JP4053292B2 - Thermoplastic resin composition - Google Patents
Thermoplastic resin composition Download PDFInfo
- Publication number
- JP4053292B2 JP4053292B2 JP2001393211A JP2001393211A JP4053292B2 JP 4053292 B2 JP4053292 B2 JP 4053292B2 JP 2001393211 A JP2001393211 A JP 2001393211A JP 2001393211 A JP2001393211 A JP 2001393211A JP 4053292 B2 JP4053292 B2 JP 4053292B2
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- JP
- Japan
- Prior art keywords
- group
- resin composition
- thermoplastic resin
- component
- composition according
- 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.)
- Expired - Fee Related
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- 229920005992 thermoplastic resin Polymers 0.000 title claims description 34
- 239000011342 resin composition Substances 0.000 title claims description 31
- -1 polypropylene Polymers 0.000 claims description 60
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- 239000000178 monomer Substances 0.000 claims description 35
- 229920002554 vinyl polymer Polymers 0.000 claims description 33
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 229920005668 polycarbonate resin Polymers 0.000 claims description 20
- 239000004431 polycarbonate resin Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 238000010526 radical polymerization reaction Methods 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 9
- 229920005990 polystyrene resin Polymers 0.000 claims description 9
- 229920005669 high impact polystyrene Polymers 0.000 claims description 8
- 239000004797 high-impact polystyrene Substances 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 2
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000005504 styryl group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000005641 methacryl group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000012463 white pigment Substances 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
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 125000006043 5-hexenyl group Chemical group 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 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
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 229940065472 octyl acrylate Drugs 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- KUGVQHLGVGPAIZ-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KUGVQHLGVGPAIZ-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- OPOGSUPDESSLJJ-UHFFFAOYSA-N 1-butoxybutane;oxolane Chemical compound C1CCOC1.CCCCOCCCC OPOGSUPDESSLJJ-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Description
【０００１】
【発明の属する技術分野】
本発明は熱可塑性樹脂組成物に関し、詳しくは、熱安定性、成形加工性に優れ、成形後は、機械的強度、色調に優れた成形品となり得る熱可塑性樹脂組成物に関する。
【０００２】
【従来の技術】
ポリカーボネート樹脂、ポリプロピレン樹脂、ポリスチレン樹脂等の熱可塑性樹脂は、エンジニアリングプラスチックとして、電気・電子機器、自動車、土木・建築等数多くの分野で使用されている。このような熱可塑性樹脂には、通常、機械的強度を向上させるためとか、色相の向上あるいは着色のために様々な無機粉体が配合されている。
ところが、この種の無機粉体は、しばしば、熱可塑性樹脂の耐熱性を低下させるという問題点があった。例えば、ポリカーボネート樹脂には酸化チタンに代表される白色顔料が配合されているが、この白色顔料は、ポリカーボネート樹脂の分子量の低下を引き起こし、その結果、ポリカーボネート樹脂本来の機械的強度を低下させるという問題点があった。また、白色顔料自体の熱安定性が低下して色調が低下する等の問題点があった。同様に、酸化チタンを配合したポリプロピレン樹脂、高衝撃ポリスチレン樹脂、ＡＢＳ樹脂等の有機樹脂についても、流動性が低下して成形性が低下したり、機械的強度が低下する等の問題点があった。従来、このような問題点を解消するために、例えば、ポリカーボネート樹脂に酸化チタンと共に、分子鎖側鎖にトリメトキシシリル基を有するジメチルポリシロキサンを配合した組成物が提案されている（特開平６−２００１４０号公報参照）。しかし、この組成物といえども、必ずしも十分とはいえず用途によっては、使用できないものであった。
【０００３】
【発明が解決しようとする課題】
本発明者らは上記問題点を解決すべく鋭意検討した結果、熱可塑性樹脂に特定のビニル系重合体を配合すれば上記問題点が大幅に解消されることを見出し本発明に到達した。
即ち、本発明の目的は、熱安定性、成形加工性に優れ、成形後は、機械的強度、色調に優れた成形品となり得る熱可塑性樹脂組成物を提供することにある。
【０００４】
【課題を解決するための手段】
本発明は、
