JP4136117B2 - Thermoplastic resin composition - Google Patents
Thermoplastic resin composition Download PDFInfo
- Publication number
- JP4136117B2 JP4136117B2 JP27697598A JP27697598A JP4136117B2 JP 4136117 B2 JP4136117 B2 JP 4136117B2 JP 27697598 A JP27697598 A JP 27697598A JP 27697598 A JP27697598 A JP 27697598A JP 4136117 B2 JP4136117 B2 JP 4136117B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- meth
- component
- 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.)
- Expired - Fee Related
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- 229920005992 thermoplastic resin Polymers 0.000 title claims description 36
- 239000011342 resin composition Substances 0.000 title claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 229920002554 vinyl polymer Polymers 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000000962 organic group Chemical group 0.000 claims description 22
- 239000000412 dendrimer Substances 0.000 claims description 21
- 229920000736 dendritic polymer Polymers 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- 125000005353 silylalkyl group Chemical group 0.000 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000005504 styryl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000005641 methacryl group Chemical group 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- -1 methylmethylene group Chemical group 0.000 description 53
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- 229920005989 resin Polymers 0.000 description 31
- 239000011347 resin Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000035699 permeability Effects 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 14
- 238000000465 moulding Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 8
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 8
- 239000004926 polymethyl methacrylate Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 125000004837 1-methylpentylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 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
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 239000003999 initiator Substances 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
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004711 α-olefin 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
- 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 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- 150000002009 diols Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 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
- 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
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-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
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- INTFCWANRCGCRZ-UHFFFAOYSA-N 3-tris(dimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound C[SiH](C)O[Si](O[SiH](C)C)(O[SiH](C)C)CCCOC(=O)C(C)=C INTFCWANRCGCRZ-UHFFFAOYSA-N 0.000 description 1
- FMBJBXGKLDTRLU-UHFFFAOYSA-N 3-tris(dimethylsilyloxy)silylpropyl prop-2-enoate Chemical compound C[SiH](C)O[Si](O[SiH](C)C)(O[SiH](C)C)CCCOC(=O)C=C FMBJBXGKLDTRLU-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical class C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- 229920005507 ACRYPET® MF Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
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、さらに詳しくは、離型性、成形性、撥水性、酸素透過性等の特性が優れた各種成形品を与え得る熱可塑性樹脂組成物に関するものである。
【０００２】
【従来の技術】
オレフィン系樹脂、スチレン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂およびハロゲン化ビニル系樹脂等の熱可塑性樹脂は、すぐれた物理的特性を有することから、各種成形品の材料として広く使用されている。
しかしながら、この種の熱可塑性樹脂は、離型性、成形性および撥水性等が劣るという欠点を有しているため、それらの改良を目的として従来から種々の検討がなされてきた。
【０００３】
なかでも、シリコーンオイルやシリコーン生ゴム等の線状ポリオルガノシロキサンは、すぐれた界面特性を有することから、熱可塑性樹脂の離型性、成形性および撥水性等を改良するための添加剤として使用されており、実際に特公昭５７−１０１４４号公報によりこの種の提案もなされている。
【０００４】
しかし、一般にポリオルガノシロキサンと熱可塑性樹脂とは相溶性が劣り、例えばＡＳ樹脂やＡＢＳ樹脂等の熱可塑性樹脂に対し、ポリオルガノシロキサンを微細な形態で均一に分散させることが困難であった。そのためポリオルガノシロキサンを添加混合した熱可塑性樹脂は作業性が悪く、また成形品においてもポリオルガノシロキサンがブリードアウトしたり、分離による外観不良を生じる等の不具合があるばかりか、さらには成形品ごとの離型性、成形性および撥水性等にバラツキを生じる等の問題があった。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、離型性、成形性、撥水性、酸素透過性等の特性に優れた各種成形品を与えることができる熱可塑性樹脂組成物を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意検討した結果、熱可塑性樹脂に対する添加剤成分として、従来の線状ポリオルガノシロキサンの代わりに、特定の分岐構造、つまりカルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体を用いることによつて、熱可塑性樹脂と添加剤成分との相溶性が良好で、潤滑性、離型性、成形性、撥水性、ガス透過性および機械的強度等の各種特性が均衡にすぐれ、しかも添加剤成分のブリードアウトや分離がなく、外観が良好な各種成形品を与え得る熱可塑性樹脂組成物が得られることを見出し、本発明に到達した。
