に、芳香族ビニル化合物(A)5〜98重量%および
これと共重合可能な単量体化合物CB) 95〜2重量
%からなる単量体混合物(ii)95〜20重量部をグ
ラフト共重合させた、グラフト率が20〜90%で、か
つグラフトゴム粒子の重量平均粒子径がO,OS〜0.
5μであることを特徴とするゴム変性熱可塑性樹脂、お
よび該ゴム変性熱可塑性樹脂20〜80重量部と、α−
メチルスチレン、N−置換マレイミド化合物、その他の
芳香族ビニル化合物、シアン化ビニル化合物、および(
メタ)アクリル酸アルキルエステルから選ばれた少くと
も2種の化合物の共重合体80〜20重量部からなるゴ
ム変性熱可塑性樹脂組成物を提供するものである。60 Means for Solving the Problems The present invention is a block copolymer consisting of an aromatic vinyl compound and a conjugated diene compound, and the number average molecular weight of the polymer is 5.000 to 1. ooo, 000, weight average molecular weight (M
-) and number average molecular weight (Mn) (Mw/Mn) is 10
or less, and the vinyl bond content of the diene part is 10 to 90%
and in the presence of 5 to 80 parts by weight of a hydrogenated diene polymer in which at least 70% of the olefinic unsaturated bonds of the polymer are hydrogenated by hydrogenating the diene polymer portion, 95 to 20 parts by weight of a monomer mixture (ii) consisting of 5 to 98% by weight of an aromatic vinyl compound (A) and 95 to 2% by weight of a monomer compound CB) copolymerizable therewith were graft copolymerized. , the grafting rate is 20 to 90%, and the weight average particle diameter of the grafted rubber particles is O, OS to 0.
a rubber-modified thermoplastic resin characterized by having a particle diameter of 5μ, and 20 to 80 parts by weight of the rubber-modified thermoplastic resin, and α-
Methylstyrene, N-substituted maleimide compounds, other aromatic vinyl compounds, vinyl cyanide compounds, and (
The present invention provides a rubber-modified thermoplastic resin composition comprising 80 to 20 parts by weight of a copolymer of at least two types of compounds selected from alkyl meth)acrylates.
以下、本発明をさらに詳しく説明する。The present invention will be explained in more detail below.
本発明に使用される芳香族ビニル化合物と共役ジエン化
合物からなるブロック共重合体は、たとえばスチレンと
ブタジェンのブロック共重合体を水素添加し、共役ジエ
ン化合物に基づく脂肪族二重結合を実質的に飽和させ、
オレフィン性重合体に変換させたものである。The block copolymer composed of an aromatic vinyl compound and a conjugated diene compound used in the present invention can be obtained by hydrogenating a block copolymer of styrene and butadiene to substantially eliminate the aliphatic double bonds based on the conjugated diene compound. saturate,
It is converted into an olefinic polymer.
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、ビニルトルエンなどがあり、中でもスチレンが好
ましい。また共役ジエン化合物としては、ブタジェン、
イソプレン、1.3−ペンタジェン、2.3−ジメチル
−1,3−ブタジェンなどがあり、中でもブタジェン、
イソプレンおよびこれらの組合せが好ましい。Examples of the aromatic vinyl compound include styrene, α-methylstyrene, and vinyltoluene, with styrene being preferred. Conjugated diene compounds include butadiene,
Isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. Among them, butadiene,
Isoprene and combinations thereof are preferred.
芳香族ビニル化合物と共役ジエン化合物の割合は、特に
限定するものではないが、樹脂とした場合の耐衝撃強度
を維持するためには、芳香族ビニル化合物/共役ジエン
化合物=5〜60/95〜40(重量%)が好ましく、
とくに10〜50/90〜50重量%が好ましい。The ratio of the aromatic vinyl compound and the conjugated diene compound is not particularly limited, but in order to maintain the impact resistance strength when used as a resin, the ratio of the aromatic vinyl compound/conjugated diene compound is 5 to 60/95 to 60/95. 40 (wt%) is preferable,
Particularly preferred is 10-50/90-50% by weight.
このブロック共重合体の分子構造は直鎖状、分岐状、放
射状あるいはこれらの組合せのいずれでもよく、さらに
ブロック構造としてはジブロック、トリブロックまたは
マルチブロック、さらにトリフロックでも左右の構造が
非対称であるものでもよく、特に限定されるものではな
い。The molecular structure of this block copolymer may be linear, branched, radial, or a combination thereof, and the block structure may be diblock, triblock, or multiblock, and even trifloc may have an asymmetric left and right structure. It may be any one, and is not particularly limited.
なおこれらの中ではAB型のジブロックが好ましい。Among these, AB type diblock is preferred.
これらブロック共重合体は、そのオレフィン性不飽和結
合の少なくとも70%以上を水素添加することが必要で
あり、好ましくは80%以上が水素添加される。これ以
下では、耐候性を実質的に維持することが困難となる。In these block copolymers, at least 70% or more of the olefinic unsaturated bonds must be hydrogenated, preferably 80% or more. Below this, it becomes difficult to substantially maintain weather resistance.
また、これらブロック共重合体の数平均分子量(Mn)
は5.000〜1,000,000であり、好ましくは
30.000〜800,000 、さらに好ましくは5
0 、000〜600,000である。この数平均分子
量は、重合触媒で制御できる。In addition, the number average molecular weight (Mn) of these block copolymers
is 5,000 to 1,000,000, preferably 30,000 to 800,000, more preferably 5
0,000 to 600,000. This number average molecular weight can be controlled by a polymerization catalyst.
数平均分子量が5,000以下の場合、グラフト重合樹
脂の耐衝撃性が低く、1,000,000以上の場合、
着色性およびウェルド外観を改良することができない。When the number average molecular weight is 5,000 or less, the impact resistance of the graft polymer resin is low, and when it is 1,000,000 or more,
Colorability and weld appearance cannot be improved.
さらに、ブロック共重合体の重量平均分子量(Mw)と
数平均分子量(Mn)の比(Mh/Mn)はlO以下で
あり、好ましくは8以下、さらに好ましくは5以下、特
に好ましくは1〜3である。Mw/Mnが10以上であ
る場合、グラフト重合時に生成するグラフト粒子の粒子
径分布が広くなり、ウェルド部の外観が悪くなる。Furthermore, the ratio (Mh/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the block copolymer is 1O or less, preferably 8 or less, more preferably 5 or less, particularly preferably 1 to 3. It is. When Mw/Mn is 10 or more, the particle size distribution of graft particles generated during graft polymerization becomes wide, and the appearance of the weld portion becomes poor.
Mw/Mnは、特定の重合触媒種を用いることで制御で
きる。Mw/Mn can be controlled by using a specific polymerization catalyst species.
また、このブロック共重合体のジエン部のビニル結合含
有量は10〜90%であり、好ましくは20〜80%、
さらに好ましくは25〜75%、特に好ましくは30〜
60%である。このビニル結合含有量が10%以下また
は90%以上の場合、グラフト共重合体の低温度域での
耐衝撃性が低下する。Further, the vinyl bond content of the diene part of this block copolymer is 10 to 90%, preferably 20 to 80%,
More preferably 25 to 75%, particularly preferably 30 to 75%
It is 60%. When the vinyl bond content is 10% or less or 90% or more, the impact resistance of the graft copolymer in a low temperature range decreases.
】、2−13,4−結合などのビニル結合含有量のコン
トロールには、エーテル、3級アミン化合物、ナトリウ
ム、カリウムなどのアルカリ金属のアルコキシド、フェ
ノキシト、スルフォン酸塩が用いられる。], 2-13,4-bonds and other vinyl bonds, ethers, tertiary amine compounds, alkoxides, phenoxides, and sulfonates of alkali metals such as sodium and potassium are used.