（Ａ）熱可塑性樹脂（１００重量部）、（Ｂ）（ａ）ビニル系単量体（ただし、該単量体はケイ素原子結合水素原子を含有しない。）と（ｂ）下記式（１）で表される分子中にケイ素原子結合水素原子を含有するビニル系単量体とをラジカル重合して得られた分子中にケイ素原子結合水素原子を有するビニル系重合体（０．０１〜５０重量部）
【化３】
【０００５】
【発明の実施の形態】
これを説明すると、（Ａ）熱可塑性樹脂は、成形可能な熱可塑性を有する有機樹脂であり、これには、一般に、熱可塑性樹脂と呼称されている有機樹脂および熱可塑性エラストマーと呼称されている有機樹脂が含まれる。このような熱可塑性樹脂の具体的例としては、ポリエチレン（ＰＥ）樹脂、低密度ポリエチレン（ＬＤＰＥ）樹脂、中密度ポリエチレン樹脂、高密度ポリエチレン（ＨＤＰＥ）樹脂、超高分子量ポリエチレン（ＵＨＭＰＥ）樹脂、エチレンとプロピレン,ブテン−１,ペンテン−１,ヘキセン−１,４−メチルペンテン−１,オクテン−１,デセン−１等の炭素数３〜１２のα−オレフィンとの共重合体、ポリプロピレン（ＰＰ）樹脂、プロピレンとブテン−１,ペンテン−１,ヘキセン−１,４−メチルペンテン−１,オクテン−１,デセン−１等の炭素数３〜１２のα−オレフィンとの共重合体、エチレン−プロピレン−ジエン共重合体、ポリメチルペンテン樹脂（ＭＰＸ），エチレン−メタアクリル酸エステル共重合体樹脂、エチレンと酢酸ビニル、マレイン酸、無水マレイン酸等のビニル系モノマーとの共重合体樹脂等のポリオレフィン系樹脂；ポリメチルメタアクリレート（ＰＭＭＡ）樹脂などのアクリル系樹脂；ポリスチレン（ＰＳ）樹脂、高衝撃性ポリスチレン（ＨＩＰＳ）樹脂、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）共重合体樹脂、アクリロニトリル−スチレン（ＡＳ）共重合体樹脂、アクリロニトリル−アクリルゴム−スチレン（ＡＡＳ）共重合体樹脂、アクリロニトリル−エチレンプロピレンゴム−スチレン（ＡＥＳ）共重合体樹脂などのスチレン系樹脂；ポリ酢酸ビニル樹脂、ポリ塩化ビニル（ＰＶＣ）樹脂、ポリ塩化ビニリデン（ＰＶＤＣ）樹脂、ポリビニルアルコール樹脂（ＰＶＡ）、ポリテトラフルオロエチレン樹脂（ＰＴＦＥ）などの他のビニル系樹脂；ポリブチレンテレフタレート（ＰＢＴ）樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂などのポリエステル樹脂；ナイロン６、ナイロン６６、ナイロン６１０、ナイロン１１、ナイロン１２等のポリアミド樹脂；ポリアセタール（ＰＯＭ）等のポリオキシアルキレン樹脂；ポリカーボネート（ＰＣ）樹脂；変性ポリフェニレンエーテル（変性ＰＰＥ）樹脂；ポリ酢酸ビニル（ＰＶＡＣ）樹脂；ポリサルフォン（ＰＳＵ）樹脂、ポリエーテルサルフォン（ＰＥＳ）樹脂、ポリフェニレンサルファイド（ＰＰＳ）樹脂等のポリサルファイド系樹脂；ポリアレート（ＰＡＲ）樹脂；ポリアミドイミド（ＰＡＩ）樹脂；ポリエーテルイミド（ＰＥＩ）樹脂；ポリエーテルエーテルケトン（ＰＥＥＫ）樹脂；ポリイミド（ＰＩ）樹脂；液晶ポリエステル（ＬＣＰ）樹脂およびこれらの共重合体が挙げられる。また、一般に、熱可塑性エラストマーと呼称されているポリスチレン系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリアミド系樹脂、ポリフッ素系樹脂、ポリ塩化ビニル系樹脂等も使用することもができる。これらの中でも、ポリカーボネート系樹脂、ポリオレフィン系樹脂、ポリスチレン系樹脂が好ましい。
【０００６】
（Ｂ）ケイ素原子結合水素原子を含有するビニル系重合体は本発明の特徴となる成分であり、（Ａ）成分中に（Ｃ）成分を均一に分散させる働きをすると共に、（Ｃ）成分に起因する（Ａ）成分の劣化を防止する働きをする。（Ｂ）成分の性状は特に限定されないが、粉体処理能の点で室温において液状であることが好ましい。
このようなビニル系重合体は、（ａ）ビニル系単量体（ただし、該単量体はケイ素原子結合水素原子を含有しない。）と（ｂ）分子中にケイ素原子結合水素原子を含有するビニル系単量体をラジカル重合して得られる。ここで使用される（ａ）ビニル系単量体は、ラジカル重合性のビニル基を有するものであり、かつ、ケイ素原子結合水素原子を含有しないものであればよく、その種類等については特に限定されない。
【０００７】
このような（ａ）成分としては、例えば、アクリル酸メチル、メタアクリル酸メチル、アクリル酸エチル、メタアクリル酸エチル、アクリル酸ｎ−プロピル、メタアクリル酸ｎ−プロピル、アクリル酸イソプロピル、メタアクリル酸イソプロピル等の低級アルキルアクリレートもしくはメタアクリレート；アクリル酸ｎ−ブチル、メタアクリル酸ｎ−ブチル、アクリル酸イソブチル、メタアクリル酸イソブチル、アクリル酸ｔｅｒｔ−ブチル、メタアクリル酸ｔｅｒｔ−ブチル、メタアクリル酸ｎ−ヘキシル、アクリル酸−シクロヘキシル、アクリル酸２−エチルヘキシル、アクリル酸オクチル、アクリル酸ラウリル、アクリル酸ステアリル等の高級アルキルアクリレートもしくはメタアクリレート；酢酸ビニル、プロピオン酸ビニル等の低級脂肪酸ビニルエステル；酪酸ビニル、カプロン酸ビニル、２−エチルヘキサン酸ビニル、ラウリル酸ビニル、ステアリン酸ビニル等の高級脂肪酸ビニルエステル；スチレン、ビニルトルエン等のスチレン系単量体；ベンジルアクリレート、ベンジルメタアクリレート、フェノキシエチルアクリレート、フェノキシエチルメタアクリレート、ビニルピロリドン等の芳香族基含有アクリレートもしくはメタアクリレート；アクリルアミド、メタアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタアクリルアミド、Ｎ−メトキシメチルアクリルアミド、Ｎ−メトキシメチルメタアクリルアミド、イソブトキシメトキシアクリルアミド、イソブトキシメトキシメタアクリルアミド、Ｎ,Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルメタアクリルアミド等のアミド基含有ビニル系単量体；アクリル酸グリシジル、メタアクリル酸グリシジル、３，４−エポキシシクロヘキシルメチルアクリレート、３，４−エポキシシクロヘキシルメチルメタアクリレート等のエポキシ基含有ビニル系単量体；２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタアクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシプロピルメタアクリレート、２−ヒドロキシブチルアクリレート、２−ヒドロキシブチルメタアクリレート等の水酸基含有ビニル系単量体：アクリル酸、メタアクリル酸、イタコン酸、クロトン酸、フマル酸、マレイン酸等のカルボン酸基含有ビニル単量体；テトラヒドロフルフリルアクリレート、テトラヒドロフルフリルメタアクリレート，ブトキシエチルアクリレート、ブトキシエチルアクリレート、ブトキシエチルメタアクリレート、エトキシジエチレングリコールアクリレート、エトキシジエチレングリコールメタアクリレート、ポリエチレングリコールアクリレート、ポリエチレングリコールメタアクリレート、ポリプロピレングリコールモノアクリレート、ポリプロピレングリコールモノメタアクリレート、ヒドロキシブチルビニルエーテル、セチルビニルエーテル、２ーエチルヘキシルビニルエーテル等のエーテル結合含有ビニル系単量体；ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタアクリレート、ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタアクリレート等のアミノ基含有ビニル系単量体；トリフルオロプロピルアクリレート、トリフルオロプロピルメタアクリレート、パーフルオロブチルエチルメタアクリレート、パーフルオロブチルエチルアクリレート、パーフルオロオクチルエチルメタアクリレート等のフッ素含有ビニル系単量体；ブタジエン、イソプレン等のジエン系単量体類；塩化ビニル、塩化ビニリデン等のハロゲン化ビニル系単量体類；アクリロニトリル等のニトリル系単量体類；分子鎖片末端にアクリル基もしくはメタアクリル基、スチリル基等のラジカル重合性官能基を含有するジオルガノポリシロキサン類；フマル酸ジブチル；無水マレイン酸；ドデシル無水コハク酸；スチレンスルホン酸のようなスルホン酸基を有するラジカル重合性不飽和単量体、およびそれらのアルカリ金属塩、アンモニウム塩、有機アミン塩；２−ヒドロキシ−３−メタクリロキシプロピルトリメチルアンモニウムクロライドのようなメタクリル酸から誘導される４級アンモニウム塩、メタクリル酸ジエチルアミンエステルのような３級アミン基を有するアルコールのメタクリル酸エステル、およびそれらの４級アンモニウム塩等が例示される。