【０００７】
本発明の熱可塑性樹脂組成物は、下記式で示される基であるカルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体（Ａ）および該（Ａ）成分以外の熱可塑性樹脂（Ｂ）からなり、該（Ｂ）成分１００重量部に対し前記（Ａ）成分を０．０１〜５００重量部含有することを特徴とするものである。
【化８】
【化９】
【０００８】
【発明の実施の形態】
以下に、本発明の熱可塑性樹脂組成物について具体的に説明する。
本発明の熱可塑性樹脂組成物における一方の成分であるビニル系重合体（Ａ）とは、カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体である。かかる成分（Ａ）は、その重合体の側鎖にカルボシロキサンデンドリマー構造を含有するのであるが、本発明において、デンドリマー構造とは、一つの核から放射線状に高度に規則的に枝分れした高分子量の基を意味する。このような構造を有するカルボシロキサンデンドリマーとしては、例えば、高分岐状シロキサン・シルアルキレン共重合体がある（特願平９−１７１１５４号明細書参照）。
本発明において、ビニル系重合体（Ａ）中のカルボシロキサンデンドリマー構造は、次に示す一般式で示される基である。
【０００９】
【化１０】
上記の式中、Ｚは２価有機基であり、アルキレン基、アリーレン基、アラルキレン基、エステル含有２価有機基、エーテル含有２価有機基、ケトン含有２価有機基、アミド基含有２価有機基が例示され、これらの中でも、次式で示される有機基が好ましい。
【００１１】
【化１１】
【化１２】
【化１３】
上式中、Ｒ9 は炭素原子数１〜１０のアルキレン基であり、メチレン基、エチレン基、プロピレン基、ブチレン基が例示され、メチレン基、プロピレン基が好ましく、Ｒ10は炭素原子数１〜１０のアルキル基であり、メチル基、エチル基はプロピル基、ブチル基が例示され、これらの中でもメチル基が好ましく、Ｒ11は炭素原子数１〜１０のアルキレン基であり、メチレン基、エチレン基、プロピレン基、ブチレン基が例示され、これらの中でもエチレン基が好ましく、ｄは０〜４の整数であり、ｅは０または１である。Ｒ1 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。Ｘ1 はｉ＝１とした場合の次式で示されるシリルアルキル基である。
【００１５】
【化１４】
（式中、Ｒ1 は前記と同じであり、Ｒ2 は炭素原子数２〜１０のアルキレン基であり、エチレン基，プロピレン基，ブチレン基，ヘキシレン基等の直鎖状アルキレン基；メチルメチレン基，メチルエチレン基，１−メチルペンチレン基，１, ４−ジメチルブチレン基等の分岐状アルキレン基が例示される。これらの中でも、エチレン基，メチルエチレン基，ヘキシレン基，１−メチルペンチレン基，１, ４−ジメチルブチレン基が好ましい。Ｒ3 は炭素原子数１〜１０のアルキル基であり、メチル基，エチル基，プロピル基，ブチル基，イソプロピル基が例示される。ｉは該シリルアルキル基の階層を示している１〜１０の整数であり、 ａi は０〜３の整数である。）。
【００１７】
本発明の熱可塑性樹脂組成物においては、なかでも次のようなカルボシロキサンデンドリマー構造を含有する分岐状オルガノシロキサン系重合体（Ａ）が好ましく用いられる。
すなわち、（ａ）ビニル系単量体０〜９９．９重量部と、（ｂ）一般式：
【００１８】
【化１５】
｛式中、Ｙはラジカル重合可能な有機基であり、Ｒ1 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。Ｘ1 はｉ＝１とした場合の次式で示されるシリルアルキル基である。
【００２０】
【化１６】
（式中、Ｒ1 は前記と同じであり、Ｒ2 は炭素原子数２〜１０のアルキレン基であり、Ｒ3 は炭素原子数１〜１０のアルキル基であり、メチレン基、エチレン基、プロピレン基、ブチレン基が例示される。Ｘi+1 は水素原子，炭素原子数１〜１０のアルキル基，アリール基および上記シリルアルキル基からなる群から選択される基である。i は該シリルアルキル基の階層を示している１〜１０の整数であり、ａi は０〜３の整数である。）｝で示されるラジカル重合可能な有機基を含有するカルボシロキサンデンドリマー１００〜０．１重量部を重合させてなるカルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体である。 このビニル系重合体（Ａ）についてさらに説明するに、（ａ）成分のビニル系単量体は、ラジカル重合性のビニル基を有するものであればよく、その種類等については特に限定されない。かかるビニル系単量体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−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（メタ）アクリレート；（メタ）アクリル酸グリシジル；（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸ｎ−ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル等の高級（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エステル；スチレン、ビニルトルエン、ベンジル（メタ）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ビニル型単量体；（メタ）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（メタ）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（メタ）アクリルアミド等のアミド基含有ビニル型単量体；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル等の水酸基含有ビニル型単量体；（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含有ビニル型単量体、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（メタ）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（メタ）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型単量体；（メタ）アクリロキシプロピルトリメトキシシラン、片末端に（メタ）アクリル基を含有した（分岐状あるいは、直鎖状）ポリジメチルシロキサン、片末端にスチリル基を含有するポリジメチルシロキサン等の不飽和基含有シリコ−ン化合物；ブタジエン；塩化ビニル；塩化ビニリデン；（メタ）アクリロニトリル；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；（メタ）アクリルグリシジルエーテル：（メタ）アクリル酸、イタコン酸、クロトン酸、フマル酸、マレイン酸等のラジカル重合性不飽和カルボン酸のアルカリ金属塩、アンモニウム塩、有機アミン塩；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−メタクリルオ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）ア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級アンモニウム塩が例示される。
【００２２】
また多官能ビニル系単量体も使用可能であり、例えば、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（メタ）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（メタ）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（メタ）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（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（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（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（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の付加体のジオールのジ（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の付加体のジオールのシ（メタ）アクリレート、トリエチレングリコールジビニルエーテル等の（メタ）アクリロイル基含有単量体、ジビニルベンゼン、両末端スチリル基封鎖ポリジメチルシロキサン等の不飽和基含有シリコ−ン化合物等が例示される。
【００２３】
（ｂ）成分のカルボシロキサンデンドリマーは、一般式：
【化１７】
【００２４】
上記の式中、Ｙはラジカル重合可能な有機基であり、ラジカル付加反応可能な有機基であればよいが、具体的には、下記一般式で表されるで示される（メタ）アクリロキシ基含有有機基、（メタ）アクリルアミド基含有有機基、スチリル基含有有機基または炭素原子数２〜１０のアルケニル基が挙げられる。
【００２５】
【化１８】
【化１９】
【化２０】