前記ジエン系重合体は、例えば、有機リチウム開始剤を
用い炭化水素溶媒中でアニオンリビング重合を行なうこ
とにより得られる。また、分岐状重合体は、3官能以上
のカップリング剤を、前記重合終了時に必要量添加して
カップリング反応を行なうことにより得られる。The diene polymer can be obtained, for example, by carrying out anionic living polymerization in a hydrocarbon solvent using an organolithium initiator. Further, the branched polymer can be obtained by adding a required amount of a trifunctional or more functional coupling agent at the end of the polymerization to perform a coupling reaction.
有機リチウム開始剤としては、n−ブチルリチウム、5
ec−ブチルリチウム、ter t−ブチルリチウムな
どが用いられる。炭化水素溶媒としては、ヘキサン、ヘ
プタン、メチルシクロペンタン、シクロヘキサン、ベン
ゼン、トルエン、キシレン、2−メチルブテン−1,2
−メチルブテン−2などが用いられる。As the organolithium initiator, n-butyllithium, 5
Ec-butyllithium, tert-butyllithium, etc. are used. Hydrocarbon solvents include hexane, heptane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, 2-methylbutene-1,2
-Methylbutene-2, etc. are used.
重合はバッチ方式でも連続方式でもよく、重合温度は通
常0〜120°Cの範囲で、重合時間は10分〜3時間
の範囲で行なわれる。カップリング剤は3官能以上のカ
ップリング剤で、その例としてはテトラクロロケイ素、
ブチルトリクロロケイ素、テトラクロロスズ、ブチルト
リクロロスズ、テトラクロロゲルマニウム、ビス(トリ
クロロシリル)エタン、ジビニルベンゼン、アジピン酸
ジエステル、エポキシ化液状ポリブタジェン、エポキシ
化大豆油、エポキシ化亜麻仁油、トリレンジイソシアナ
ート、ジフェニルメタンジイソシアナート、1,2.4
−ベンゼントリイソシアナートなどが挙げられる。The polymerization may be carried out in a batch manner or in a continuous manner, and the polymerization temperature is usually in the range of 0 to 120°C and the polymerization time is in the range of 10 minutes to 3 hours. The coupling agent is a trifunctional or more functional coupling agent, examples of which include tetrachlorosilicon,
Butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis(trichlorosilyl)ethane, divinylbenzene, adipic acid diester, epoxidized liquid polybutadiene, epoxidized soybean oil, epoxidized linseed oil, tolylene diisocyanate, diphenylmethane diisocyanate, 1,2.4
-Benzene triisocyanate and the like.
こうして重合されたジエン系重合体を水素添加すること
により、本発明の水添ジエン系重合体(1)が得られる
。By hydrogenating the diene polymer thus polymerized, the hydrogenated diene polymer (1) of the present invention can be obtained.
水素化反応は前記の共役ジエン系重合体を炭化水素溶媒
中に溶解し、20〜150°C,1kg/cffl−1
00kg/cdの加圧水素下、水素化触媒の存在下で行
なわれる。In the hydrogenation reaction, the above conjugated diene polymer is dissolved in a hydrocarbon solvent, and heated at 20 to 150°C and 1 kg/cffl-1.
It is carried out under pressurized hydrogen at 00 kg/cd in the presence of a hydrogenation catalyst.
水素化触媒としてはパラジウム、ルテニウム、ロジウム
、白金などの貴金属をシリカ、カーボン、ケイソウ土な
どに担持した触媒、ロジウム、ルテニウム、白金などの
錯体触媒、コバルト、ニッケルなどの有機カルボン酸と
有機アルミニウムまたは有機リチウムからなる触媒、ジ
シクロペンタジェニルチタンジクロリド、ジシクロペン
タジェニルジフェニルチタン、ジシクロペンタジェニル
チタンジトリル、ジシクロペンタジェニルチタンジベン
ジルなどのチタン化合物とリチウム、アルミニウム、マ
グネシウムよりなる有機金属化合物からなる水素化触媒
などが用いられる。Hydrogenation catalysts include catalysts in which noble metals such as palladium, ruthenium, rhodium, and platinum are supported on silica, carbon, diatomaceous earth, etc., complex catalysts such as rhodium, ruthenium, and platinum, organic carboxylic acids such as cobalt, nickel, and organic aluminum or Catalysts consisting of organolithium, titanium compounds such as dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentajenyl titanium ditolyl, dicyclopentadienyl titanium dibenzyl, and lithium, aluminum, and magnesium. Hydrogenation catalysts made of organometallic compounds are used.
本発明のゴム変性熱可塑性樹脂の製造方法としては、水
添ジエン系重合体(i)の存在下に、ビニル単量体をラ
ジカル重合する各種の方法、例えば乳化重合法、塊状重
合法、懸濁重合法などを採用することができる。The rubber-modified thermoplastic resin of the present invention can be produced by various methods including radical polymerization of vinyl monomers in the presence of the hydrogenated diene polymer (i), such as emulsion polymerization, bulk polymerization, suspension polymerization, etc. A turbidity polymerization method or the like can be adopted.
本発明において使用される単量体は、芳香族ビニル化合
物(A)、およびこれと共重合可能な単量体化合物(B
)である。The monomers used in the present invention include an aromatic vinyl compound (A) and a monomer compound copolymerizable therewith (B).
).
芳香族ビニル化合物(A)としては、スチレン、α−メ
チルスチレン、メチルスチレン、ビニルキシレン、モノ
クロルスチレン、ジクロルスチレン、モノブロムスチレ
ン、ジブロムスチレン、フルオロスチレン、P−ターシ
ャリープチルスチレン、エチルスチレン、ビニルナフタ
レンなどがあり、これらは1種または2種以上で使用さ
れる。好ましい芳香族ビニル化合物は、スチレンまたは
芳香族ビニル化合物中スチレンを50重量%以上含んだ
ものである。Examples of the aromatic vinyl compound (A) include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, dibromostyrene, fluorostyrene, P-tertiarybutylstyrene, and ethylstyrene. , vinylnaphthalene, etc., and these may be used alone or in combination of two or more. A preferred aromatic vinyl compound is styrene or an aromatic vinyl compound containing 50% by weight or more of styrene.
共重合可能な単量体化合物(B)としては、アクリロニ
トリル、メタクリレートリルなどのシアン化ビニル化合
物があり、これらは1種または2種以上で使用される。Examples of the copolymerizable monomer compound (B) include vinyl cyanide compounds such as acrylonitrile and methacrylate trile, which may be used alone or in combination of two or more.
とくにアクリロニトリルが好ましい。Acrylonitrile is particularly preferred.