【０００８】
また、（a）成分として多官能ビニル単量体を使用することもできる。このような単量体としては、アリルアクリレート、アリルメタクリレート等のアルケニルアクリレートもしくはメタクリレート類；トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタアクリレート、エチレングリコールジアクリレート、エチレングリコールジメタアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ポリエチレングリコールジメタアクリレート、１,４−ブタンジオールジアクリレート、１,４−ブタンジオールジメタアクリレート、１，６−ヘキサンジオールジアクリレート、１，６−ヘキサンジオールジメタアクリレート、 ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタアクリレート、トリメチロールプロパントリオキシエチルアクリレート、トリメチロールプロパントリオキシエチルメタアクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートジアクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートジメタアクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリアクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリメタアクリレート、ビスフェノールＡのエチレンオキサイドまたはプロピレンオキサイド付加体ジオールのジアクリレートもしくはジメタアクリレート、水添ビスフェノールＡのエチレンオキサイドまたはプロピレンオキサイド付加体、ジオールのジアクリレートもしくはジメタアクリレート、メタクリロキシプロピル基含有ポリジメチルシロキサン、ジビニルベンゼン、トリエチレングリコールジビニルエーテル、スチリル基含有ポリジメチルシロキサンが例示される。
【０００９】
これらの中でも（a）成分は、アクリル酸メチル、メタアクリル酸メチル、アクリル酸エチル、メタアクリル酸エチル、アクリル酸ｎ−プロピル、メタアクリル酸ｎ−プロピル、アクリル酸イソプロピル、メタアクリル酸イソプロピル等の低級アルキルアクリレートもしくはメタアクリレート；アクリル酸ｎ−ブチル、メタアクリル酸ｎ−ブチル、アクリル酸イソブチル、メタアクリル酸イソブチル、アクリル酸ｔｅｒｔ−ブチル、メタアクリル酸ｔｅｒｔ−ブチル、アクリル酸ｎ−ヘキシル、メタアクリル酸ｎ−ヘキシル、アクリル酸シクロヘキシル、アクリル酸２−エチルヘキシル、アクリル酸オクチル、アクリル酸ラウリル、アクリル酸ステアリル等の高級アルキルアクリレートもしくはメタアクリレートが好ましい。
【００１０】
（ｂ）分子中にケイ素原子結合水素原子を含有するビニル系単量体は、下記化学構造式（１）で示される化合物をラジカル重合して得られる。
【化４】
また、Ｒ2は炭素原子数１〜１０のアルキル基もしくはアリール基、炭素数１〜１０アルコキシ基もしくはアリーロキシ基であり、アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、イソプロピル基、イソブチル基、シクロペンチル基、シクロヘキシル基が例示され、アリール基としては、フェニル基、ナフチル基が例示される。これらの中でもメチル基が好ましい。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ペンチロキシ基、イソプロポキシ基、イソブトキシ基、シクロペンチロキシ基、シクロヘキシロキシ基が例示され、アリーロキシ基としては、フェノキシ基、ナフチロキシ基が例示される。これらの中でもメトキシ基が好ましい。また、分子鎖片末端にメタクリロキシ基、アクリロキシ基、スチリル基、アルケニル基等のラジカル重合性基を有し、側鎖または末端にケイ素原子結合水素原子を有するオルガノポリシロキサンが挙げられる。
【００１１】
Ｘはラジカル重合可能な有機基であり、例えば、一般式：
【化５】
【化６】
【化７】
一般式：
ａは０を含まない３以下の整数で、ｂは０もしく３未満の整数であり、ｃは０もしくは３未満の整数であり、ａ＋ｂ＋ｃ＝３である。
【００１２】
このような（ｂ）成分としては、下記化学構造式で示される化合物が例示される。式中、Ｍｅはメチル基である。
【化８】
【００１３】
（Ｂ）成分は上記のような（a）成分と（b）成分をラジカル重合させることによって製造できる。このラジカル重合は、有機溶媒の存在下、または非存在下で行われる。有機溶剤を使用する場合は、このラジカル重合は、ラジカル開始剤の存在下、５０〜１５０℃で３〜２０時間反応させることにより進行する。このとき用いる有機溶媒としては、ヘキサン、オクタン、デカン、シクロヘキサン等の脂肪族炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素；ジエチルエーテル、ジブチルエーテルテトラヒドロフラン、ジオキサン等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン等のケトン類；酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル等のエステル類；メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類が例示される。これらの中でもトルエンまたはキシレンが好適に使用される。ラジカル開始剤としては、通常、ラジカル重合法に使用される従来公知のものが用いられるが、具体的には、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、 ２，２’−アゾビス（２，４−ジメチルバレロニトリル）等のアゾビス系化合物；過酸化ベンゾイル、過酸化ラウロイル、ｔｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート等の有機過酸化物が例示される。ラジカル開始剤の使用量は、上記（a）成分と（b）成分の合計１００重重部に対して０、１〜５重量部の範囲であることが好ましい。また、ラジカル重合する際には、更に連鎖移動剤を添加することができる。この連鎖移動剤としては、具体的には、２−メルカプトエタノール、ブチルメルカプタン、ｎ−ドデシルメルカプタン、３−メルカプトプロピルトリメトキシシラン等のメルカプト化合物；塩化メチレン、クロロホム、四塩化炭素、臭化ブチル、３−クロロプロピルトリメトキシシラン等のハロゲン化物が挙げられる。
【００１４】
（Ｂ）成分は分子中にケイ素原子結合水素原子を有することを必須とするものであるが、このケイ素原子結合水素原子に加えて、ケイ素原子結合のアルコキシ基を含有していてもよい。このケイ素原子結合アルコキシ基を含有する化合物は、(a)成分(ｂ)成分に加えて (c) 分子中にアルコキシシリル基を有するビニル系単量体を共重合することによって得られる。このような（ｃ）成分は、一般式：
【化１７】
上式中、Ｘはラジカル重合可能な有機基であり、例えば、一般式：
【化１８】
【化１９】
【化２０】