（上式中、Ｒ4 およびR6は水素原子もしくはメチル基であり、Ｒ5 およびＲ8 は炭素原子数１〜１０のアルキレン基であり、Ｒ7 は炭素原子数１〜１０のアルキル基である。ｂは０〜４の整数であり、ｃは０または１である。）
このようなラジカル重合可能な有機基としては、例えば、アクリロキシメチル基，３−アクリロキシプロピル基，メタクリロキシメチル基，３−メタクリロキシプロピル基，４−ビニルフェニル基，３−ビニルフェニル基，４−（２−プロペニル）フェニル基，３−（２−プロペニル）フェニル基，２−（４−ビニルフェニル）エチル基，２−（３−ビニルフェニル）エチル基，ビニル基，アリル基，メタリル基，５−ヘキセニル基が挙げられる。Ｒ1 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、Ｘ1 はｉ＝１とした場合の次式で示されるシリルアルキル基である。
【００２９】
【化２１】
上記の式中、Ｒ2 は炭素原子数２〜１０のアルキレン基であり、エチレン基，プロピレン基，ブチレン基，ヘキシレン基等の直鎖状アルキレン基；メチルメチレン基，メチルエチレン基，１−メチルペンチレン基，１, ４−ジメチルブチレン基等の分岐状アルキレン基が例示される。これらの中でも、エチレン基，メチルエチレン基，ヘキシレン基，１−メチルペンチレン基，１, ４−ジメチルブチレン基が好ましい。Ｒ3 は炭素原子数１〜１０のアルキル基であり、メチル基，エチル基，プロピル基，ブチル基，イソプロピル基が例示される。Ｒ1 は前記と同じである。Ｘi+1 は水素原子，炭素原子数１〜１０のアルキル基，アリール基および上記シリルアルキル基からなる群から選択される基である。ａi は０〜３の整数である。i は１〜１０の整数であり、これは該シリルアルキル基の階層数、すなわち該シリルアルキル基の繰り返し数を示している。したがって、階層数が１である場合に、本成分のカルボシロキサンデンドリマーは、一般式：
【００３１】
【化２２】
（式中、Ｙ，Ｒ1 ，Ｒ2 およびＲ3 は前記と同じであり、Ｒ12は水素原子または前記R1と同じである。ａ1 は前記ａi と同じであるが、１分子中のａ1 の平均合計数は０〜７である。）で示さる。階層数が２である場合には、本成分のカルボシロキサンデンドリマーは、一般式：
【００３３】
【化２３】
【００３４】
【化２４】
（式中、Ｙ，Ｒ1 ，Ｒ2 ，Ｒ3 およびＲ12は前記と同じである。ａ1,ａ2 およびａ3 は前記ａi と同じであるが、１分子中のａ1 とａ2 とａ3 の平均合計数は０〜７９である。）で示される。
本成分のラジカル重合可能な有機基を含有するカルボキシデンドリマーとしては、下記平均組成式で示されるカルボシロキサンデンドリマーが例示される。
【００３６】
【化２５】
【化２６】
【化２７】
【化２８】
【化２９】
【化３０】
【化３１】
【化３２】
【化３３】
【化３４】
【化３５】
【化３６】
【化３７】
【化３８】
このようなカルボシロキサンデンドリマーは、特願平９−１７１１５４号明細書に記載された分岐状シロキサン・シルアルキレン共重合体の製造方法にしたがって製造できる。例えば、一般式：
【００５１】
【化３９】
（式中、Ｒ1 およびＹは前記と同じである。）で示されるケイ素原子結合水素原子含有ケイ素化合物と、アルケニル基含有有機ケイ素化合物とを、ヒドロシリル化反応させることにより製造することができる。上式で示されるケイ素化合物としては、例えば３−メタクリロキシプロピルトリス（ジメチルシロキシ）シラン，３−アクリロキシプロピルトリス（ジメチルシロキシ）シラン，４−ビニルフェニルトリス（ジメチルシロキシ）シランが用いられ、アルケニル基含有有機ケイ素化合物としては、ビニルトリス（トリメチルシロキシ）シラン，ビニルトリス（ジメチルフェニルシロキシ）シラン，５−ヘキセニルトリス（トリメチルシロキシ）シランが用いられる。なお、このヒドロシリル化反応は塩化白金酸や白金ビニルシロキサン錯体等の遷移金属触媒の存在下に行なうのが好ましい。
【００５３】
本発明に使用される（Ａ）カルボシロキサンデンドリマー構造を側鎖に有するビルニ系重合体において、上記（ａ）成分と（ｂ）成分の重合比率は、（ａ）成分と（ｂ）成分が重量比で、０：１００〜９９．９：０．１となる範囲であり、好ましくは、１：９９〜９９：１となる範囲である。なお、（ａ）成分と（ｂ）成分が０：１００ということは、（ｂ）成分のホモポリマーであってもよいことを意味している。
【００５４】
本発明に使用される（Ａ）カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体は、上記のような（ａ）成分と（ｂ）成分を共重合させるか、（ｂ）成分のみを重合させてなるものである。重合方法としては、ラジカル重合法やイオン重合法が使用されるが、これらの中でも特にラジカル重合法が好ましい。このラジカル重合においては溶液重合法が好適に使用される。この溶液重合は、溶媒中で、（ａ）成分と（ｂ）成分とを、ラジカル開始剤の存在下、５０〜１５０℃の温度条件下で３〜２０時間反応させることにより行われることが好ましい。
【００５５】
このとき用いる溶媒としては、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，イソプロピルアルコール，ブタノール等のアルコール類；オクタメチルテシクロテトラシロキサン，デカメチルシクロペンタシロキサン，ヘキサメチルジシロキサン，オクタメチルトリシロキサン等のオルガノシロキサンオリゴマーが例示される。
【００５６】
ラジカル開始剤としては、一般にラジカル重合法に使用される従来公知の化合物が用いられ、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。このラジカル開始剤は１種を単独で使用してもよく、また２種類以上を混合して使用してもよい。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重量部に対して０．１〜５重量部の範囲であることが好ましい。
【００５７】
また、重合に際しては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、メルカプトプロピル基を有するポリジメチルシロキサン等のメルカプト化合物；塩化メチレン，クロロホルム，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。なお、本発明のビニル系重合体を製造する場合には、重合後、加熱下、減圧処理して、残存する未反応のビニル系単量体を除去することが好ましい。
【００５８】
本発明で使用されるカルボシロキサン構造を側鎖に有するビニル系重合体（Ａ）の数平均分子量は、熱可塑性樹脂に対する配合のしやすさから、好ましくは、３，０００〜２，０００，０００であり、さらに好ましくは、５，０００〜８００，０００である。また、その性状は、液状、ガム状、ペースト状、固体状、粉体状等が例示される。
【００５９】
本発明の熱可塑性樹脂組成物において、もう一方の成分である前記（Ａ）成分以外の熱可塑性樹脂（Ｂ）とは、前記（Ａ）成分と相溶性或いは（Ａ）成分を分散できるものであれば、その性状は特に限定されるものでなく、例えば室温でエラストマー状のものであってもよい。
【００６０】
この（Ｂ）熱可塑性樹脂としては、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１ペンテン等のα−オレフィンの単独重合体または共重合体からなるポリエチレン、低密度ポリエチレン、高密度ポリエチレン、超高分子量ポリエチレン、ポリプロピレン、エチレン／プロピレン共重合体、これらα−オレフィンと酢酸ビニル、メチルメタクリレート、マレイン酸等のα−オレフィン以外の単量体との共重合体からなるエチレン／酢酸ビニル共重合体、エチレン（メタ）アクリル酸エステル共重合体等のオレフィン系樹脂；アクリル酸、メタアクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルシクロヘキシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸ジエチルアミノエチル等の（メタ）アクリル酸エステル類、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等の多官能（メタ）アクリレート類等のアクリル系単量体の単独重合体または共重合体、これらのアクリル系単量体とスチレン、α−メチルスチレン等のスチレン系単量体、酢酸ビニル、塩化ビニル、塩化ビニリデン等のビニル系単量体、フェニルマレイミド、シクロヘキシルマレイミド、無水マレイミド等のマレイミド系単量体との共重合体等のアクリル系樹脂；ポリ塩化ビニル、ポリ塩化ビニリデン、ポリフッ化ビニル、ポリフッ化ビニリデン等のハロゲン化ビニル系樹脂；ポリスチレン、高衝撃性ポリスチレン、アクリロニトリル／ブタジエン／スチレン共重合体（ＡＢＳ樹脂）、アクリロニトリル／スチレン共重合体、アクリロニトリル／アクリルゴム／スチレン共重合体、アクリロニトリル／エチレンプロピレンゴム／スチレン共重合体等のスチレン系樹脂；ポリエチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエチレンテレフタレート／イソフタレート、ポリブチレンテレフタレート／イソフタレート等のポリエステル系樹脂；ナイロン６、ナイロン６６、ナイロン６／６６、ナイロン６／１２、ナイロン６１０、ナイロン６１２、ナイロン１１、ナイロン１２等のポリアミド系樹脂；ポリビニルアルコール系樹脂；ポリアセタール等のポリオキシアルキレン系樹脂；ポリカーボネート系樹脂；ポリ酢酸ビニル系樹脂；ポリサルフォン系樹脂；ポリエーテルサルフォン系樹脂；ポリフェニレンサルファイド等のポリアリーレンサルファイド系樹脂；ポリアリレート系樹脂；ポリイミド系樹脂；ポリアミドイミド系樹脂、ポリエーテルイミド系樹脂；ポリエーテルエーテルケトン系樹脂；液晶ポリエステル系樹脂；ポリテトラフルオロエチレン、エチレン／テトラフルオロエチレン共重合体等のフッ素系樹脂、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、フッソ系エラストマー、塩化ビニル系エラストマー、ポリアミド系エラストマー、ポリエステル系エラストマー等の熱可塑性エラストマー樹脂；およびこれら熱可塑性樹脂の二種以上の混合物や共重合体が例示される。