さらにメチルアクリレート、エチルアクリレート、プロ
ピレンアクリレート、ブチルアクリレート、アミルアク
リレート、ヘキシルアクリレート、オクチルアクリレー
ト、2−エチルへキシルアクリレート、シクロへキシル
アクリレート、ドデシルアクリレート、オクタデシルア
クリレート、フェニルアクリレート、ベンジルアクリレ
ートなどのアクリル酸アルキルエステル;メチルメタク
リレ−1・、エチルメタクリレート、プロピレンメタク
リレート、ブチルメタクリレート、アミルメタクリレー
ト、ヘキシルメタクリレート、オクチルメタクリレート
、2−エチルヘキシルメタクリレート、シクロへキシル
メタクリレート、ドデシルメタクリレート、オクタデシ
ルメタクリレート、フェニルメタクリレート、ベンジル
メタクリレートなどのメタクリル酸アルキルエステル;
無水マレイン酸、無水イクコン酸、無水シトラコン酸な
どの不飽和酸無水物;アクリル酸、メタクリル酸などの
不飽和酸など、また、マレイミド、N−メチルマレイミ
ド、N−ブチルマレイミド、N−(p−メチルフェニル
)マレイミド、N−フェニルマレイミド、N−シクロヘ
キシルマレイミドなどのα・β−不飽和ジカルボン酸の
イミド化合物などがあげられ、これらは、本発明のゴム
変性熱可塑性樹脂に支障のない範囲で、1種または2種
以上で使用される。Furthermore, alkyl acrylates such as methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, etc. Ester; methyl methacrylate-1, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, etc. Methacrylic acid alkyl ester;
Unsaturated acid anhydrides such as maleic anhydride, iconic anhydride, and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; also maleimide, N-methylmaleimide, N-butylmaleimide, N-(p- Examples include imide compounds of α/β-unsaturated dicarboxylic acids such as methylphenylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Used alone or in combination of two or more.
単量体化合物(B) としては、シアン化ビニルおよび
/または(メタ)アクリル酸アルキルエステル(アクリ
ル酸アルキルエステルとメタアクリル酸アルキルエステ
ルの総称)が好ましく、これらによると本発明の目的と
する効果の一段と優れたものが得られる。例えば、シア
ン化ビニルを使用すると、耐衝撃性、耐薬品性および塗
装性がさらに優れたものが得られ、(メタ)アクリル酸
アルキルエステルを用いると、耐候性がさらに優れたも
のが得られる。As the monomer compound (B), vinyl cyanide and/or (meth)acrylic acid alkyl ester (general term for acrylic acid alkyl ester and methacrylic acid alkyl ester) are preferable, and according to these, the desired effects of the present invention can be achieved. You can get something even better. For example, when vinyl cyanide is used, a product with even better impact resistance, chemical resistance, and paintability can be obtained, and when an alkyl (meth)acrylate ester is used, a product with even better weather resistance can be obtained.
シアン化ビニルとしてはアクリロニトリル、(メタ)ア
クリル酸アルキルエステルとしてはメチルメタクリレー
トが好ましい。As the vinyl cyanide, acrylonitrile is preferred, and as the alkyl (meth)acrylate ester, methyl methacrylate is preferred.
芳香族ビニル化合物(A)と単量体化合物(B)の使用
比率は、5〜98/95〜2(重量%)である。The ratio of the aromatic vinyl compound (A) to the monomer compound (B) is 5 to 98/95 to 2 (wt%).
芳香族ビニル化合物(A)が5重量%以下であると成形
加工性が劣り、98重量%以上であると、着色性、ウェ
ルド部の外観、耐薬品性および耐候性が劣る。If the amount of the aromatic vinyl compound (A) is 5% by weight or less, the molding processability is poor, and if it is 98% by weight or more, the colorability, the appearance of the weld part, the chemical resistance, and the weather resistance are poor.
単量体成分として、芳香族ビニル化合′JjyJ(A)
とシアン化ビニル化合物を用いることが好ましいが、好
ましい使用比率は芳香族ビニル化合物(^)/単量体化
合物(B) =30〜98 / 70〜2、さらに好ま
しくは60〜95/40〜5(重量%)である。As a monomer component, an aromatic vinyl compound 'JjyJ (A)
It is preferable to use a vinyl cyanide compound and a preferable ratio of aromatic vinyl compound (^)/monomer compound (B) = 30 to 98/70 to 2, more preferably 60 to 95/40 to 5. (% by weight).
本発明のゴム変性熱可塑性樹脂中の水添ジエン系重合体
(i)の含有量は、5〜80重量部である。80重量部
より多い場合は、重合後のグラフト率が低く耐11撃性
が低い。また、5重量部より少い場合も同様に耐衝撃性
が低くなる。The content of the hydrogenated diene polymer (i) in the rubber-modified thermoplastic resin of the present invention is 5 to 80 parts by weight. If the amount is more than 80 parts by weight, the grafting rate after polymerization will be low and the 11 shot resistance will be low. Furthermore, if the amount is less than 5 parts by weight, the impact resistance will similarly decrease.
本発明において用いる好ましい単量体との組合せの具体
例を以下に示す。この中で好ましいのは■である。Specific examples of preferred combinations of monomers used in the present invention are shown below. Among these, ■ is preferable.
■ スチレン−アクリロニトリル
■ スチレンーメチルメタクリレート
■ スチレン−アクリロニトリル−メチルメタクリレー
ト
上記のスチレンの一部または全部をα−メチルスチレン
に置換えることで、耐熱性を付与することができる。ま
たスチレンの一部または全部をハロゲン化スチレンで置
換えることで、難燃性を付与することができる。また、
上記の単量体の組合せにおいて、さらにメチルメタクリ
レートを併用すると、ゴム変性熱可塑性樹脂の透明性が
向上し、優れた着色性が得られる。■ Styrene-acrylonitrile ■ Styrene-methyl methacrylate ■ Styrene-acrylonitrile-methyl methacrylate Heat resistance can be imparted by replacing part or all of the above styrene with α-methylstyrene. Furthermore, flame retardancy can be imparted by replacing part or all of styrene with halogenated styrene. Also,
In the above monomer combination, when methyl methacrylate is further used in combination, the transparency of the rubber-modified thermoplastic resin is improved and excellent colorability can be obtained.
本発明のゴム変性熱可塑性樹脂は、グラフト率が20〜
90%の範囲のものであり、好ましくは25〜85%、
さらに好ましくは30〜80%、特に好ましくは35〜
80%のものである。ここでグラフト率とは、グラフト
重合体のゴム量に対しするゴムに直接グラフト結合して
いる共重合体成分の割合をいう、グラフト率は、重合開
始剤の量、重合温度などにより制御できる。The rubber-modified thermoplastic resin of the present invention has a graft ratio of 20 to
90%, preferably 25-85%,
More preferably 30 to 80%, particularly preferably 35 to 80%
It is 80%. The graft ratio here refers to the ratio of the copolymer component directly graft-bonded to the rubber to the amount of rubber in the graft polymer. The graft ratio can be controlled by the amount of polymerization initiator, polymerization temperature, etc.
グラフト率が20%以下の場合、特開昭51−9183
号に示されているごとく、実質的にグラフトしていなく
とも衝撃強度は十分ではあるが、耐灯油性、耐ガソリン
性などの耐溶剤性が著しく低下し、また着色性、ウェル
ド外観などの成形外観も悪くなる。When the grafting rate is less than 20%, JP-A-51-9183
As shown in the above issue, impact strength is sufficient even without substantial grafting, but solvent resistance such as kerosene resistance and gasoline resistance is significantly reduced, and moldability such as coloration and weld appearance is reduced. The appearance also deteriorates.
一方、グラフト率が90%以上の場合、水素添加共重合
体へのグラフト率が上昇し、実質的にゴムとしての機能
を果たすことができず、耐衝撃性が低下する。On the other hand, when the grafting rate is 90% or more, the grafting rate to the hydrogenated copolymer increases, and the rubber cannot substantially function as a rubber, resulting in a decrease in impact resistance.
本発明のゴム変性熱可塑性樹脂のグラフトゴム粒子の重
量平均粒子径は、0.05〜0.5μであり、好ましく
は0.07〜0.45μ、さらに好ましくは0.08〜
0.4//である0粒子径は重合時の攪拌速度によって
制御することができる。0.05μ以下の場合、グラフ
ト共重合体の耐衝撃性が低く、0.5μ以上の場合、着
色性、ウェルド部外観などの成形外観を改良することが
できない。The weight average particle diameter of the grafted rubber particles of the rubber-modified thermoplastic resin of the present invention is 0.05 to 0.5μ, preferably 0.07 to 0.45μ, more preferably 0.08 to 0.5μ.