上式中、R9は炭素原子数１〜１０のアルキル基もしくはアリール基であり、アルキル基としては、メチル基，エチル基，プロピル基，ブチル基，ペンチル基，イソプロピル基，イソブチル基，シクロペンチル基，シクロヘキシル基が例示され、アリール基としては、フェニル基，ナフチル基が例示される。これらの中でもメチル基，フェニル基が好ましく、メチル基が特に好ましい。また、R10は炭素原子数１〜１０のアルキル基もしくはアリール基であり、アルキル基としてはメチル基，エチル基，プロピル基，ブチル基，ペンチル基，イソプロピル基，イソブチル基，シクロペンチル基，シクロヘキシル基が例示され、アリール基としては、フェニル基，ナフチル基が例示される。これらの中でもメチル基、エチル基が好ましく、メチル基が特に好ましい。ａは０を含まない３以下の正数で、ｂは０もしく３未満の正数であり、ａ＋ｂ＝３である。
【００１５】
このような（ｃ）成分としては、下記平均組成式で示される化合物が例示される。
【化２１】
【００１６】
（Ｃ）無機粉体は、熱可塑性樹脂に配合することが公知とされる無機粉体であればよく、その種類等は特に限定されない。このような無機粉体としては、例えば、酸化チタン、酸化亜鉛、アルミナ、シリカ、酸化カルシウム、酸化マグネシウム、酸化鉄、酸化アンチモン、フェライト等の金属酸化物；水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム等の金属水酸化物；炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸バリウム、ドーソナイト、ハイドロタルサイト等の炭酸塩；硫酸カルシウム、硫酸バリウム、石膏等の硫酸塩；シリカ、珪酸カルシウム、タルク、クレー、マイカ、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、ガラス繊維、ガラスビーズ等のケイ酸塩；窒化アルミニウム、窒化ホウ素、窒化ケイ素等の窒化物等が挙げられる。これらの中でも、酸化チタンが好ましい。
【００１７】
（Ｃ）成分の配合量は、（Ａ）成分１００重量部に対して、０．０１〜２００重量部であるが、好ましくは、０．１〜１００重量部であり、さらに好ましくは０．２〜５０重量部である。０．１重量部未満では、（Ｃ）成分の配合効果がなく、２００重量部以上では得られた熱可塑性樹脂組成物の機械的強度が損なわれるためである。
【００１８】
本発明の熱可塑性樹脂組成物は、上記のような（Ａ）成分〜（Ｃ）成分からなるが、これらの成分に加えて、熱可塑性樹脂に添加配合することが公知とされる各種添加剤、例えば、紫外線吸収剤、耐光安定剤、耐熱安定剤、酸化防止剤、可塑剤、発泡剤、滑剤、帯電防止剤、導電性付与剤、顔料や染料などの着色剤、相溶化剤、架橋剤、難燃剤、防カビ剤、低収縮剤、増粘剤、離型剤、防曇剤、ブルーイング剤、シランカップリング剤等を配合することは、本発明の目的を損なわない限り差支えない。
【００１９】
本発明の熱可塑性樹脂組成物は、上記のような（Ａ）成分〜（Ｃ）成分およびこれらの成分に加えて必要に応じて各種添加剤を均一に混合することにより、容易に製造される。製造装置としては、バンバリーミキサー、ニーダーミキサー、熱２ロールミル等に代表される回分式混練機、あるいは単軸押出機、２軸押出機等に代表される連続混練押出機等の熱可塑性樹脂組成物の製造に使用されている従来周知の混練装置が適用可能である。
【００２０】
【実施例】
次に、本発明を実施例にて詳細に説明する。
実施例中、部とあるのは重量部のことであり、Ｍeはメチル基であり、粘度は２５℃における値である。熱可塑性樹脂組成物成形品の外観、白色度、アイゾット衝撃強度およびポリカーボネート樹脂の分子量は次に示す方法に従って測定した。
＜成形品の外観＞
表面がクロムメッキされた鏡面仕上げ金型を備えた小型の射出成形機（ＣＳＩ製）を用いて、直径４ｃｍ、厚さ２ｍｍの円板状成形品を成形した。この成形品の外観を肉眼にて観察した。
＜成形品の白色度＞
上記で得られた直径４ｃｍ、厚さ２ｍｍの円板状成形品の表面を、色彩色差計｛ミノルタカメラ（株）製、ＣＲ−２００｝を用いて測定し、下式により白色度（％）を求めた。なお、下式においてＬはＬａｂ系色標における明度であり、ａおよびｂはＬａｂ系色標における知覚色度指数である。
白色度（％）＝１００−〔（１００−Ｌ）2 ＋（ａ2＋ｂ2）〕1/2
＜成形品のアイゾット衝撃強度＞
ＪＩＳ Ｋ７１１０に準じて測定した。即ち、小型の射出成形機（ＣＳＩ製）を用いて、アイゾット衝撃用試験用成形片を成形し、ＪＩＳ Ｋ７１１０に基づいてアイゾット衝撃強度（ノッチ付）を測定した。
＜成形品中のポリカーボネート樹脂の分子量＞
ポリカーボネート樹脂をクロロホルムに溶解し遠心分離した後、上澄み液をゲル透過クロマトグラフィー（ＧＰＣ）にて分析した。検出器は屈折率（ＲＩ）および紫外線（ＵＶ）検出機を用いた。得られた溶出曲線を標準分子量ポリスチレン樹脂で検量し標準分子量ポリスチレン樹脂にて換算した分子量｛数平均分子量（Ｍｎ）｝を測定した。
【００２１】
【参考例１】
攪拌装置、温度計、還流管を取付けた２００ｍＬの４つ口フラスコに、ｎ−ブチルアクリレート（以下、ｎＢＡ）６５ｇ、下記化学構造式（２）で示されるケイ素原子結合水素原子含有ビニル単量体｛γ−メタクリロキシプロピルトリス（ジメチルハイドロジェンシロキシ）シラン｝３０ｇ、メルカプトプロピルトリメトキシシラン５ｇ、２，２’−アゾビス−２−メチルブチロニトリル｛大塚化学（株）製｝（以下、ＡＭＢＮ）２ｇ、トルエン１００ｇを仕込み、窒素雰囲気下、７０℃にて６時間加熱攪拌した。次いでアスピレーターおよび真空ポンプにて減圧下、加熱攪拌することにより、低揮発成分を除去した。得られた反応混合物を２００メッシュの金網でろ過し、分子中にケイ素原子結合水素原子を含有するポリブチルアクリレート共重合体｛以下、ＰＢＡ重合体 （Ｂ−１）｝８８ｇを得た。この共重合体の仕込み組成を表１に示した。また、このビニル系共重合体の色相、粘度、分子量を測定し、それらの結果を表１に示した。分子量はゲル透過クロマトグラフィー（ＧＰＣ）にて測定し、標準分子量ポリスチレン樹脂にて換算した分子量｛数平均分子量（Ｍｎ）｝を測定した。
【化２９】
【参考例２】
参考例１において、化学構造式（２）で示されるケイ素原子結合水素原子含有ビニル重合体３０ｇの代わりに、化学構造式（２）で示されるケイ素原子結合水素原子含有ビニル単量体１５ｇと下記化学構造式（３）で示されるケイ素原子結合メトキシ基含有ビニル単量体１５ｇを使用した以外は、参考例１と同様にして、分子中にケイ素原子結合水素原子とケイ素原子結合メトキシ基とを含有するポリブチルアクリレート共重合体｛以下、ＰＢＡ重合体 （Ｂ−２）｝９３ｇを得た。この共重合体の仕込み組成を表１に示した。また、この共重合体の色相、粘度、数平均分子量（Ｍｎ）を測定し、それらの結果を表１に示した。
【化３０】
【表１】
【実施例１】
ラボプラストミル（３０ｃｃ、東洋精機製作所製）に、芳香族ポリカーボネート樹脂｛出光石油化学（株）製、商品名タフロンＡ１９００、数平均分子量Ｍｎ＝１８０００｝１００部、参考例１で得られたＰＢＡ重合体 （Ｂ−１）１部、ルチル型酸化チタン粉末（石原産業株式会社製、商品名タイペークＣＲ−６０、平均粒子径０．２１μm）１０部を仕込み、２８０℃、１００ｒｐｍにて１０分間混練し、ポリカーボネート樹脂組成物を製造した。得られた熱可塑性樹脂組成物の特性を測定して、それらの結果を表２および表３に示した。
【００２５】
【実施例２】
実施例１において、ＰＢＡ重合体 （Ｂ−１）１部の替わりに、参考例２で得られたＰＢＡ重合体 （Ｂ−２）１部を配合した以外は、実施例１と同様にして、ポリカーボネート樹脂組成物を製造した。このポリカーボネート樹脂組成物の特性を測定して、それらの結果を表２および表３に示した。
【００２６】
【比較例１】
実施例１において、ＰＢＡ重合体 （Ｂ−１）１部を配合しなかった以外は、実施例１と同様にして、ポリカーボネート樹脂組成物を製造した。このポリカーボネート樹脂組成物の特性を実施例１と同様にして測定して、それらの結果を表２および表３に示した。
【００２７】
【比較例２】
実施例１において、ＰＢＡ重合体 （Ｂ−１）１部の替わりに、粘度２０mPa・sの両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン｛東レ・ダウコーニング・シリコーン（株）製、商品名ＳＨ１１０７｝１部を配合した以外は、実施例１と同様にして、ポリカーボネート樹脂組成物を製造した。このポリカーボネート樹脂組成物の特性を実施例１と同様に測定して、それらの結果を表２および表３に示した。