【００６１】
上記両成分（Ａ）および（Ｂ）の混合割合は、（Ｂ）成分１００重量部に対し（Ａ）成分が０．０１〜５００重量部であり、好ましくは０．０１〜１００重量部、より好ましくは０．１〜５０重量部の範囲である。（Ａ）成分の割合が０．０１重量部未満では目的とする特性の向上効果が小さく、また５００重量部を越えると熱可塑性樹脂（Ｂ）本来の機械的性質の低下等が招かれるため好ましくない。
【００６２】
なお、上記両成分（Ａ）および（Ｂ）の混合割合は、（Ｂ）成分の熱可塑性樹脂の種類に応じて適宜選択される。即ち、（Ａ）成分と（Ｂ）成分の相溶性などを考慮して、（Ｂ）成分の熱可塑性樹脂の種類に応じた最適範囲が存在する。
本発明の熱可塑性樹脂組成物を調製する方法は特に限定されるものではなく、例えば（Ａ）および（Ｂ）成分をヘンシェルミキサー等の混合装置により予め混合した後、これをニーターミキサー、バンバリーミキサー、一軸連続混練機、二軸連続混練機等の混練装置により溶融混合する方法、前記両成分を前記混練装置に供給して直接溶融混練する方法等が使用されるが、場合によっては適宜の溶媒を使用してこれに前記両成分を溶解した後、溶媒を除去する方法等も使用することができる。
【００６３】
なお、本発明の熱可塑性樹脂組成物の調製に当たっては、ガラス繊維、炭素繊維、熱可塑性樹脂繊維、黒鉛、マイカ、タルク、シリカ微粉末等の補強剤あるいは充填剤、滑剤等の成形加工性改良剤、耐候剤、耐光剤、酸化防止剤、紫外線防止剤等の安定剤、難燃剤、帯電防止剤、顔料等の着色剤、界面活性剤、抗菌剤等の慣用の添加剤を、本発明の効果を損なわない範囲で添加することができる。
【００６４】
本発明の熱可塑性樹脂組成物は、熱可塑性樹脂（Ｂ）に対するビニル系重合体（Ａ）の相溶性が良好であることから、そのまま射出成形、押出成形、圧縮成形、ブロー成形等の各種成形手段に供することが可能である。かくして得られる成形品は、潤滑性、離型性、成形性、撥水性、ガス透過性および機械的強度等の各種特性が均衡にすぐれ、しかも添加剤成分のブリードアウトや分離がなく、外観が良好な特性を有しているため、各種用途への適用が広く期待できる。
【００６５】
【実施例】
以下、本発明を実施例にてさらに詳しく説明する。
実施例における構造式中のＭｅはメチル基を示すものである。また、実施例における粘度は２５℃で測定した値である。
なお、以下の実施例および比較例における各物性値は、次の方法により測定した値である。
【００６６】
〔成形品の成形条件及び離型性〕
１００ｍｍ×１００ｍｍ×３ｍｍの寸法の板状成形片が１枚採れるステンレス鋼製の金型に適当量の樹脂組成物を載せ、２２０℃にて１０分間加熱圧縮した。次いで冷却後に金型から板状成形片を手で取り出す際に、その離型性を感触で相対比較した。ここで、熱冷プレスは東洋マシナリー製のものを用いた。
【００６７】
〔成形品の外観〕
得られた成形品の外観を目視にて観察した。
〔潤滑性〕
ポリプロピレン樹脂（住友化学工業（株）製「リープレンＹ１０１」）から成形して得られた円筒状の成形片と、以下の実施例および比較例の熱可塑性樹脂組成物から成形して得られた円板状の成形片を用いて、スラスト摩擦摩耗試験機（東洋精機製作所製）により、圧力１Ｋｇｆ／ｃｍ、滑り速度２．１０ｃｍ／ｓｅｃの条件で摺動させた場合の滑り摩擦係数を測定した。
【００６８】
〔撥水性〕
板状成形品の水に対する接触角を測定した。ここで装置は自動接触角計（協和界面化学株式会社製）を用いた。
〔酸素透過性〕
ＪＩＳ Ｋ−７１２６に規定する酸素透過性試験に準じて、温度２３℃、湿度０％、酸素濃度５％の条件下で酸素透過性を測定した。ここで測定機は酸素透過試験機（モダンコントロール社製１０／５０）を使用し、組成物の試料は皮膜面積５０ｃｍ2 の試験片を使用した。測定値Ｐは酸素透過係数の１００億倍の値であり、単位は ｃｍ3 ・ｃｍ／（ｃｍ2 ・ｓｅｃ・ｍｍＨｇ）である。
【００６９】
また、以下の実施例および比較例で使用したポリメチルメタクリレート樹脂、ポリスチレン樹脂およびポリブチレンテレフタレート樹脂の内容は、それぞれ次のとおりである。
ポリメチルメタクリレート樹脂…三菱レイヨン（株）製「アクリペットＭＦ」
ポリスチレン樹脂 …旭化成工業（株）製「スタイロン６６６」
ポリブチレンテレフタレート樹脂…東レ（株）製「ＰＢＴ１４００×０４」。
【００７０】
〔参考例１〕
撹拌装置、温度計および還流冷却管を取付けた２００ｍｌの４つ口フラスコに、メチルメタクリレート単量体２４．０ｇ、下記式
【００７１】
【化４０】
で表される「メタクリル基を含有するカルボシロキサンデンドリマー」６．０ｇおよびトルエン９０ｇを投入し、これらを窒素雰囲気下で撹拌しながら７０℃に加熱した。さらに、これにα，α´−アゾビスイソブチロニトリル（以下、ＡＩＢＮと称する。）０．３ｇを加えて、６時間撹拌した。
【００７３】
次いで、アスピレーターにて減圧下、加熱撹拌することによりトルエンの一部を除去した。残余の反応溶液を大過剰のメタノール中に投入して撹拌後、静置して沈殿物を分離し、これを減圧乾燥することにより、無色透明固体状物２６．２ｇを得た。これを「重合体−１」とする。
【００７４】
〔参考例２〕
撹拌装置、温度計および還流冷却管を取付けた２００ｍｌの４つ口フラスコに、トルエン９０ｇを投入し、これを窒素雰囲気下で撹拌しながら７０℃に加熱した。これに、メチルメタクリレート単量体２１．０ｇ、ｎ−ブチルアクリレート単量体３．０ｇ、参考例１で使用した「メタクリル基を含有するカルボシロキサンデンドリマー」６．０ｇおよびＡＩＢＮ０．３ｇからなる混合物を、フラスコ内の温度が７５℃を越えないように制御しながら徐々に滴下した。
【００７５】
滴下終了後も加熱撹拌を継続し、計６時間重合を行った。
次いで、アスピレーターにて減圧下、加熱撹拌することによりトルエンの一部を除去した。残余の反応溶液を大過剰のメタノール中に投入して撹拌後、静置して沈殿物を分離し、これを減圧乾燥することにより、無色透明固体状物２５．８ｇを得た。これを「重合体−２」とする。
【００７６】
〔実施例１〕
ポリメチルメタクリレート樹脂２５ｇ（１００重量部）と、参考例１で得た「重合体−１」１００．０ｇ（４００重量部）とを、東洋精機製作所製「ラボプラストミル」に仕込み、２２０℃、１００ｒｐｍにて１０分間加熱混合した。
これを成形して得た成形品の外観、撥水性および酸素透過性を評価した。これらの結果を表１に示した。
【００７７】
〔実施例２〕
ポリメチルメタクリレート樹脂１２５ｇ（１００重量部）と、参考例１で得た「重合体−１」３．７５ｇ（３．０重量部）とを、東洋精機製作所製「ラボプラストミル」に仕込み、２２０℃、１００ｒｐｍにて１０分間加熱混合して、熱可塑性樹脂組成物を得た。
これを成形して得た成形品の外観、撥水性および酸素透過性を評価した。これらの結果を表１に示した。
【００７８】
〔実施例３〕
ポリスチレン樹脂７５ｇ（１００重量部）と、参考例１で得た「重合体−１」３７．５ｇ（５０重量部）とを、東洋精機製作所製「ラボプラストミル」に仕込み、２２０℃、１００ｒｐｍにて１０分間加熱混合した。
これを成形して得た成形品の外観、撥水性および酸素透過性を評価した。これらの結果を表１に示した。
【００７９】
〔実施例４〕
ポリブチレンテレフタレート樹脂６０ｇ（１００重量部）と、参考例１で得た「重合体−１」６０ｇ（１００重量部）とを、東洋精機製作所製「ラボプラストミル」に仕込み、２６０℃、１００ｒｐｍにて１０分間加熱混合した。
これを成形して得た成形品の外観、撥水性および酸素透過性を評価した。これらの結果を表１に示した。
【００８０】
〔実施例５〕
ポリメチルメタクリレート樹脂７５ｇ（１００重量部）と、参考例２で得た「重合体−２」３７．５ｇ（５０重量部）とを、東洋精機製作所製「ラボプラストミル」に仕込み、２２０℃、１００ｒｐｍにて１０分間加熱混合した。
これを成形して得た成形品の外観、撥水性および酸素透過性を評価した。これらの結果を表１に示した。
【００８１】
〔比較例１〕
ポリメチルメタクリレート樹脂７５ｇ（１００重量部）と、粘度１００万センチストークスのポリジメチルシロキサン３７．５ｇ（５０重量部）とを、東洋精機製作所製「ラボプラストミル」に仕込み、２２０℃、１００ｒｐｍにて１０分間加熱混合した。
これを成形して得た成形品の外観、撥水性および酸素透過性を評価した。これらの結果を表１に示した。
【００８２】
〔比較例２〕
ポリメチルメタクリレート樹脂７５ｇ（１００重量部）と、ポリメチルメタクリレート／ポリジメチルシロキサン−グラフトコポリマー３７．５ｇ（５０重量部）とを、東洋精機製作所製「ラボプラストミル」に仕込み、２２０℃、１００ｒｐｍにて１０分間加熱混合した。
これを成形して得た成形品の外観、撥水性および酸素透過性を評価した。これらの結果を表１に示した。
【００８３】
【表１】
【００８４】
【発明の効果】
以上説明したように、本発明の熱可塑性樹脂組成物は、離型性、成形性、撥水性、酸素透過性等の特性に優れ、しかも添加剤成分のブリードアウトや分離がない外観良好な特性を有しているため、各種成形手段に適応することができ、得られた成形品は上記特性を生かして種々の用途に広く適用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition capable of providing various molded articles having excellent properties such as releasability, moldability, water repellency and oxygen permeability.