The zero particle size, which is 0.4//, can be controlled by the stirring speed during polymerization. If it is less than 0.05μ, the impact resistance of the graft copolymer will be low, and if it is more than 0.5μ, it will not be possible to improve the molding appearance such as the colorability or the appearance of the weld area.
また、メチルエチルケトン可溶分の固有粘度〔η](3
0°Cで測定)は、好ましくは0.15di/g以上、
さらに好ましくは0.18〜1.5、特に好ましくは0
.18〜1.2である。固有粘度が0.15以上の場合
、室温および低温域での衝撃強度が優れる。In addition, the intrinsic viscosity of methyl ethyl ketone soluble component [η] (3
(measured at 0°C) is preferably 0.15 di/g or more,
More preferably 0.18 to 1.5, particularly preferably 0
.. It is 18-1.2. When the intrinsic viscosity is 0.15 or more, the impact strength at room temperature and low temperature range is excellent.
本発明のゴム変性熱可塑性樹脂は、目的に応じて他の重
合体とブレンドすることが可能であり、耐熱性を改良す
るために、α−メチルスチレンと、その他の芳香族ビニ
ル化合物、シアン化ビニル化合物、(メタ)クリル酸エ
ステル化合物から選ばれた少くとも1種以上の化合物と
の共重合体をブレンドする。The rubber-modified thermoplastic resin of the present invention can be blended with other polymers depending on the purpose, and in order to improve heat resistance, α-methylstyrene, other aromatic vinyl compounds, cyanide A copolymer with at least one compound selected from vinyl compounds and (meth)acrylic acid ester compounds is blended.
このとき、共重合体中のα−メチルスチレン量は耐熱性
を確保するためには、30重星%以上であり、またブレ
ンド後の耐衝撃性を確保するためには、85重量%以下
であり、さらに好ましくは50〜80重世%である。ま
た、ゴム変性熱可塑性樹脂と共重合体とのブレンド比率
は、耐衝撃性を確保するため、グラフト共重合体は20
重量%以上、耐熱性を確保するためには80重量%以下
であり、さらに好ましくは30〜70重四%である。At this time, the amount of α-methylstyrene in the copolymer must be at least 30% by weight to ensure heat resistance, and at most 85% by weight to ensure impact resistance after blending. It is more preferably 50-80%. In addition, the blend ratio of the rubber-modified thermoplastic resin and the copolymer is 20% for the graft copolymer to ensure impact resistance.
The content is at least 80% by weight to ensure heat resistance, and more preferably from 30 to 70% by weight.
さらに耐熱性の改良および熱安定性改良のためには、ゴ
ム変性熱可塑性樹脂20〜80重世部に対して、N−置
換マレイミド化合物と、芳香族ビニル化合物、(メタ)
クリル酸エステル化合物、シアン化ビニル化合物から選
ばれた少くとも1種以上の化合物からなる共重合体をブ
レンドする。このとき、共重合体中のN−置換マレイミ
ド″化合物量は耐熱性を発現させるためには2重量%以
上であり、一方、耐衝撃性を1員わないためには50重
量%以下であり、さらに好ましくは5〜30重量%であ
る。ゴム変性熱可塑性樹脂と共重合体とのブレンド比率
は、耐衝撃性を確保するため、ゴム変性熱可塑性樹脂量
は20重量%以上、一方、耐衝熱性を確保するためには
、80重四%以下であり、さらに好ましくは30〜70
重量%である。Furthermore, in order to improve heat resistance and thermal stability, an N-substituted maleimide compound, an aromatic vinyl compound, (meth)
A copolymer consisting of at least one compound selected from acrylic acid ester compounds and vinyl cyanide compounds is blended. At this time, the amount of N-substituted maleimide compound in the copolymer is 2% by weight or more in order to develop heat resistance, and on the other hand, it is 50% by weight or less in order to not affect impact resistance. , more preferably 5 to 30% by weight.The blend ratio of the rubber-modified thermoplastic resin and the copolymer is such that the amount of the rubber-modified thermoplastic resin is 20% by weight or more in order to ensure impact resistance. In order to ensure thermal resistance, the content is 80% by weight or less, more preferably 30 to 70%.
Weight%.
また、着色性などの成形外観をさらに良くするためには
、(メタ)グリル酸エステル化合物と芳香族ビニル化合
物、シアン化ビニル化合物のうち少くとも1種以上の化
合物との共重合体をブレンドする。In addition, in order to further improve the molding appearance such as colorability, a copolymer of a (meth)grilled ester compound and at least one compound selected from aromatic vinyl compounds and vinyl cyanide compounds is blended. .
このとき、着色性を改良するためには、共重合体中の(
メタ)クリル酸エステル化合物は35重量%以上であり
、耐衝撃性を確保するためには、95重置火以下であり
、さらに好ましくは45〜85重星%である。At this time, in order to improve the colorability, (
The content of the meth)acrylic acid ester compound is 35% by weight or more, and in order to ensure impact resistance, the content is 95% by weight or less, more preferably 45 to 85% by weight.
またブレンド樹脂の着色性を良くするには、ゴム変性熱
可塑性樹脂量は80重量%以下であり、耐衝撃性を維持
するには、20重量%以上であり、さらに好ましくは3
0〜70重量%である。In addition, in order to improve the colorability of the blended resin, the amount of rubber-modified thermoplastic resin is 80% by weight or less, and in order to maintain impact resistance, it is 20% by weight or more, more preferably 3% by weight or less.
It is 0 to 70% by weight.
以上の項目以外に本発明のゴム変性熱可塑性樹脂は、他
の目的に応して他の重合体とブレンドすることが可能で
あり、ブレンドすることにより、ガラス状の重合体、た
とえばスチレン−アクリロニトリル共重合体やポリスチ
レンの耐衝撃性を改良することができる。このブレンド
体に含まれるゴム質重合体量は5〜45重量部であり、
好ましくは8〜40重量部、さらに好ましくは10〜3
5重量部である。In addition to the above items, the rubber-modified thermoplastic resin of the present invention can be blended with other polymers for other purposes. The impact resistance of copolymers and polystyrene can be improved. The amount of rubbery polymer contained in this blend is 5 to 45 parts by weight,
Preferably 8 to 40 parts by weight, more preferably 10 to 3 parts by weight
5 parts by weight.