【００２８】
【比較例３】
実施例１において、参考例１で得られたＰＢＡ重合体（Ｂ−１）１部の替わりに、粘度が４０ｍＰａ・ｓである分子鎖両末端がトリメチルシロキシ基で封鎖され、分子鎖側鎖のメチル基の一部がトリメトキシシリル基に置換されたポリジメチルシロキサン（このポリジメチルシロキサンは、分子中にケイ素原子結合水素原子を有さない。）｛東レ・ダウコーニング・シリコーン（株）製、商品名ＢＹ１６−１６０｝１部を配合した以外は、実施例１と同様にして、ポリカーボネート樹脂組成物を製造した。このポリカーボネート樹脂組成物の特性を実施例１と同様に測定して、それらの結果を表２および表３に示した。
【００２９】
【表２】
【表３】
【実施例３】
ラボプラストミル（３０ｃｃ、東洋精機製作所製）に、ポリプロピレン樹脂（住友化学工業製、商品名ノーブレンＹ１０１）１００部、参考例１で得られたＰＢＡ重合体 （Ｂ−１）１部、ルチル型酸化チタン粉末（石原産業株式会社製、商品名タイペークＴＴＯ−５５（Ｂ）、粒子径０．０２〜０．０５μm）１０部を仕込み、２４０℃、１００ｒｐｍにて１０分間混練し、ポリプロピレン樹脂組成物を製造した。得られたポリプロピレン樹脂組成物の外観を観察して、その結果を表４に示した。
【００３２】
【比較例４】
実施例３において、参考例１で得られたビニル系樹脂（Ｂ−１）１部を配合しなかった以外は、実施例３と同様にして、ポリプロピレン樹脂組成物を調製した。このポリプロピレン樹脂組成物の特性を測定して、それらの結果を表４に示した。
【００３３】
【実施例４】
ラボプラストミル（３０ｃｃ、東洋精機製作所製）に、高衝撃ポリスチレン樹脂（旭化成工業株式会社製、商品名スタイロン４９２）１００部、参考例１で得られたＰＢＡ重合体 （Ｂ−１）１部、ルチル型酸化チタン粉末（石原産業株式会社製、商品名タイペークＴＴＯ−５５（Ｂ）、粒子径０．０２〜０．０５μm）１０部を仕込み、２２０℃、１００ｒｐｍにて１０分間混練し、高衝撃ポリスチレン樹脂組成物を製造した。この高衝撃ポリスチレン樹脂組成物の外観を観察し、その結果を表４に示した。
【００３４】
【比較例５】
実施例４において、参考例１で得られたビニル系樹脂（Ｂ−１）１部を配合しなかった以外は、実施例４と同様にして、高衝撃ポリスチレン樹脂組成物を調製した。この高衝撃ポリスチレン樹脂組成物の特性を測定して、それらの結果を表４に示した。
【００３５】
【表４】
【発明の効果】
本発明の熱可塑性樹脂組成物は、（Ａ）成分〜（Ｃ）成分からなり、特に（Ｂ）分子中にケイ素原子結合水素原子を有するビニル系重合体を含有しているので、熱安定性、成形加工性に優れ、成形後は、機械的強度、色調に優れた成形品となり得るという特徴を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition that is excellent in thermal stability and molding processability, and can be a molded product excellent in mechanical strength and color tone after molding.
[0002]
[Prior art]
Thermoplastic resins such as polycarbonate resin, polypropylene resin and polystyrene resin are used as engineering plastics in many fields such as electric / electronic devices, automobiles, civil engineering / architecture. Such thermoplastic resins are usually blended with various inorganic powders for improving mechanical strength, improving hue, or coloring.
However, this type of inorganic powder often has the problem of reducing the heat resistance of the thermoplastic resin. For example, a white pigment typified by titanium oxide is blended in a polycarbonate resin, but this white pigment causes a decrease in the molecular weight of the polycarbonate resin, resulting in a problem that the original mechanical strength of the polycarbonate resin is reduced. There was a point. In addition, there is a problem that the thermal stability of the white pigment itself is lowered and the color tone is lowered. Similarly, organic resins such as polypropylene resin, high-impact polystyrene resin, and ABS resin blended with titanium oxide have problems such as poor fluidity and moldability and mechanical strength. It was. Conventionally, in order to solve such problems, for example, a composition in which polycarbonate resin is blended with titanium oxide and dimethylpolysiloxane having a trimethoxysilyl group in the side chain of the molecular chain has been proposed (Japanese Patent Laid-Open No. Hei 6). -Refer to -200140 gazette). However, even this composition is not necessarily sufficient and cannot be used depending on the application.
[0003]
[Problems to be solved by the invention]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be largely solved by blending a specific vinyl polymer into a thermoplastic resin, and have reached the present invention.
That is, an object of the present invention is to provide a thermoplastic resin composition that is excellent in thermal stability and molding processability, and can be a molded product having excellent mechanical strength and color tone after molding.