[0002]
[Prior art]
Thermoplastic resins such as olefin-based resins, styrene-based resins, polyamide-based resins, polyester-based resins, and halogenated vinyl-based resins have excellent physical properties and are widely used as materials for various molded products.
However, since this type of thermoplastic resin has the disadvantage of poor mold release, moldability, water repellency, etc., various studies have been made for the purpose of improving them.
[0003]
Among these, linear polyorganosiloxanes such as silicone oil and silicone raw rubber have excellent interfacial properties and are therefore used as additives to improve the release properties, moldability, water repellency, etc. of thermoplastic resins. In fact, this kind of proposal is also made by Japanese Patent Publication No. 57-10144.
[0004]
However, in general, the polyorganosiloxane and the thermoplastic resin are inferior in compatibility, and for example, it has been difficult to uniformly disperse the polyorganosiloxane in a fine form in a thermoplastic resin such as an AS resin or an ABS resin. Therefore, the thermoplastic resin added and mixed with polyorganosiloxane has poor workability, and there are not only defects such as bleeding out of the polyorganosiloxane in the molded product and appearance failure due to separation, but also for each molded product. There have been problems such as variations in the releasability, moldability, and water repellency.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a thermoplastic resin composition capable of providing various molded articles having excellent properties such as releasability, moldability, water repellency and oxygen permeability.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that a specific branched structure, that is, a carbosiloxane dendrimer structure, is used instead of a conventional linear polyorganosiloxane as an additive component for a thermoplastic resin. By using a vinyl polymer in the chain, the compatibility between the thermoplastic resin and the additive component is good, lubricity, releasability, moldability, water repellency, gas permeability, mechanical strength, etc. The inventors have found that a thermoplastic resin composition can be obtained in which various properties of the above are excellent in balance, and there are no bleedout and separation of additive components and can give various molded articles having a good appearance.
[0007]
The thermoplastic resin composition of the present invention isIt is a group represented by the following formulaIt consists of a vinyl polymer (A) having a carbosiloxane dendrimer structure in the side chain and a thermoplastic resin (B) other than the component (A). The component (A) is added to 100 parts by weight of the component (B). 0.01 to 500 parts by weight is contained.
[Chemical 8]
[Chemical 9]
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Below, the thermoplastic resin composition of this invention is demonstrated concretely.
The vinyl polymer (A) as one component in the thermoplastic resin composition of the present invention is a vinyl polymer having a carbosiloxane dendrimer structure in the side chain. The component (A) contains a carbosiloxane dendrimer structure in the side chain of the polymer. In the present invention, the dendrimer structure is highly regularly branched from one nucleus in a radial manner. It means a high molecular weight group. An example of a carbosiloxane dendrimer having such a structure is a highly branched siloxane / silalkylene copolymer (see Japanese Patent Application No. 9-171154).
In the present invention, the carbosiloxane dendrimer structure in the vinyl polymer (A) is a group represented by the following general formula.The
[0009]
[Chemical Formula 10]
In the above formula, Z is a divalent organic group, an alkylene group, an arylene group, an aralkylene group, an ester-containing divalent organic group, an ether-containing divalent organic group, a ketone-containing divalent organic group, an amide group-containing divalent organic group. A group is illustrated, and among these, an organic group represented by the following formula is preferable.
[0011]
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In the above formula, R9Is an alkylene group having 1 to 10 carbon atoms such as methylene group, ethylene group, propylene group and butylene group, preferably methylene group and propylene group, RTenIs an alkyl group having 1 to 10 carbon atoms, and a methyl group and an ethyl group are exemplified by a propyl group and a butyl group. Among these, a methyl group is preferable, and R11Is an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group is preferable, d is an integer of 0 to 4, and e is 0 or 1. R1Is 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. X1Is a silylalkyl group represented by the following formula when i = 1.
[0015]
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(Wherein R1Is the same as above and R2Is an alkylene group having 2 to 10 carbon atoms, linear alkylene group such as ethylene group, propylene group, butylene group, hexylene group; methylmethylene group, methylethylene group, 1-methylpentylene group, 1, 4 -Branched alkylene groups, such as a dimethyl butylene group, are illustrated. Among these, an ethylene group, a methylethylene group, a hexylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group are preferable. RThreeIs an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group; aiIs an integer from 0 to 3. ).
[0017]
In the thermoplastic resin composition of the present invention, the branched organosiloxane polymer (A) containing the following carbosiloxane dendrimer structure is preferably used.
That is, (a) 0 to 99.9 parts by weight of a vinyl monomer, and (b) a general formula:
[0018]
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{Wherein Y is a radically polymerizable organic group, R1Is 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. X1Is a silylalkyl group represented by the following formula when i = 1.
[0020]
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(Wherein R1Is the same as above and R2Is an alkylene group having 2 to 10 carbon atoms, and RThreeIs an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. Xi + 1Is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group and the silylalkyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, and aiIs an integer from 0 to 3. )} Is a vinyl polymer having a carbosiloxane dendrimer structure in the side chain obtained by polymerizing 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing an organic group capable of radical polymerization. The vinyl polymer (A) will be further described. The vinyl monomer as the component (a) is not particularly limited as long as it has a radical polymerizable vinyl group. Examples of such vinyl monomers include lower alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate; Glycidyl acrylate; n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) Higher (meth) acrylates such as 2-ethylhexyl acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl butyrate, Vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate Higher fatty acid esters such as vinyl stearate; aromatic vinyl-type monomers such as styrene, vinyl toluene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, vinylpyrrolidone; (meth) acrylamide, N-methylol (meta ) Amide group-containing vinyl monomers such as acrylamide, N-methoxymethyl (meth) acrylamide, isobutoxymethoxy (meth) acrylamide, N, N-dimethyl (meth) acrylamide; hydroxyethyl (meth) acrylate, (meta ) Hydroxyl-containing vinyl monomers such as hydroxypropyl acrylate; (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and other carboxylic acid-containing vinyl monomers, tetrahydrofurfuryl (meth) acrylate , Butoxyethyl (meth) Ether type vinyl monomers such as acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether; (meth) acrylic Unsaturated group-containing silicone such as loxypropyltrimethoxysilane, polydimethylsiloxane containing (meth) acrylic group at one end (branched or linear), polydimethylsiloxane containing styryl group at one end Compound; butadiene; vinyl chloride; vinylidene chloride; (meth) acrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; (meth) acryl glycidyl ether: (meth) acrylic acid Alkali metal salts, ammonium salts, organic amine salts of radically polymerizable unsaturated carboxylic acids such as rilic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid; radical polymerizable non-polymerizable groups having a sulfonic acid group such as styrenesulfonic acid Saturated monomers, and alkali metal salts, ammonium salts, organic amine salts thereof; quaternary ammonium salts derived from (meth) acrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, methacrylic acid Examples include methacrylic acid esters of alcohols having tertiary amine groups such as diethylamine esters, and quaternary ammonium salts thereof.