このとき、ブレンドできる重合体としては上記2種以外
に次のものが挙げられる。例えばポリ塩化ビニル、ポリ
フェニレンエーテル、ポリカーボネート、ポリエチレン
テレフタレート、ポリブチレンテレフタレート、ポリア
セタール、ポリアミド、ポリフッ化ビニリデン、ハイイ
ンパクトポリスチレン、ABS樹脂、スチレン−無水マ
レイン酸共重合体、塩素化ポリエチレン、ABS樹脂、
EPR、EPDM、1.2−ポリブタジェンなどが挙げ
られる。これらは1種または2種以上で使用することが
できる。At this time, in addition to the above two types of polymers that can be blended, the following may be mentioned. For example, polyvinyl chloride, polyphenylene ether, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polyvinylidene fluoride, high impact polystyrene, ABS resin, styrene-maleic anhydride copolymer, chlorinated polyethylene, ABS resin,
Examples include EPR, EPDM, 1,2-polybutadiene, and the like. These can be used alone or in combination of two or more.
e、実施例 次に、本発明を実施例によりさらに詳しく説明する。e. Example Next, the present invention will be explained in more detail with reference to Examples.
cベースゴムNo、 1の製造〕
■ ベースポリマーの重合
50fオートクレーブに脱気脱水したシクロヘキサン5
00重量部およびスチレン30重量部を仕込んだのち、
テトラヒドロフラン0.5重量部およびn−ブチルリチ
ウム0.07部を加え、50°Cで重合し、重合転化率
がほぼ100%になったのち、1.3−ブタジェン70
重量部を入れ重合を継続し、重合転化率がほぼ100%
になったならば、2.6−シーtert−ブチルカテコ
ールを加えてスチームストリッピング法により脱溶し、
120°C熱ロールにて乾燥して重合体を得た。こうし
て得られたスチレン−ブタジェンブロック共重合体は、
スチレン含!!30重量%、ビニル結合含有M40%、
数平均分子量130,000、分子量分布1.3であっ
た。Production of base rubber No. 1] ■ Polymerization of base polymer Cyclohexane 5 degassed and dehydrated in a 50f autoclave
After charging 00 parts by weight and 30 parts by weight of styrene,
0.5 parts by weight of tetrahydrofuran and 0.07 parts of n-butyllithium were added and polymerized at 50°C. After the polymerization conversion rate reached almost 100%, 70 parts of 1,3-butadiene was added.
Add the weight part and continue polymerization until the polymerization conversion rate is almost 100%.
, add 2.6-tert-butylcatechol and remove the solution by steam stripping.
A polymer was obtained by drying with a hot roll at 120°C. The styrene-butadiene block copolymer thus obtained is
Contains styrene! ! 30% by weight, M40% containing vinyl bonds,
The number average molecular weight was 130,000, and the molecular weight distribution was 1.3.
■ 水素添加
■で重合した共役ジエン系ブロック共重合体を30!オ
ートクレーブに仕込み、15%シクロヘキサン溶液とし
た。系内を窒素で置換したのち、予め別容器で調製した
ナフテン酸ニッケル:n−ブチルリチウム:テトラヒド
ロフラン=1:8:20(モル比)の触媒液を、オレフ
ィン部分2000モルに対しニッケルとして1モルにな
るように仕込んだ。そののち、反応系内に水素を導入し
、70°Cで水素添加反応を行なった。水素の吸収消費
量によって水添率をコントロールしたのち、窒素で系内
の水素を置換し、老化防止剤2.6−ジ−ターシャリ−
ブチルバラクレゾールをI PHR添加した。肌触、凝
固をくり返したのち、常法によりロール乾燥を行ない、
水添率95%の水添ジエン共重合体(ベースゴムNαl
)を得た。■ Conjugated diene block copolymer polymerized by hydrogenation ■ 30! The mixture was charged into an autoclave and made into a 15% cyclohexane solution. After purging the system with nitrogen, a catalyst solution of nickel naphthenate:n-butyllithium:tetrahydrofuran=1:8:20 (mole ratio) prepared in advance in a separate container was added to 1 mole of nickel per 2000 moles of the olefin portion. I prepared it so that it would be. Thereafter, hydrogen was introduced into the reaction system, and a hydrogenation reaction was carried out at 70°C. After controlling the hydrogenation rate depending on the amount of hydrogen absorbed and consumed, the hydrogen in the system is replaced with nitrogen, and the anti-aging agent 2.6-di-tertiary
Butylvalacresol was added IPHR. After repeated touch and solidification, roll drying is carried out using the usual method.
Hydrogenated diene copolymer with hydrogenation rate of 95% (base rubber Nαl
) was obtained.
〔ベースゴムN112〜8の製造〕
■の方法に準じて、七ツマ−の添加方法、テトラヒドロ
フランの添加量、n−ブチルリチウムの添加量、重合温
度を変更し、表−1のベースゴム欄に示した阻2〜9の
構造のスチレン−ブタジェンブロック共重合体を得、そ
の後■の方法に準じ、水素添加を行い目的の水添ジエン
共重合体を得た。[Manufacture of base rubbers N112 to 8] According to the method of (2), the addition method of 7-mer, the amount of tetrahydrofuran, the amount of n-butyllithium added, and the polymerization temperature were changed, and the results were as shown in the base rubber column of Table 1. Styrene-butadiene block copolymers having structures 2 to 9 shown were obtained, and hydrogenation was then carried out according to the method (2) to obtain the desired hydrogenated diene copolymer.
また、比較例においてはEPDFf、 8Rとして日本
合成ゴム■製EP82、BRO2LLを用いた。In the comparative example, EP82 and BRO2LL manufactured by Japan Synthetic Rubber were used as EPDFf and 8R.
■ 結合スチレン量は、699cts−’のフェニル基
の吸収に基づいた赤外法による検量線から求めた。(2) The amount of bound styrene was determined from a calibration curve using an infrared method based on the absorption of phenyl groups at 699cts-'.
■ ビニル結合含有量は、赤外法(モレロ法)によって
求めた。■ The vinyl bond content was determined by an infrared method (Morello method).
■ 分子量および分子量分布は、ゲルパーミェーション
クロマトグラフィー(GPC)から求めた。(2) Molecular weight and molecular weight distribution were determined by gel permeation chromatography (GPC).
■ 水素添加率(水添率)は、四塩化エチレンを溶媒と
して用い、15部濃度で測定した100旧1zの°H−
N M Rスペクトルの不飽和結合部のスペクトルの減
少から算出した。■ Hydrogenation rate (hydrogenation rate) is 100% H-1z measured using ethylene tetrachloride as a solvent at a concentration of 15 parts.
It was calculated from the decrease in the spectrum of unsaturated bonds in the NMR spectrum.
(グラフト重合体の製造〕
〔実施例1〕
リボン型撹拌翼を備えた内容積101のステンレス製オ
ートクレーブに、予め均一溶液にした水添ベースゴム)
Jal:30重量部、スチレン70重量部、トルエン1
20重量部およびターシャリ−ドデシルメルカプタン0
.1重量部を仕込み、攪拌しながら昇温し、50°Cに
てベンゾイルパーオキサイド0.5重量部およびジクミ
ルパーオキサイドO81重量部を添加し、さらに昇温し
、80℃に達したのちは80゛Cで一定に制御しながら
攪拌回転数200rpa+にて重合反応を行なわせた。(Production of graft polymer) [Example 1] Hydrogenated base rubber made into a homogeneous solution in advance in a stainless steel autoclave with an internal volume of 101 mm equipped with a ribbon-type stirring blade)
Jal: 30 parts by weight, 70 parts by weight of styrene, 1 part by weight of toluene
20 parts by weight and 0 tertiary dodecyl mercaptan
.. 1 part by weight was charged, the temperature was raised while stirring, 0.5 parts by weight of benzoyl peroxide and 81 parts by weight of dicumyl peroxide O were added at 50°C, and the temperature was further raised to reach 80°C. The polymerization reaction was carried out at a constant stirring speed of 200 rpm while controlling the temperature at 80°C.
反応開始後6時間目から1時間かけて120’Cまで昇
温し、さらに2時間反応を行なって終了した0重合転化
率は97%であった。The temperature was raised to 120'C over 1 hour from 6 hours after the start of the reaction, and the reaction was continued for an additional 2 hours, and the zero polymerization conversion was 97%.
