WO2022210492A1 - ポリオルガノシロキサン含有重合体、組成物、及び成形体 - Google Patents
ポリオルガノシロキサン含有重合体、組成物、及び成形体 Download PDFInfo
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- WO2022210492A1 WO2022210492A1 PCT/JP2022/014884 JP2022014884W WO2022210492A1 WO 2022210492 A1 WO2022210492 A1 WO 2022210492A1 JP 2022014884 W JP2022014884 W JP 2022014884W WO 2022210492 A1 WO2022210492 A1 WO 2022210492A1
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- WIPO (PCT)
- Prior art keywords
- mass
- polyorganosiloxane
- polymer
- containing polymer
- vinyl
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 168
- 239000000203 mixture Substances 0.000 title claims description 44
- 239000002245 particle Substances 0.000 claims abstract description 49
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 28
- 229920002554 vinyl polymer Polymers 0.000 claims description 102
- 239000000178 monomer Substances 0.000 claims description 97
- 229920005992 thermoplastic resin Polymers 0.000 claims description 28
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- 125000004436 sodium atom Chemical group 0.000 claims description 5
- 229920005989 resin Polymers 0.000 abstract description 22
- 239000011347 resin Substances 0.000 abstract description 22
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 58
- 229920000126 latex Polymers 0.000 description 55
- 239000004816 latex Substances 0.000 description 53
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 53
- 229920000578 graft copolymer Polymers 0.000 description 40
- -1 polydimethylsiloxane Polymers 0.000 description 38
- 238000004519 manufacturing process Methods 0.000 description 37
- 125000005375 organosiloxane group Chemical group 0.000 description 36
- 239000000843 powder Substances 0.000 description 29
- 229920001577 copolymer Polymers 0.000 description 26
- 239000011342 resin composition Substances 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000003995 emulsifying agent Substances 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 18
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003377 acid catalyst Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000701 coagulant Substances 0.000 description 12
- 230000000379 polymerizing effect Effects 0.000 description 12
- 239000007870 radical polymerization initiator Substances 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 9
- 239000004417 polycarbonate Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 229920006351 engineering plastic Polymers 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 6
- 239000012966 redox initiator Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 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 5
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 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
- VLZDYNDUVLBNLD-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C(C)=C VLZDYNDUVLBNLD-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
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- 235000011092 calcium acetate Nutrition 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 3
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- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001599 direct drying Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- SDIXRDNYIMOKSG-UHFFFAOYSA-L disodium methyl arsenate Chemical compound [Na+].[Na+].C[As]([O-])([O-])=O SDIXRDNYIMOKSG-UHFFFAOYSA-L 0.000 description 3
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
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- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
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- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-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
- 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 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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- 239000004970 Chain extender Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 2
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 2
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- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
Definitions
- the present invention relates to polyorganosiloxane-containing polymers, compositions, and molded articles.
- This application claims priority based on Japanese Patent Application No. 2021-056873 filed in Japan on March 30, 2021, the content of which is incorporated herein.
- a rubber-containing polymer obtained by polymerizing a vinyl monomer with a rubber-like polymer can be dispersed in a wide variety of resins while maintaining a predetermined rubber particle size and rubber structure, so impact strength is required. Suitable for resins.
- silicone rubber is more resistant to hardening and discoloration due to heat and ultraviolet rays, and has excellent durability. It is preferably used.
- Polyorganosiloxanes represented by polydimethylsiloxane are used as silicone-based rubbers, and various graft copolymers using rubbers containing such polyorganosiloxanes are known.
- Patent Document 1 discloses a polyorganosiloxane having a specific glass transition temperature (Tg) obtained by graft-polymerizing a monofunctional vinyl monomer and a polyfunctional vinyl monomer in a specific ratio to a rubber containing polyorganosiloxane. Siloxane-containing graft copolymers are described.
- Patent Document 2 describes a polyorganosiloxane-containing graft copolymer having a volume average particle size of 300 to 2000 nm and a polyorganosiloxane content of 70 to 98% by mass.
- An object of the present invention is to provide a polyorganosiloxane-containing polymer which, when added to a resin, can yield a molded article exhibiting excellent flame retardancy without significantly deteriorating impact resistance.
- the present invention has the following aspects.
- the polyorganosiloxane-containing polymer of [1] which has a mass average particle diameter Dw of 1000 nm or less.
- a polymer having a composite and a graft portion, The composite comprises polyorganosiloxane and a first vinyl polymer, The polyorganosiloxane-containing polymer of [1] or [2], wherein the graft portion contains a second vinyl polymer.
- the polyorganosiloxane contains a structural unit derived from a siloxane-based cross-linking agent, and the proportion of the structural unit derived from the siloxane-based cross-linking agent in 100% by mass of the polyorganosiloxane is 3% by mass or less, [3]- The polyorganosiloxane-containing polymer according to any one of [6]. [8] The polyorganosiloxane-containing polymer of any one of [1] to [7], wherein the proportion of polyorganosiloxane in 100% by mass of the polyorganosiloxane-containing polymer is 70% by mass or more and 98% by mass or less.
- a polyorganosiloxane-containing polymer that, when added to a resin, can yield a molded article that exhibits excellent flame retardancy without significantly deteriorating impact resistance.
- a vinyl monomer means a compound having a polymerizable double bond.
- (meth)acryl means one or both of acrylic and methacrylic
- (meth)acrylic acid ester means one or both of acrylic acid ester and methacrylic acid ester.