[0022]
Polyfunctional vinyl monomers can also be used. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) Acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene oxide or bisphenol A Di (meth) acrylates of diols of pyrene oxide adducts, di (meth) acrylates of diols of hydrogenated bisphenol A ethylene oxide or propylene oxide adducts, and (meth) acryloyl group-containing simple substances such as triethylene glycol divinyl ether Examples thereof include unsaturated group-containing silicone compounds such as dimer, divinylbenzene, and styryl group-blocked polydimethylsiloxane.
[0023]
The component (b) carbosiloxane dendrimer has the general formula:
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[0024]
In the above formula, Y is an organic group capable of radical polymerization and may be any organic group capable of radical addition reaction. Specifically, it contains a (meth) acryloxy group represented by the following general formula: Examples thereof include an organic group, a (meth) acrylamide group-containing organic group, a styryl group-containing organic group, or an alkenyl group having 2 to 10 carbon atoms.
[0025]
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(In the above formula, RFourAnd R6 is a hydrogen atom or a methyl group;FiveAnd R8Is an alkylene group having 1 to 10 carbon atoms, and R7Is an alkyl group having 1 to 10 carbon atoms. b is an integer of 0 to 4, and c is 0 or 1. )
Examples of such radical polymerizable organic groups include acryloxymethyl group, 3-acryloxypropyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group, 2- (3-vinylphenyl) ethyl group, vinyl group, allyl group, methallyl group , 5-hexenyl group. R1Is 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.
X1Is a silylalkyl group represented by the following formula when i = 1.
[0029]
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In the above formula, R2Is an alkylene group having 2 to 10 carbon atoms, linear alkylene group such as ethylene group, propylene group, butylene group, hexylene group; methylmethylene group, methylethylene group, 1-methylpentylene group, 1, 4 -Branched alkylene groups, such as a dimethyl butylene group, are illustrated. Among these, an ethylene group, a methylethylene group, a hexylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group are preferable. RThreeIs an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. R1Is the same as above. Xi + 1Is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group and the silylalkyl group. aiIs an integer from 0 to 3. i is an integer of 1 to 10, which indicates the number of layers of the silylalkyl group, that is, the number of repetitions of the silylalkyl group. Therefore, when the number of layers is 1, the carbosiloxane dendrimer of this component has the general formula:
[0031]
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(Where Y, R1, R2And RThree Is the same as above and R12Is the same as a hydrogen atom or R1. a1Is aiThe same as a in a molecule1The average total number of is 0-7. ). When the number of layers is 2, the carbosiloxane dendrimer of this component has the general formula:
[0033]
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[0034]
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(Where Y, R1, R2, RThreeAnd R12Is the same as above. a1, a2And aThreeIs aiThe same as a in a molecule1 And a2And aThree The average total number of is 0-79. ).
Examples of the carboxydendrimer containing an organic group capable of radical polymerization of this component include carbosiloxane dendrimers represented by the following average composition formula.
[0036]
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Such a carbosiloxane dendrimer can be produced according to the method for producing a branched siloxane-silalkylene copolymer described in Japanese Patent Application No. 9-171154. For example, the general formula:
[0051]
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(Wherein R1 And Y are as defined above. And a silicon atom-bonded hydrogen atom-containing silicon compound and an alkenyl group-containing organosilicon compound can be produced by a hydrosilylation reaction. Examples of the silicon compound represented by the above formula include 3-methacryloxypropyltris (dimethylsiloxy) silane, 3-acryloxypropyltris (dimethylsiloxy) silane, 4-vinylphenyltris (dimethylsiloxy) silane, and alkenyl As the group-containing organosilicon compound, vinyltris (trimethylsiloxy) silane, vinyltris (dimethylphenylsiloxy) silane, and 5-hexenyltris (trimethylsiloxy) silane are used. This hydrosilylation reaction is preferably carried out in the presence of a transition metal catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.
[0053]
In the Virni polymer having a carbosiloxane dendrimer structure in the side chain used in the present invention, the polymerization ratio of the component (a) and the component (b) is such that the component (a) and the component (b) are weight. The ratio is in the range of 0: 100 to 99.9: 0.1, and preferably in the range of 1:99 to 99: 1. In addition, that (a) component and (b) component are 0: 100 means that the homopolymer of (b) component may be sufficient.
[0054]
(A) The vinyl polymer having a carbosiloxane dendrimer structure in the side chain used in the present invention is copolymerized with the above components (a) and (b) or polymerized only with component (b). It is something to be made. As the polymerization method, a radical polymerization method or an ionic polymerization method is used, and among these, the radical polymerization method is particularly preferable. In this radical polymerization, a solution polymerization method is preferably used. This solution polymerization is preferably carried out in a solvent by reacting the component (a) and the component (b) in the presence of a radical initiator at a temperature of 50 to 150 ° C. for 3 to 20 hours. .
[0055]
Solvents 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 , Ketones such as methyl isobutyl ketone and diisobutyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; alcohols such as methanol, ethanol, isopropyl alcohol and butanol; octamethyl tecyclotetrasiloxane and decamethyl Illustrative are organosiloxane oligomers such as cyclopentasiloxane, hexamethyldisiloxane and octamethyltrisiloxane.
[0056]
As the radical initiator, conventionally known compounds generally used for radical polymerization are used. Specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methyl) is used. Azobis compounds such as butyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-2-ethyl An organic peroxide such as hexanoate is exemplified. This radical initiator may be used individually by 1 type, and may mix and use 2 or more types. It is preferable that the usage-amount of a radical initiator is the range of 0.1-5 weight part with respect to a total of 100 weight part of the said (a) component and (b) component.
[0057]
A chain transfer agent can be added during the polymerization. Specific examples of the chain transfer agent include mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having a mercaptopropyl group; methylene chloride, chloroform, four Halides such as carbon chloride, butyl bromide and 3-chloropropyltrimethoxysilane are exemplified. In addition, when manufacturing the vinyl polymer of this invention, it is preferable after a superposition | polymerization to carry out pressure reduction treatment with heating and to remove the remaining unreacted vinyl monomer.
[0058]
The number average molecular weight of the vinyl polymer (A) having a carbosiloxane structure in the side chain used in the present invention is preferably 3,000 to 2,000,000 from the ease of blending with a thermoplastic resin. More preferably, it is 5,000 to 800,000. Examples of the properties include liquid, gum, paste, solid, and powder.
[0059]
In the thermoplastic resin composition of the present invention, the thermoplastic resin (B) other than the component (A), which is the other component, is compatible with the component (A) or can disperse the component (A). If it exists, the property is not particularly limited, and may be, for example, an elastomer at room temperature.