100℃まで冷却後2.2−メチレンビス−4−メチル
−6−t−ブチルフェノール0.2重量部を添加したの
ち、反応混合物をオートクレーブより抜き出し、水蒸気
蒸留により未反応物と溶媒を留去し細かく粉砕してから
40mφベント付押出機(220℃、700m+Hg真
空)にて実質的に揮発分を留去するとともに重合体をベ
レット化した。After cooling to 100°C and adding 0.2 parts by weight of 2.2-methylenebis-4-methyl-6-t-butylphenol, the reaction mixture was taken out of the autoclave, and unreacted substances and solvent were distilled off by steam distillation. After pulverizing, the volatile matter was substantially distilled off using a 40 mφ vented extruder (220° C., 700 m+Hg vacuum), and the polymer was pelletized.
〔実施例2〜13、比較例1〜13〕
実施例1と同様の方法にて表−1に記したモノマー組成
でターシャリ−ドデシルメルカプタン量、ベンゾイルパ
ーオキサイド量、ジクミルパーオキサイド量、およびこ
れらの比率、トルエン量、重合温度、ベースゴム量、攪
拌回転数を変更し、目的の構造のグラフト共重合体を得
た。[Examples 2 to 13, Comparative Examples 1 to 13] Using the same method as in Example 1, the amount of tertiary dodecyl mercaptan, the amount of benzoyl peroxide, the amount of dicumyl peroxide, and the monomer composition shown in Table 1 were prepared. By changing the ratio, amount of toluene, polymerization temperature, amount of base rubber, and stirring rotation speed, a graft copolymer with the desired structure was obtained.
また、実施例3.10.1112.13.14.15に
おいては、ブレンドポリマーとして、下記ポリマーまた
は下記重合方法で得たものを使用した。Moreover, in Example 3.10.1112.13.14.15, the following polymer or one obtained by the following polymerization method was used as the blend polymer.
〈麹−1〉三井東圧製LITAC−A I20PC<N
i1−2>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、窒素気流中でイオン交換水
200重量部およびラウリン酸カリウム2重量部を添加
して、攪拌しなからα−メチルスチレン70部、アクリ
ロニトリル30部、ターシャリ−ドデシルメルカプタン
0.2 Ni1部、ホルムアルデヒドスルホン酸ナトリ
ウムニ水塩0.4重量部、エチレンジアミンテトラ酢酸
ナトリウム062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0.4重量部を加え
、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98%であった。<Koji-1> Mitsui Toatsu LITAC-A I20PC<N
i1-2> 200 parts by weight of ion-exchanged water and 2 parts by weight of potassium laurate were added to a stainless steel autoclave with an internal volume of 50 cm equipped with a ribbon-type stirring blade in a nitrogen stream, and α-methylstyrene was added without stirring. 70 parts, 30 parts of acrylonitrile, 0.2 parts of tertiary dodecyl mercaptan, 1 part of Ni, 0.4 parts by weight of sodium formaldehyde sulfonate dihydrate, 062 parts by weight of sodium ethylenediaminetetraacetate, 0.005 parts by weight of ferrous sulfate, and cumenehydro. 0.4 parts by weight of peroxide was added, and a polymerization reaction was carried out at 70° C. for 4 hours while stirring was continued. The polymerization yield at this time was 98%.
硫酸マグネシウム水溶液を用いて凝固したのち、脱水乾
燥を行ない重合体を得た。After coagulating using an aqueous magnesium sulfate solution, dehydration and drying were performed to obtain a polymer.
<Nct−3> α−メチルスチレン量65部、アクリ
ロニトリル・20部、メタクリル酸メチル8部、スチレ
ン7部とした以外は、NIIL−2を得た方法と同様の
方法にて重合体を得た。<Nct-3> A polymer was obtained in the same manner as in obtaining NIIL-2, except that the amount of α-methylstyrene was 65 parts, acrylonitrile 20 parts, methyl methacrylate 8 parts, and styrene 7 parts. .
〈Na−4H4a−2の重合に用いたものと同一のオー
トクレーブを用い、窒素気流中でイオン交換水20Of
flffi部、n−フェニルマレイミド12.5部、α
−メチルスチレン17部、アクリロニトリル8.5重を
部、スチレン17重量部、ターシャリ−ドデシルメルカ
プタン0.15重量部、ホルムアルデヒドスルホン酸ナ
トリウムニ水塩0.3重量部、エチレンジアミンテトラ
酢酸ナトリウム0.15重量部、硫酸第1鉄0.003
重量部およびクメンヒドロパーオキサイド0.2重量部
を加え、攪拌を続けながら60℃で2時間重合反応を行
なった。この時の重合収率は95%であった。そののち
、イオン交換水を除く他の化合物を同量仕込み、同様に
して60°Cで2時間重合反応を行ない、重合収率97
%のものを得た。これを阻−2を得た方法と同様の方法
で重合体を回収した。<Using the same autoclave as that used for the polymerization of Na-4H4a-2, 20 ml of ion-exchanged water was added in a nitrogen stream.
flffi part, n-phenylmaleimide 12.5 parts, α
- 17 parts by weight of methylstyrene, 8.5 parts by weight of acrylonitrile, 17 parts by weight of styrene, 0.15 parts by weight of tertiary dodecyl mercaptan, 0.3 parts by weight of sodium formaldehyde sulfonate dihydrate, 0.15 parts by weight of sodium ethylenediaminetetraacetate. part, ferrous sulfate 0.003
Parts by weight and 0.2 parts by weight of cumene hydroperoxide were added, and a polymerization reaction was carried out at 60°C for 2 hours while stirring. The polymerization yield at this time was 95%. After that, the same amount of other compounds except ion-exchanged water was added, and a polymerization reaction was similarly carried out at 60°C for 2 hours, with a polymerization yield of 97.
I got %. The polymer was recovered in the same manner as the method used to obtain I-2.
<NIk−5>単量体化合物のn−フェニルマレイミド
の代わりにn−シクロへキシルマレイミドを用い、スチ
レンの代わりにメタクリル酸メチルを用いた以外は、N
114の重合体を得た方法と同じ方法で重合体を得た。<NIk-5> N-cyclohexylmaleimide was used instead of n-phenylmaleimide as a monomer compound, and methyl methacrylate was used instead of styrene
The polymer was obtained in the same manner as the polymer No. 114 was obtained.
<Na−6>リボン型攪拌翼を備えた内容積50j2の
ステンレス製オートクレーブに、予め均一溶液としたメ
チルメタクリレート55重量部、スチレン20重量部、
アクリロニトリル25重量部、トルエン30重量部およ
びターシャリ−ドデシルメルカプタンo、3 重1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、さらに昇温し120
’Cに達したのちは、120″Cで一定に制御しながら
攪拌回転数1100rpにて、10時間反応を行なった
。<Na-6> In a stainless steel autoclave with an internal volume of 50j2 equipped with a ribbon-type stirring blade, 55 parts by weight of methyl methacrylate, 20 parts by weight of styrene, which had been made into a homogeneous solution in advance, were placed.
25 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 1 part of tertiary dodecyl mercaptan O, 3 were charged, and the temperature was raised while stirring. 0.1 part by weight of dicumyl peroxide was added at 50°C, and the temperature was further raised. 120
After reaching 'C, the reaction was carried out for 10 hours at a stirring rotational speed of 1100 rpm while controlling the temperature to be constant at 120"C.
この時の重合収率は90%であった。以後の処理は石−
2を得た方法と同様の方法で行ない、重合体を得た。The polymerization yield at this time was 90%. Subsequent processing is stone-
A polymer was obtained in the same manner as in obtaining 2.