[0004]
[Means for Solving the Problems]
The present invention
(A) Thermoplastic resin (100 parts by weight), (B)(A) vinyl monomer (however, this monomer does not contain a silicon atom-bonded hydrogen atom) and (b) a molecule represented by the following formula (1) contains a silicon atom-bonded hydrogen atom. Obtained by radical polymerization with vinyl monomersVinyl polymer having silicon-bonded hydrogen atoms in the molecule (0.01-50 parts by weight)
[Chemical 3]
[0005]
DETAILED DESCRIPTION OF THE INVENTION
To explain this, (A) the thermoplastic resin is an organic resin having a moldable thermoplasticity, and is generally called an organic resin and a thermoplastic elastomer generally called a thermoplastic resin. Organic resin is included. Specific examples of such thermoplastic resins include polyethylene (PE) resin, low density polyethylene (LDPE) resin, medium density polyethylene resin, high density polyethylene (HDPE) resin, ultra high molecular weight polyethylene (UHMPE) resin, ethylene A copolymer of propylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, octene-1, decene-1, etc., and an α-olefin having 3 to 12 carbon atoms, polypropylene (PP) Resin, copolymer of propylene and α-olefin having 3 to 12 carbon atoms such as butene-1, pentene-1, hexene-1,4-methylpentene-1, octene-1, decene-1, etc., ethylene-propylene -Diene copolymer, polymethylpentene resin (MPX), ethylene-methacrylate copolymer resin, ethylene and vinyl acetate, Ynoic acid, with vinyl monomers such as maleic anhydrideCopolymerPolyolefin resins such as resins; Acrylic resins such as polymethyl methacrylate (PMMA) resins; Polystyrene (PS) resins, High impact polystyrene (HIPS) resins, Acrylonitrile-butadiene-styrene (ABS) copolymer resins, Acrylonitrile -Styrene resins such as styrene (AS) copolymer resin, acrylonitrile-acrylic rubber-styrene (AAS) copolymer resin, acrylonitrile-ethylene propylene rubber-styrene (AES) copolymer resin; polyvinyl acetate resin, poly Other vinyl resins such as vinyl chloride (PVC) resin, polyvinylidene chloride (PVDC) resin, polyvinyl alcohol resin (PVA), polytetrafluoroethylene resin (PTFE); polybutylene terephthalate (PBT) resin, polyethylene Polyester resin such as terephthalate (PET) resin; Polyamide resin such as nylon 6, nylon 66, nylon 610, nylon 11 and nylon 12; Polyoxyalkylene resin such as polyacetal (POM); Polycarbonate (PC) resin; Modified polyphenylene ether ( Modified PPE) resin; polyvinyl acetate (PVAC) resin; polysulfone resin such as polysulfone (PSU) resin, polyethersulfone (PES) resin, polyphenylene sulfide (PPS) resin; polyarate (PAR) resin; polyamideimide (PAI) ) Resin; polyetherimide (PEI) resin; polyetheretherketone (PEEK) resin; polyimide (PI) resin; liquid crystal polyester (LCP) resin and copolymers thereof.In addition, polystyrene resins, polyolefin resins, polyester resins, polyurethane resins, polyamide resins, polyfluorine resins, polyvinyl chloride resins, etc., generally called thermoplastic elastomers can also be used. . Among these, polycarbonate resins, polyolefin resins, and polystyrene resins are preferable.
[0006]
(B) The vinyl polymer containing a silicon atom-bonded hydrogen atom is a component that characterizes the present invention, and functions to uniformly disperse the component (C) in the component (A) and the component (C). It functions to prevent the deterioration of the component (A) caused by. Although the property of (B) component is not specifically limited, It is preferable that it is liquid at room temperature from the point of powder processing ability.
Such a vinyl polymer contains (a) a vinyl monomer (provided that the monomer does not contain a silicon atom-bonded hydrogen atom) and (b) a silicon atom-bonded hydrogen atom in the molecule. It can be obtained by radical polymerization of vinyl monomers. The (a) vinyl monomer used here has only to have a radical-polymerizable vinyl group and does not contain a silicon atom-bonded hydrogen atom. Not.
[0007]
Examples of the component (a) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, and methacrylic acid. Lower alkyl acrylate or methacrylate such as isopropyl; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-methacrylate Higher alkyl acrylates or methacrylates such as hexyl, acrylate-cyclohexyl, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate; low such as vinyl acetate, vinyl propionate Fatty acid vinyl esters; higher fatty acid vinyl esters such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate and vinyl stearate; styrene monomers such as styrene and vinyltoluene; benzyl acrylate and benzyl methacrylate , Aromatic group-containing acrylates or methacrylates such as phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone; acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylate Acrylamide, isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide, N, N-dimethylacrylamide, N, N-dimethyl Amide group-containing vinyl monomers such as rumethacrylamide; epoxy group-containing vinyl monomers such as glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate Body; hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate and 2-hydroxybutyl methacrylate: Carboxylic acid group-containing vinyl monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid; tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate Butoxyethyl acrylate, butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethylene glycol acrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2 -Ether-containing vinyl monomers such as ethylhexyl vinyl ether; amino group-containing vinyl monomers such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate; trifluoropropyl acrylate , Fluorine-containing vinyl monomers such as trifluoropropyl methacrylate, perfluorobutyl ethyl methacrylate, perfluorobutyl ethyl acrylate and perfluorooctyl ethyl methacrylate; diene monomers such as butadiene and isoprene; Vinyl halide monomers such as vinyl and vinylidene chloride; nitrile monomers such as acrylonitrile; difunctional monomers containing radically polymerizable functional groups such as acryl, methacryl and styryl groups at one end of the molecular chain Organopolysiloxanes; Dibutyl fumarate; Maleic anhydride; Dodecyl succinic anhydride; Radical polymerizable unsaturated monomers having sulfonic acid groups such as styrene sulfonic acid, and alkali metal salts, ammonium salts, organic amines thereof Salt; 2-hydroxy-3- Examples include quaternary ammonium salts derived from methacrylic acid such as tacryloxypropyltrimethylammonium chloride, methacrylic acid esters of alcohols having tertiary amine groups such as diethylamine methacrylate, and quaternary ammonium salts thereof. The
[0008]
A polyfunctional vinyl monomer can also be used as the component (a). Such monomers include alkenyl acrylates or methacrylates such as allyl acrylate and allyl methacrylate; trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethylene glycol diacrylate , Ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol di Acrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate Rate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl acrylate, trimethylolpropane trioxyethyl methacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, tris (2-hydroxyethyl) isocyanurate dimethacrylate , Tris (2-hydroxyethyl) isocyanurate triacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, bisphenol A ethylene oxide or propylene oxide adduct diol diacrylate or dimethacrylate, hydrogenated bisphenol A Ethylene oxide or propylene oxide adduct, diol diacrylate or dimethacrylate, Methacryloxypropyl group-containing polydimethylsiloxane, divinylbenzene, triethylene glycol divinyl ether, styryl group-containing polydimethyl siloxane and the like.
[0009]
Among these, the component (a) includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and the like. Lower alkyl acrylate or methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, methacryl Higher alkyl acrylates or methacrylates such as acid n-hexyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate and stearyl acrylate are preferred.
[0010]
(B) A vinyl monomer containing a silicon-bonded hydrogen atom in the molecule is a compound represented by the following chemical structural formula (1)Obtained by radical polymerization of.
[Formula 4]
R2Is an alkyl group or aryl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryloxy group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, Examples include an isobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Among these, a methyl group is preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a pentyloxy group, an isopropoxy group, an isobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group, and examples of the aryloxy group include a phenoxy group and a naphthyloxy group. . Among these, a methoxy group is preferable. Moreover, organopolysiloxane having a radical polymerizable group such as a methacryloxy group, an acryloxy group, a styryl group, and an alkenyl group at one end of the molecular chain and a silicon atom-bonded hydrogen atom at the side chain or the terminal can be mentioned.