[0060]
Examples of the thermoplastic resin (B) include polyethylenes composed of homopolymers or copolymers of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and the like. From high density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene, ethylene / propylene copolymers, and copolymers of these α-olefins with monomers other than α-olefins such as vinyl acetate, methyl methacrylate, maleic acid, etc. Olefin resins such as ethylene / vinyl acetate copolymer and ethylene (meth) acrylic acid ester copolymer; acrylic acid, methacrylic acid, methyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic Cyclohexyl acid, 2-ethylcyclohexyl (meth) acrylate, (meth) (Meth) acrylates such as phenyl crylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ethylene glycol di (meth) ) Homopolymers or copolymers of acrylic monomers such as polyfunctional (meth) acrylates such as acrylate, trimethylolpropane tri (meth) acrylate, neopentylglycol di (meth) acrylate, and these acrylic monomers A monomer and a styrene monomer such as styrene and α-methylstyrene, a vinyl monomer such as vinyl acetate, vinyl chloride, and vinylidene chloride, and a maleimide monomer such as phenyl maleimide, cyclohexyl maleimide, and maleimide anhydride. Acrylic resins such as copolymers; polyvinyl chloride, Vinyl halide resins such as polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride; polystyrene, high-impact polystyrene, acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene copolymer, acrylonitrile / acrylic rubber / Styrene resins such as styrene copolymer, acrylonitrile / ethylene propylene rubber / styrene copolymer; polyester resins such as polyethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate / isophthalate; Nylon 6, nylon 66, nylon 6/66, nylon 6/12, nylon 610, nylon 612, nylon 11, nylon 12, etc. Amide resin; Polyvinyl alcohol resin; Polyoxyalkylene resin such as polyacetal; Polycarbonate resin; Polyvinyl acetate resin; Polysulfone resin; Polyethersulfone resin; Polyarylene sulfide resin such as polyphenylene sulfide; Arylate resins; polyimide resins; polyamideimide resins, polyetherimide resins; polyetheretherketone resins; liquid crystal polyester resins; fluorine resins such as polytetrafluoroethylene and ethylene / tetrafluoroethylene copolymers; Heat of styrene elastomer, olefin elastomer, urethane elastomer, fluorine elastomer, vinyl chloride elastomer, polyamide elastomer, polyester elastomer, etc. Plastic elastomer resin; and mixtures or copolymers of two or more of these thermoplastic resins.
[0061]
The mixing ratio of the two components (A) and (B) is such that the component (A) is 0.01 to 500 parts by weight, preferably 0.01 to 100 parts by weight, based on 100 parts by weight of the component (B). Preferably it is the range of 0.1-50 weight part. If the proportion of the component (A) is less than 0.01 parts by weight, the effect of improving the target properties is small, and if it exceeds 500 parts by weight, the thermoplastic resin (B) is preferably deteriorated in its original mechanical properties. Absent.
[0062]
The mixing ratio of the two components (A) and (B) is appropriately selected according to the type of the thermoplastic resin as the component (B). That is, in consideration of the compatibility between the component (A) and the component (B), there is an optimum range according to the type of the thermoplastic resin of the component (B).
The method for preparing the thermoplastic resin composition of the present invention is not particularly limited. For example, the components (A) and (B) are previously mixed by a mixing apparatus such as a Henschel mixer, and then mixed with a neat mixer or a banbury mixer. , A method of melt-mixing with a kneading apparatus such as a uniaxial continuous kneader or a biaxial continuous kneader, a method of supplying both the components to the kneading apparatus and directly melt-kneading are used. It is also possible to use a method of removing the solvent after dissolving both the components in
[0063]
In preparation of the thermoplastic resin composition of the present invention, glass fiber, carbon fiber, thermoplastic resin fiber, reinforcing agent such as graphite, mica, talc, silica fine powder, etc., improvement of molding processability such as filler, lubricant, etc. Conventional additives such as stabilizers, weathering agents, light-proofing agents, antioxidants, anti-ultraviolet agents, etc., flame retardants, antistatic agents, pigments and other colorants, surfactants, antibacterial agents, etc. It can add in the range which does not impair an effect.
[0064]
Since the thermoplastic polymer composition of the present invention has good compatibility of the vinyl polymer (A) with the thermoplastic resin (B), various moldings such as injection molding, extrusion molding, compression molding, blow molding, etc. It can be provided to the means. The molded product thus obtained has an excellent balance of various properties such as lubricity, releasability, moldability, water repellency, gas permeability and mechanical strength, and there is no bleedout or separation of additive components and appearance. Since it has good characteristics, it can be widely expected to be used in various applications.
[0065]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
Me in the structural formulas in the examples represents a methyl group. Moreover, the viscosity in an Example is the value measured at 25 degreeC.
In addition, each physical property value in the following examples and comparative examples is a value measured by the following method.
[0066]
[Molding conditions and releasability of molded products]
An appropriate amount of the resin composition was placed on a stainless steel mold capable of taking one plate-shaped molded piece having dimensions of 100 mm × 100 mm × 3 mm, and heated and compressed at 220 ° C. for 10 minutes. Next, when the plate-shaped molded piece was manually taken out from the mold after cooling, the release properties were relatively compared by touch. Here, the hot and cold press used was made by Toyo Machinery.
[0067]
[Appearance of molded product]
The appearance of the obtained molded product was visually observed.
(Lubricity)
A cylindrical molded piece obtained by molding from a polypropylene resin ("Leeprene Y101" manufactured by Sumitomo Chemical Co., Ltd.) and a circle obtained by molding from the thermoplastic resin compositions of the following examples and comparative examples. The sliding friction coefficient was measured when the plate-shaped molded piece was slid under the conditions of a pressure of 1 kgf / cm and a sliding speed of 2.10 cm / sec using a thrust frictional wear tester (manufactured by Toyo Seiki Seisakusho).
[0068]
[Water repellency]
The contact angle of the plate-shaped molded product with water was measured. Here, an automatic contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.) was used as the apparatus.
[Oxygen permeability]
In accordance with the oxygen permeability test specified in JIS K-7126, the oxygen permeability was measured under conditions of a temperature of 23 ° C., a humidity of 0%, and an oxygen concentration of 5%. Here, an oxygen permeation tester (Modern Control 10/50) is used as a measuring device, and a sample of the composition has a film area of 50 cm.2The test piece was used. The measured value P is 10 billion times the oxygen transmission coefficient, and the unit is cmThree・ Cm / (cm2 · Sec · mmHg).
[0069]
The contents of the polymethyl methacrylate resin, polystyrene resin and polybutylene terephthalate resin used in the following examples and comparative examples are as follows.
Polymethylmethacrylate resin: “Acrypet MF” manufactured by Mitsubishi Rayon Co., Ltd.
Polystyrene resin: "Stylon 666" manufactured by Asahi Kasei Corporation
Polybutylene terephthalate resin: “PBT1400 × 04” manufactured by Toray Industries, Inc.
[0070]
[Reference Example 1]
In a 200 ml four-necked flask equipped with a stirrer, thermometer and reflux condenser, methyl methacrylate monomer 24.0 g, the following formula
[0071]
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The methacryl group-containing carbosiloxane dendrimer 6.0g and toluene 90g were added, and these were heated to 70 ° C. with stirring under a nitrogen atmosphere. Furthermore, 0.3 g of α, α′-azobisisobutyronitrile (hereinafter referred to as AIBN) was added thereto and stirred for 6 hours.
[0073]
Subsequently, a part of toluene was removed by heating and stirring under reduced pressure with an aspirator. The remaining reaction solution was poured into a large excess of methanol and stirred, and then allowed to stand to separate a precipitate, which was dried under reduced pressure to obtain 26.2 g of a colorless transparent solid. This is designated as “Polymer-1”.