<Ha−7>撹拌機付ステンレス反応器内部を窒素で十
分置換したのち、窒素気流中でイオン交換水200 f
f11部およびロジン酸カリウム2重量部を添加して、
撹拌しながらメチルメタクリレート70重量部、スチレ
ン5重量部、アクリロニトリル15重量部、α−メチル
スチレン10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
ムニ水塩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重世部を加える
。攪拌を続けながら、70’C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。硫酸水溶液
を用いて凝固したのち、脱水乾燥を行ない重合体を得た
。<Ha-7> After sufficiently replacing the inside of the stainless steel reactor with a stirrer with nitrogen, 200 f of ion-exchanged water was added in a nitrogen stream.
Adding 11 parts of f and 2 parts by weight of potassium rosinate,
While stirring, 70 parts by weight of methyl methacrylate, 5 parts by weight of styrene, 15 parts by weight of acrylonitrile, 10 parts by weight of α-methylstyrene, 0.2 parts by weight of tertiary dodecyl mercaptan, 0.4 parts by weight of sodium formaldehyde sulfonate dihydrate, Add 0.2 parts by weight of sodium ethylenediaminetetraacetate, 0.005 parts by weight of ferrous sulfate, 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 sulfuric acid solution, dehydration and drying were performed to obtain a polymer.
上記の方法で得たベレットを、40ma+φ押出機(2
20℃)にて溶融混練して、表−1に示す如き樹脂組成
物を得た。90TON射出成形機(220°C)にて試
験片を成形し、物性を測定した。また、得られた樹脂組
成物を、下記配合にて、押出機を通して着色ベレットを
得、それを成形して色調評価プレートを得た。黒色配合
着色性については、色差計にて明度を測定し、マンセル
色表値(値が大きい程着色性は悪い)で表わした。他の
着色配合については、彩度を目視判定した。The pellets obtained by the above method were processed using a 40ma+φ extruder (2
The resin compositions shown in Table 1 were obtained by melt-kneading at 20°C. A test piece was molded using a 90TON injection molding machine (220°C), and its physical properties were measured. Further, the obtained resin composition was passed through an extruder in the following formulation to obtain a colored pellet, which was then molded to obtain a color tone evaluation plate. Regarding the colorability of the black blend, the lightness was measured using a color difference meter and expressed as a Munsell color table value (the larger the value, the worse the colorability). For other coloring formulations, saturation was determined visually.
黒色配合 樹脂 100カーボン
ブラツク 0.05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耐候性につい
ては、サンシャインウェザオメータで1000時間照射
後のアイゾツト衝撃値および光沢を測定した。結果を表
−1に示した。Black compound resin 100 carbon black 0.05 Ca stearate
O,3 red compound resin
100 red iron 1.0 Ca stearate O, 5 blue color combination resin
100 ultramarine blue
1.0 Ca Stearate O,5 Regarding weather resistance, Izot impact value and gloss after 1000 hours of irradiation were measured using a sunshine weatherometer. The results are shown in Table-1.
表−1において、各特性の測定は下記によって行なった
。In Table 1, each characteristic was measured as follows.
(1) inドア0−レー) :JIS K7
210 (22°C10kg)(2) Tzod
lap :ASTM D−256(断面% X +A
インチ、 ノフチイ寸)(3) 光沢 :AST
M D−523(450)(4)耐候性
試験条件 :サンシャインウェザオメーター(スガ試験
機■畦L−6X5−DC)、ブラックパネル温度63±
3°C
槽内湿度 63部5%RH
降雨サイクル 1B/120分
カーボン交換サイ゛クル6011r
測定方法 :ASTM D−256
(断面1/8 Xi/2インチ)
(5)耐灯油性 :黒色ベレット (配合 樹脂100
重量部、カーボンブラック0.5
重量部、ステアリン酸Ca O,3重
量部)による成形品をJIS 6号
灯油に浸漬し、50°Cで1時間放
置後表面を拭き取り、乾燥復興
常の有無を判断した。(1) Indoor 0-lay): JIS K7
210 (22°C 10kg) (2) Tzod
lap: ASTM D-256 (cross section %
Inch, Noft size) (3) Gloss: AST
M D-523 (450) (4) Weather resistance test conditions: Sunshine Weatherometer (Suga Test Instruments ■Raw L-6X5-DC), black panel temperature 63±
3°C Tank humidity 63 parts 5% RH Rain cycle 1B/120 minutes Carbon exchange cycle 6011r Measurement method: ASTM D-256 (cross section 1/8 Xi/2 inch) (5) Kerosene resistance: Black pellet ( Compound Resin 100
Parts by weight of carbon black, 0.5 parts by weight of carbon black, 3 parts by weight of CaO stearate) were immersed in JIS No. 6 kerosene, left at 50°C for 1 hour, and then wiped off the surface to check for dry recovery. It was judged.
判定良−・・・−・変色が認められない。Good judgment: No discoloration observed.
判定不良−白化、光沢低下などの変化が認められる。Poor judgment - Changes such as whitening and decreased gloss are observed.
(6)落錘衝撃強度
デュポンインパクトテスターを用いて打撃棒先@ R=
’A″で、厚み1.6 amの成形品の落錘衝撃強度
を測定した。(6) Falling weight impact strength Using a DuPont impact tester, the tip of the striking rod @ R =
At 'A', the falling weight impact strength of a molded product with a thickness of 1.6 am was measured.
(7)ウェルド外観
90TON射出成形機にてウェルドの出る金型を用い成
形したのち、標準光源の下にて目視で判定した。(7) Weld appearance After molding using a mold that produces a weld using a 90TON injection molding machine, the appearance was visually judged under a standard light source.
(8)熱変形温度;ASTM D−648(荷重18.
6kg/cシ アニールなし)(9)グラフト率および
極限粘度の測定方法グラフト率およびグラフト効率ニゲ
ラフト重合体の一定1 (X)をアセトン中に投入し、
振とう機で2時間振とうし、遊離の共重合体を溶解させ
る。遠心分離機を用いて、この溶液を23.000rp
w+で30分間遠心分離し、不溶分を得る。次に真空乾
燥機を用いて120 ”Cで1時間乾燥し、不溶分(y
)および遊離の共重合体を得る。グラフト率は次式より
算出した。(8) Heat distortion temperature; ASTM D-648 (load 18.
6kg/c (without cyanyl) (9) Grafting rate and intrinsic viscosity measurement method Grafting rate and grafting efficiency A constant amount of Niger raft polymer 1 (X) was poured into acetone,
Shake on a shaker for 2 hours to dissolve free copolymer. Using a centrifuge, spin this solution at 23,000 rpm.
Centrifuge at w+ for 30 minutes to obtain insoluble matter. Next, the insoluble matter (y
) and free copolymer are obtained. The grafting rate was calculated using the following formula.
00)粒子径の測定方法
射出成形で得た成形品を用い、超薄切片を作製したのち
、四酸化ルテニウムにて染色し、透過型電子顕微鏡にて
観察し、測定した。00) Method for Measuring Particle Size Using a molded article obtained by injection molding, ultrathin sections were prepared, stained with ruthenium tetroxide, observed with a transmission electron microscope, and measured.
表=1に示す結果から明らかなように、ABA 、 A
Bなど各タイプの特定構造のブロック共重合体をベース
ゴムとした特定構造のグラフト重合体(実施例1〜15
)は、着色性、ウェルド部外観などの成形外観に優れ、
さらに低温衝撃強度および耐薬品性に優れた耐候性樹脂
である。As is clear from the results shown in Table 1, ABA, A
Graft polymers with a specific structure using each type of block copolymer with a specific structure such as B as a base rubber (Examples 1 to 15)
) has excellent molding appearance such as colorability and weld area appearance,
Furthermore, it is a weather-resistant resin with excellent low-temperature impact strength and chemical resistance.