[0011]
X is a radically polymerizable organic group, for example, the general formula:
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
General formula:
a is an integer of 3 or less not including 0, b is an integer of 0 or less than 3, c is an integer of 0 or less than 3, and a + b + c = 3.
[0012]
Examples of such component (b) include compounds represented by the following chemical structural formulas. In the formula, Me is a methyl group.
[Chemical 8]
[0013]
The component (B) can be produced by radical polymerization of the above components (a) and (b). This radical polymerization is performed in the presence or absence of an organic solvent. When an organic solvent is used, this radical polymerization proceeds by reacting at 50 to 150 ° C. for 3 to 20 hours in the presence of a radical initiator. Examples of the organic solvent used here include aliphatic hydrocarbons such as hexane, octane, decane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, dibutyl ether tetrahydrofuran and dioxane; acetone and methyl ethyl ketone And ketones such as methyl isobutyl ketone and diisobutyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; and alcohols such as methanol, ethanol, isopropanol and butanol. Of these, toluene or xylene is preferably used. As the radical initiator, conventionally known ones used in radical polymerization methods are usually used. Specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2 -Methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) and other azobis compounds; benzoyl peroxide, lauroyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-2 -Organic peroxides such as ethyl hexanoate are exemplified. It is preferable that the usage-amount of a radical initiator is the range of 0, 1-5 weight part with respect to the total 100 weight part of the said (a) component and (b) component. Further, a chain transfer agent can be further added during radical polymerization. Specific examples of the chain transfer agent include mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan and 3-mercaptopropyltrimethoxysilane; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, Halides such as 3-chloropropyltrimethoxysilane are exemplified.
[0014]
The component (B) essentially has a silicon-bonded hydrogen atom in the molecule, but may contain a silicon-bonded alkoxy group in addition to the silicon-bonded hydrogen atom. The compound containing a silicon atom-bonded alkoxy group can be obtained by copolymerizing a vinyl monomer having an alkoxysilyl group in the molecule in addition to the component (a) and the component (b). Such component (c) has the general formula:
Embedded image
In the above formula, X is a radically polymerizable organic group, for example, the general formula:
Embedded image
Embedded image
Embedded image
In the above formula, R9Is an alkyl group or aryl group having 1 to 10 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. RTenIs an alkyl group or aryl group having 1 to 10 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable. a is a positive number of 3 or less not including 0, b is a positive number of 0 or less than 3, and a + b = 3.
[0015]
Examples of such component (c) include compounds represented by the following average composition formula.
Embedded image
[0016]
(C) Inorganic powder should just be an inorganic powder known to mix | blend with a thermoplastic resin, The kind etc. are not specifically limited. Examples of such inorganic powder include metal oxides such as titanium oxide, zinc oxide, alumina, silica, calcium oxide, magnesium oxide, iron oxide, antimony oxide, and ferrite; calcium hydroxide, magnesium hydroxide, hydroxide Metal hydroxides such as aluminum; carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite and hydrotalcite; sulfates such as calcium sulfate, barium sulfate and gypsum; silica, calcium silicate, talc and clay Silicates such as mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber and glass beads; nitrides such as aluminum nitride, boron nitride and silicon nitride. Among these, titanium oxide is preferable.
[0017]
(C) The compounding quantity of component is 0.01-200 weight part with respect to 100 weight part of (A) component, Preferably, it is 0.1-100 weight part, More preferably, it is 0.2. ~ 50 parts by weight. If it is less than 0.1 part by weight, there is no blending effect of component (C), and if it is 200 parts by weight or more, the mechanical strength of the obtained thermoplastic resin composition is impaired.
[0018]
The thermoplastic resin composition of the present invention comprises the components (A) to (C) as described above. In addition to these components, various additives known to be added and blended with thermoplastic resins are known. , For example, UV absorbers, light stabilizers, heat stabilizers, antioxidants, plasticizers, foaming agents, lubricants, antistatic agents, conductivity-imparting agents, colorants such as pigments and dyes, compatibilizers, crosslinking agents Incorporating a flame retardant, an antifungal agent, a low shrinkage agent, a thickening agent, a mold release agent, an antifogging agent, a bluing agent, a silane coupling agent and the like can be carried out as long as the object of the present invention is not impaired.
[0019]
The thermoplastic resin composition of the present invention is easily produced by uniformly mixing components (A) to (C) as described above and various additives as necessary in addition to these components. . As a production apparatus, a thermoplastic resin composition such as a batch kneader represented by a Banbury mixer, a kneader mixer, a hot two-roll mill or the like, or a continuous kneading extruder represented by a single screw extruder, a twin screw extruder or the like A conventionally known kneading apparatus used in the production of can be applied.
[0020]
【Example】
Next, the present invention will be described in detail with reference to examples.
In the examples, parts are parts by weight, Me is a methyl group, and the viscosity is a value at 25 ° C. The appearance, whiteness, Izod impact strength, and molecular weight of the polycarbonate resin were measured according to the following methods.
<Appearance of molded product>
A disk-shaped molded product having a diameter of 4 cm and a thickness of 2 mm was molded using a small injection molding machine (manufactured by CSI) equipped with a mirror-finished mold whose surface was chrome-plated. The appearance of this molded product was observed with the naked eye.
<Whiteness of molded products>
The surface of the disk-shaped molded product having a diameter of 4 cm and a thickness of 2 mm obtained above was measured using a color difference meter {CR-200} manufactured by Minolta Camera Co., Ltd., and the whiteness (%) was calculated according to the following formula. Asked. In the following equation, L is the lightness in the Lab color target, and a and b are the perceptual chromaticity index in the Lab color target.
Whiteness (%) = 100 − [(100−L)2 + (A2+ B2)]1/2
<Izod impact strength of molded products>
It measured according to JIS K7110. That is, using a small injection molding machine (manufactured by CSI), Izod impact test pieces were molded, and Izod impact strength (notched) was measured based on JIS K7110.
<Molecular weight of polycarbonate resin in molded product>
The polycarbonate resin was dissolved in chloroform and centrifuged, and then the supernatant was analyzed by gel permeation chromatography (GPC). The detector used was a refractive index (RI) and ultraviolet (UV) detector. The obtained elution curve was calibrated with a standard molecular weight polystyrene resin, and the molecular weight {number average molecular weight (Mn)} converted with the standard molecular weight polystyrene resin was measured.
[0021]
[Reference Example 1]
In a 200 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, 65 g of n-butyl acrylate (hereinafter, nBA), a silicon atom-bonded hydrogen atom-containing vinyl monomer represented by the following chemical structural formula (2) {Γ-methacryloxypropyltris (dimethylhydrogensiloxy) silane} 30 g, mercaptopropyltrimethoxysilane 5 g, 2,2′-azobis-2-methylbutyronitrile {manufactured by Otsuka Chemical Co., Ltd.} (hereinafter AMBN) 2 g of toluene and 100 g of toluene were charged, and the mixture was heated and stirred at 70 ° C. for 6 hours in a nitrogen atmosphere. Subsequently, the low volatile component was removed by heating and stirring under reduced pressure with an aspirator and a vacuum pump. The obtained reaction mixture was filtered through a 200-mesh wire mesh to obtain 88 g of a polybutyl acrylate copolymer {hereinafter referred to as PBA polymer (B-1)} containing silicon-bonded hydrogen atoms in the molecule. The charge composition of this copolymer is shown in Table 1. Further, the hue, viscosity, and molecular weight of this vinyl copolymer were measured, and the results are shown in Table 1. The molecular weight was measured by gel permeation chromatography (GPC), and the molecular weight {number average molecular weight (Mn)} converted by standard molecular weight polystyrene resin was measured.