[0074]
[Reference Example 2]
To a 200 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 90 g of toluene was charged and heated to 70 ° C. with stirring in a nitrogen atmosphere. A mixture of 21.0 g of methyl methacrylate monomer, 3.0 g of n-butyl acrylate monomer, 6.0 g of “carbosiloxane dendrimer containing methacryl group” used in Reference Example 1 and 0.3 g of AIBN was added thereto. The flask was gradually dropped while controlling the temperature in the flask so as not to exceed 75 ° C.
[0075]
Heating and stirring were continued even after completion of dropping, and polymerization was carried out for a total of 6 hours.
Subsequently, a part of toluene was removed by heating and stirring under reduced pressure with an aspirator. The remaining reaction solution was poured into a large excess of methanol and stirred, and then allowed to stand to separate a precipitate, which was dried under reduced pressure to obtain 25.8 g of a colorless transparent solid. This is designated as “Polymer-2”.
[0076]
[Example 1]
25 g (100 parts by weight) of a polymethyl methacrylate resin and 100.0 g (400 parts by weight) of “Polymer-1” obtained in Reference Example 1 were charged into “Lab Plast Mill” manufactured by Toyo Seiki Seisakusho, 220 ° C., The mixture was heated and mixed at 100 rpm for 10 minutes.
The appearance, water repellency and oxygen permeability of the molded product obtained by molding this were evaluated. These results are shown in Table 1.
[0077]
[Example 2]
125 g (100 parts by weight) of a polymethyl methacrylate resin and 3.75 g (3.0 parts by weight) of “Polymer-1” obtained in Reference Example 1 were charged in “Lab Plast Mill” manufactured by Toyo Seiki Seisakusho, 220 The mixture was heated and mixed at 100 ° C. for 10 minutes to obtain a thermoplastic resin composition.
The appearance, water repellency and oxygen permeability of the molded product obtained by molding this were evaluated. These results are shown in Table 1.
[0078]
Example 3
75 g (100 parts by weight) of polystyrene resin and 37.5 g (50 parts by weight) of “Polymer-1” obtained in Reference Example 1 were charged into “Lab Plast Mill” manufactured by Toyo Seiki Seisakusho at 220 ° C. and 100 rpm. For 10 minutes.
The appearance, water repellency and oxygen permeability of the molded product obtained by molding this were evaluated. These results are shown in Table 1.
[0079]
Example 4
60 g (100 parts by weight) of polybutylene terephthalate resin and 60 g (100 parts by weight) of “Polymer-1” obtained in Reference Example 1 were charged in “Lab Plast Mill” manufactured by Toyo Seiki Seisakusho at 260 ° C. and 100 rpm. For 10 minutes.
The appearance, water repellency and oxygen permeability of the molded product obtained by molding this were evaluated. These results are shown in Table 1.
[0080]
Example 5
75 g (100 parts by weight) of polymethyl methacrylate resin and 37.5 g (50 parts by weight) of “Polymer-2” obtained in Reference Example 2 were charged into “Lab Plast Mill” manufactured by Toyo Seiki Seisakusho, 220 ° C., The mixture was heated and mixed at 100 rpm for 10 minutes.
The appearance, water repellency and oxygen permeability of the molded product obtained by molding this were evaluated. These results are shown in Table 1.
[0081]
[Comparative Example 1]
75 g (100 parts by weight) of polymethylmethacrylate resin and 37.5 g (50 parts by weight) of polydimethylsiloxane having a viscosity of 1,000,000 centistokes were charged in “Lab Plast Mill” manufactured by Toyo Seiki Seisakusho at 220 ° C. and 100 rpm. Heat mixed for 10 minutes.
The appearance, water repellency and oxygen permeability of the molded product obtained by molding this were evaluated. These results are shown in Table 1.
[0082]
[Comparative Example 2]
75 g (100 parts by weight) of a polymethyl methacrylate resin and 37.5 g (50 parts by weight) of a polymethyl methacrylate / polydimethylsiloxane-graft copolymer were charged into a “lab plast mill” manufactured by Toyo Seiki Seisakusho, at 220 ° C. and 100 rpm. For 10 minutes.
The appearance, water repellency and oxygen permeability of the molded product obtained by molding this were evaluated. These results are shown in Table 1.
[0083]
[Table 1]
[0084]
【The invention's effect】
As described above, the thermoplastic resin composition of the present invention is excellent in properties such as releasability, moldability, water repellency, oxygen permeability and the like, and has good appearance properties without bleeding out or separation of additive components. Therefore, it can be applied to various molding means, and the obtained molded product can be widely applied to various applications by taking advantage of the above characteristics.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27697598A JP4136117B2 (en) | 1998-09-30 | 1998-09-30 | Thermoplastic resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27697598A JP4136117B2 (en) | 1998-09-30 | 1998-09-30 | Thermoplastic resin composition |
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| Publication Number | Publication Date |
|---|---|
| JP2000103931A JP2000103931A (en) | 2000-04-11 |
| JP4136117B2 true JP4136117B2 (en) | 2008-08-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP27697598A Expired - Fee Related JP4136117B2 (en) | 1998-09-30 | 1998-09-30 | Thermoplastic resin composition |
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| JP (1) | JP4136117B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8808470B2 (en) | 2010-12-13 | 2014-08-19 | Nippon Steel & Sumitomo Metal Corporation | High-carbon chromium bearing steel and production method of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4615645B2 (en) * | 1998-10-27 | 2011-01-19 | 東レ・ダウコーニング株式会社 | Curable resin composition |
| US6497959B1 (en) * | 2000-03-30 | 2002-12-24 | General Electric Company | Use of dendrimers as a processing aid and surface modifier for thermoplastic resins |
| JP2006045441A (en) * | 2004-08-09 | 2006-02-16 | Soken Chem & Eng Co Ltd | Reactive modifier composition for aromatic heat resistant polymer, its resin composition for molding and its molding |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2658152B2 (en) * | 1988-04-05 | 1997-09-30 | 日本油脂株式会社 | Polysiloxane group-containing polymer |
| JP2638612B2 (en) * | 1988-06-20 | 1997-08-06 | 日信化学工業株式会社 | Silicone / acrylic copolymer composition |
| JPH07181737A (en) * | 1993-12-24 | 1995-07-21 | Shin Etsu Chem Co Ltd | Binder for electrophotographic toner |
| JPH08143675A (en) * | 1994-11-24 | 1996-06-04 | Toray Dow Corning Silicone Co Ltd | Silicone resin and its production |
| JP3053353B2 (en) * | 1995-04-18 | 2000-06-19 | 信越化学工業株式会社 | Radical polymerizable resin composition |
| JPH09151366A (en) * | 1995-11-30 | 1997-06-10 | Toray Dow Corning Silicone Co Ltd | Adhesive composition |
| US5691435A (en) * | 1996-01-25 | 1997-11-25 | Wacker-Chemie Gmbh | Crosslinkable compositions |
| JP3835890B2 (en) * | 1997-05-23 | 2006-10-18 | 東レ・ダウコーニング株式会社 | Curable organopolysiloxane composition |
| JP4270593B2 (en) * | 1997-06-12 | 2009-06-03 | 東レ・ダウコーニング株式会社 | Branched siloxane / silalkylene copolymer |
| JP3950197B2 (en) * | 1997-06-12 | 2007-07-25 | 東レ・ダウコーニング株式会社 | Method for producing silicone-containing organic polymer |
| JP4009382B2 (en) * | 1998-06-12 | 2007-11-14 | 東レ・ダウコーニング株式会社 | Cosmetic raw materials, cosmetics and methods for producing cosmetics |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8808470B2 (en) | 2010-12-13 | 2014-08-19 | Nippon Steel & Sumitomo Metal Corporation | High-carbon chromium bearing steel and production method of the same |
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| JP2000103931A (en) | 2000-04-11 |
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