一方、比較例1および2は、数平均分子量が発明の範囲
以外のものであり、5000以下である比較例1では、
衝撃強度が非常に低く、また1、000,000以上で
ある比較例2では、着色性、ウェルド外観が悪くなる。On the other hand, in Comparative Examples 1 and 2, the number average molecular weight is outside the range of the invention, and in Comparative Example 1, which is 5000 or less,
In Comparative Example 2, which has a very low impact strength and is 1,000,000 or more, the colorability and weld appearance are poor.
比較例−3は分子量分布(Mw/Mn)が10以上のも
のであり、着色性およびウェルド外観が悪いことを示し
ている。Comparative Example 3 has a molecular weight distribution (Mw/Mn) of 10 or more, indicating poor colorability and weld appearance.
比較例−4および5は、水添前のジエン部の1.2ビニ
ル含率が10%以下また90%以上のものであり、どち
らも低温度での落錘衝撃強度が低いことを示している。In Comparative Examples 4 and 5, the 1.2 vinyl content of the diene part before hydrogenation was 10% or less and 90% or more, and both showed low falling weight impact strength at low temperatures. There is.
比較例−6は、水添率が70%以下のものであり、耐候
性が悪いことを示している。Comparative Example 6 has a hydrogenation rate of 70% or less, indicating poor weather resistance.
比較例−7は、グラフトモノマーとしてスチレンを単独
で用いたものであり、衝撃強度、着色性、ウェルド外観
、耐薬品性および耐候性が悪いことを示している。Comparative Example 7 uses styrene alone as the graft monomer, and shows poor impact strength, colorability, weld appearance, chemical resistance, and weather resistance.
比較例日は、グラフト率が20%以下のものであり、着
色性、ウェルド外観および耐薬品性が悪い、一方、比較
例9は、グラフト率が90%以上のものであり、衝撃強
度が低下する。In Comparative Example 9, the grafting rate was 20% or less, and the colorability, weld appearance, and chemical resistance were poor. On the other hand, in Comparative Example 9, the grafting rate was 90% or more, and the impact strength was decreased. do.
比較例1Oは、グラフトゴム粒子径が0.05μ以下の
ものであり、耐衝撃性を維持することができず、比較例
11は、グラフトゴム粒子径が0.5μ以上のものであ
り、着色性およびウェルド外観が悪い。Comparative Example 1O has a graft rubber particle size of 0.05μ or less and cannot maintain impact resistance, and Comparative Example 11 has a graft rubber particle size of 0.5μ or more and is not colored. Poor quality and weld appearance.
比較例12は、ベースゴムとしてEPDMを用いたもの
であり、着色性およびウェルド外観が悪く、比較例13
は、ベースゴムとしてブタジェンゴム(B12)を用い
たものであり、耐候性が悪い。Comparative Example 12 uses EPDM as the base rubber, and has poor coloring and weld appearance.
uses butadiene rubber (B12) as the base rubber and has poor weather resistance.
f、 発明の効果
本発明のゴム変性熱可望性樹脂およびゴム変性熱可塑性
樹脂組成物は、着色性、ウェルド部の外観などの成形外
観に優れ、低温域での衝撃強度、特に落錘衝撃強度およ
び耐薬品性に優れている。f. Effects of the Invention The rubber-modified thermoplastic resin and rubber-modified thermoplastic resin composition of the present invention have excellent molding appearance such as colorability and welded part appearance, and have excellent impact strength at low temperatures, especially falling weight impact. Excellent strength and chemical resistance.
このため、 自動車などの車輌の外装部品・外装材 などとして好適であり、 その用途は極めて広い。For this reason, Exterior parts and materials for vehicles such as automobiles It is suitable as Its uses are extremely wide.
Claims (2)
ブロック共重合体で、その重合体の数平均分子量が5,
000〜1,000,000、重量平均分子量(Mw)
と数平均分子量(Mn)の比(Mw/Mn)が10以下
、かつジエン部のビニル結合含有量が10〜90%であ
り、ジエン重合体部分を水素添加して該重合体のオレフ
ィン性不飽和結合の少なくとも70%が水素添加された
水添ジエン系重合体(i)5〜80重量部の存在下に、
芳香族ビニル化合物(A)5〜98重量%およびこれと
共重合可能な単量体化合物(B)95〜2重量%からな
る単量体混合物(ii)95〜20重量部をグラフト共
重合させた、グラフト率が20〜90%で、かつグラフ
トゴム粒子の重量平均粒子径が0.05〜0.5μであ
ることを特徴とするゴム変性熱可塑性樹脂。(1) A block copolymer consisting of an aromatic vinyl compound and a conjugated diene compound, with a number average molecular weight of 5,
000-1,000,000, weight average molecular weight (Mw)
and number average molecular weight (Mn) (Mw/Mn) is 10 or less, and the vinyl bond content of the diene part is 10 to 90%, and the diene polymer part is hydrogenated to form an olefinic compound of the polymer. In the presence of 5 to 80 parts by weight of a hydrogenated diene polymer (i) in which at least 70% of the saturated bonds are hydrogenated,
Graft copolymerizing 95 to 20 parts by weight of a monomer mixture (ii) consisting of 5 to 98% by weight of an aromatic vinyl compound (A) and 95 to 2% by weight of a monomer compound (B) copolymerizable therewith. Further, a rubber-modified thermoplastic resin having a graft ratio of 20 to 90% and a weight average particle diameter of grafted rubber particles of 0.05 to 0.5 μ.
80重量部と、α−メチルスチレン、N−置換マレイミ
ド化合物、その他の芳香族ビニル化合物、シアン化ビニ
ル化合物、および(メタ)アクリル酸アルキルエステル
から選ばれた少くとも2種の化合物の共重合体80〜2
0重量部からなるゴム変性熱可塑性樹脂組成物。(2) Rubber-modified thermoplastic resin 20 according to claim (1)
80 parts by weight and at least two compounds selected from α-methylstyrene, N-substituted maleimide compounds, other aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic acid alkyl esters. 80-2
A rubber-modified thermoplastic resin composition consisting of 0 parts by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1080789A JP2707700B2 (en) | 1989-03-31 | 1989-03-31 | Rubber-modified thermoplastic resin and rubber-modified thermoplastic resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1080789A JP2707700B2 (en) | 1989-03-31 | 1989-03-31 | Rubber-modified thermoplastic resin and rubber-modified thermoplastic resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02258816A true JPH02258816A (en) | 1990-10-19 |
JP2707700B2 JP2707700B2 (en) | 1998-02-04 |
Family
ID=13728221
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1080789A Expired - Lifetime JP2707700B2 (en) | 1989-03-31 | 1989-03-31 | Rubber-modified thermoplastic resin and rubber-modified thermoplastic resin composition |
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JP (1) | JP2707700B2 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6176518A (en) * | 1984-08-31 | 1986-04-19 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Denatured block copolymer and manufacture |
JPS62169812A (en) * | 1985-12-23 | 1987-07-27 | ノバコア ケミカルズ(インターナショナル)ソシエテ アノニム | Production of thermoplastic composition |
JPS638410A (en) * | 1986-06-30 | 1988-01-14 | Nippon Erasutomaa Kk | Improved impact-resistance styrene resin |
-
1989
- 1989-03-31 JP JP1080789A patent/JP2707700B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6176518A (en) * | 1984-08-31 | 1986-04-19 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Denatured block copolymer and manufacture |
JPS62169812A (en) * | 1985-12-23 | 1987-07-27 | ノバコア ケミカルズ(インターナショナル)ソシエテ アノニム | Production of thermoplastic composition |
JPS638410A (en) * | 1986-06-30 | 1988-01-14 | Nippon Erasutomaa Kk | Improved impact-resistance styrene resin |
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