Embedded image
[Reference Example 2]
In Reference Example 1, instead of 30 g of the silicon atom-bonded hydrogen atom-containing vinyl polymer represented by the chemical structural formula (2), 15 g of the silicon atom-bonded hydrogen atom-containing vinyl monomer represented by the chemical structural formula (2) and A silicon atom-bonded hydrogen atom and a silicon atom-bonded methoxy group were added to the molecule in the same manner as in Reference Example 1 except that 15 g of a silicon monomer having a silicon atom-bonded methoxy group represented by the chemical structural formula (3) was used. 93 g of polybutyl acrylate copolymer contained {hereinafter referred to as PBA polymer (B-2)} was obtained. The charge composition of this copolymer is shown in Table 1. Further, the hue, viscosity and number average molecular weight (Mn) of this copolymer were measured, and the results are shown in Table 1.
Embedded image
[Table 1]
[Example 1]
Laboplast mill (30 cc, manufactured by Toyo Seiki Seisakusho Co., Ltd.), aromatic polycarbonate resin {manufactured by Idemitsu Petrochemical Co., Ltd., trade name Toughon A1900, number average molecular weight Mn = 18000}, 100 parts, PBA weight obtained in Reference Example 1 1 part of coalescence (B-1), 10 parts of rutile type titanium oxide powder (Ishihara Sangyo Co., Ltd., trade name, Taipei CR-60, average particle size 0.21 μm) are charged and kneaded at 280 ° C. and 100 rpm for 10 minutes. A polycarbonate resin composition was produced. The properties of the obtained thermoplastic resin composition were measured, and the results are shown in Table 2 and Table 3.
[0025]
[Example 2]
In Example 1, instead of 1 part of the PBA polymer (B-1), the same procedure as in Example 1 was conducted except that 1 part of the PBA polymer (B-2) obtained in Reference Example 2 was blended. A polycarbonate resin composition was produced. The properties of this polycarbonate resin composition were measured and the results are shown in Tables 2 and 3.
[0026]
[Comparative Example 1]
In Example 1, a polycarbonate resin composition was produced in the same manner as in Example 1 except that 1 part of the PBA polymer (B-1) was not blended. The properties of this polycarbonate resin composition were measured in the same manner as in Example 1, and the results are shown in Tables 2 and 3.
[0027]
[Comparative Example 2]
In Example 1, instead of 1 part of PBA polymer (B-1), both ends of a trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 20 mPa · s {trade name SH1107, manufactured by Toray Dow Corning Silicone Co., Ltd. } A polycarbonate resin composition was produced in the same manner as in Example 1 except that 1 part was blended. The properties of this polycarbonate resin composition were measured in the same manner as in Example 1, and the results are shown in Tables 2 and 3.
[0028]
[Comparative Example 3]
In Example 1, instead of 1 part of the PBA polymer (B-1) obtained in Reference Example 1, both ends of the molecular chain having a viscosity of 40 mPa · s are blocked with trimethylsiloxy groups, Polydimethylsiloxane in which a part of the methyl group is substituted with a trimethoxysilyl group (this polydimethylsiloxane does not have a silicon atom-bonded hydrogen atom in the molecule) {made by Toray Dow Corning Silicone Co., Ltd., A polycarbonate resin composition was produced in the same manner as in Example 1 except that 1 part of the trade name BY16-160} was blended. The properties of this polycarbonate resin composition were measured in the same manner as in Example 1, and the results are shown in Tables 2 and 3.
[0029]
[Table 2]
[Table 3]
[Example 3]
Laboplast mill (30cc, manufactured by Toyo Seiki Seisakusho), 100 parts of polypropylene resin (trade name Nobren Y101, manufactured by Sumitomo Chemical Co., Ltd.), 1 part of PBA polymer (B-1) obtained in Reference Example 1, rutile type oxidation 10 parts of titanium powder (made by Ishihara Sangyo Co., Ltd., trade name Typeke TTO-55 (B), particle size 0.02 to 0.05 μm) is charged and kneaded at 240 ° C. and 100 rpm for 10 minutes to obtain a polypropylene resin composition. Manufactured. The appearance of the obtained polypropylene resin composition was observed, and the results are shown in Table 4.
[0032]
[Comparative Example 4]
In Example 3, a polypropylene resin composition was prepared in the same manner as in Example 3 except that 1 part of the vinyl resin (B-1) obtained in Reference Example 1 was not blended. The properties of this polypropylene resin composition were measured and the results are shown in Table 4.
[0033]
[Example 4]
Laboplast mill (30 cc, manufactured by Toyo Seiki Seisakusho), 100 parts of high impact polystyrene resin (trade name Stylon 492, manufactured by Asahi Kasei Kogyo Co., Ltd.), 1 part of PBA polymer (B-1) obtained in Reference Example 1, 10 parts of rutile-type titanium oxide powder (Ishihara Sangyo Co., Ltd., trade name Typeke TTO-55 (B), particle size 0.02 to 0.05 μm) was charged, kneaded at 220 ° C. and 100 rpm for 10 minutes, and high impact A polystyrene resin composition was produced. The appearance of this high impact polystyrene resin composition was observed, and the results are shown in Table 4.
[0034]
[Comparative Example 5]
In Example 4, a high-impact polystyrene resin composition was prepared in the same manner as in Example 4 except that 1 part of the vinyl resin (B-1) obtained in Reference Example 1 was not blended. The properties of this high impact polystyrene resin composition were measured and the results are shown in Table 4.
[0035]
[Table 4]
【The invention's effect】
The thermoplastic resin composition of the present invention comprises (A) component to (C) component, and particularly (B) contains a vinyl polymer having a silicon atom-bonded hydrogen atom in the molecule, so that it is thermally stable. It has the characteristics that it is excellent in molding processability and can be a molded product having excellent mechanical strength and color tone after molding.
Claims (11)
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| JP2001393211A JP4053292B2 (en) | 2001-12-26 | 2001-12-26 | Thermoplastic resin composition |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001393211A JP4053292B2 (en) | 2001-12-26 | 2001-12-26 | Thermoplastic resin composition |
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| JP2003192903A JP2003192903A (en) | 2003-07-09 |
| JP2003192903A5 JP2003192903A5 (en) | 2005-07-28 |
| JP4053292B2 true JP4053292B2 (en) | 2008-02-27 |
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| JP2003192903A (en) | 2003-07-09 |
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