- "-" is used to include the numerical values before and after it as lower and upper limits. That is, the numerical value represented by "A to B" means A or more and B or less.
- the polyorganosiloxane-containing polymer (hereinafter also referred to as "polymer (C)") according to one aspect of the present invention comprises polymer (A) and a second vinyl polymer (B) (hereinafter referred to as "vinyl Also referred to as “polymer (B)").
- the polymer (A) is a composite containing at least a polyorganosiloxane (A1) and further containing a first vinyl polymer (A2) (hereinafter also referred to as "vinyl polymer (A2)").
- At least a part of the polyorganosiloxane (A1) and the vinyl polymer (B) is preferably crosslinked.
- the polyorganosiloxane-containing polymer is a graft copolymer having a composite (composite rubber-like polymer) of a polyorganosiloxane (A1) and a vinyl polymer (A2) and a graft portion containing the vinyl polymer (B1). It is preferably coalesced.
- the polymer (C) contains 100 mass ppm or more of alkali metal atoms and has a mass average particle diameter Dw of 350 nm or more.
- the alkali metal atomic weight is measured according to the measuring method described in Examples.
- the mass average particle size is measured according to the method described in Examples.
- the presence of alkali metal atoms on the surface of the polyorganosiloxane-containing polymer tends to improve the thermal decomposability of the polyorganosiloxane-containing polymer.
- the particle size of the polyorganosiloxane-containing polymer is large, the thickness of the vinyl polymer (B) increases, so that it tends to be excellent in dispersibility in the resin.
- the polyorganosiloxane-containing polymer uniformly dispersed in the resin composition instantly decomposes near the decomposition temperature of the resin to form a dense carbonized layer, and as a result, the flame retardancy of the molded article is improved. It is considered that
- the polyorganosiloxane-containing polymer can be obtained as a powdery polymer by performing a treatment including drying after obtaining a latex polymer as described later.
- a treatment method even if the latex-like polyorganosiloxane-containing polymer contains alkali metal atoms, the amount of alkali metal contained in the obtained powdery polymer may decrease.
- the polyorganosiloxane-containing polymer when producing the resin composition that is, the powdery polyorganosiloxane-containing polymer contains alkali metal atoms of 100 ppm or more, and the mass A powder group containing a polyorganosiloxane-containing polymer having an average particle diameter Dw of 350 nm or more is preferable.
- the mass average particle diameter Dw of the polyorganosiloxane-containing polymer is 350 nm or more, preferably 375 nm or more, more preferably 400 nm or more, in order to improve the appearance and moist heat resistance.
- the mass average particle diameter Dw of the polyorganosiloxane-containing polymer is preferably 1000 nm or less, more preferably 800 nm or less, even more preferably 600 nm or less, and particularly preferably 500 nm or less.
- the above upper and lower limits can be combined arbitrarily. For example, 350 to 1000 nm is preferred, 350 to 800 nm is more preferred, 375 to 600 nm is even more preferred, and 400 to 500 nm is particularly preferred.
- the amount of alkali metal atoms contained in the polyorganosiloxane-containing polymer is 100 mass ppm or more, preferably 150 mass ppm or more, more preferably 200 mass ppm or more, in order to improve flame retardancy and moist heat resistance.
- the amount of alkali metal atoms contained in the polyorganosiloxane-containing polymer is preferably 1000 mass ppm or less, more preferably 800 mass ppm or less, further preferably 600 mass ppm or less, and 400 mass ppm or less for improving impact resistance. Especially preferred.
- the above upper and lower limits can be combined arbitrarily. For example, 100 to 1000 mass ppm is preferable, 100 to 800 mass ppm is more preferable, 150 to 600 mass ppm is more preferable, and 200 to 400 mass ppm is particularly preferable.
- the alkali metal is not particularly limited, and examples include lithium atom, sodium atom, potassium atom, rubidium atom, and cesium atom.
- the polyorganosiloxane-containing polymer may contain one alkali metal atom, or two or more alkali metal atoms. When the polyorganosiloxane-containing polymer contains two or more alkali metal atoms, the amount of alkali metal atoms contained in the polyorganosiloxane-containing polymer means the total mass of the alkali metal atoms.
- the alkali metal atom is preferably a lithium atom, a sodium atom or a potassium atom, particularly preferably a sodium atom.
- the polyorganosiloxane-containing polymer may contain alkaline earth metals and aluminum due to the manufacturing method. Since alkaline earth metals and aluminum become impurities, it is preferable that the content of alkaline earth metals and aluminum in the polyorganosiloxane-containing polymer is small, but the influence of the content of alkaline earth metals and aluminum on the present invention is less.
- the process when trying to remove the alkaline earth metal and aluminum from the polyorganosiloxane-containing polymer, the process may be complicated, so the content of the alkaline earth metal and aluminum in the polyorganosiloxane-containing polymer is , from the viewpoint of improving productivity, it may be 150 ppm or more, 100 ppm or more, 50 ppm or more, 0 ppm or more, or 0 ppm.
- Polyorganosiloxane (A1) Polyorganosiloxane (A1) is a polymer containing organosiloxane units. Organosiloxane units mean Si—O units to which organic groups are attached. Polyorganosiloxane has a structure represented by the following formula (1).
- R 1 and R 2 each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group.
- n represents an integer of 2 or more.
- Polyorganosiloxane (A1) can be obtained by polymerizing an organosiloxane mixture containing organosiloxane.
- the organosiloxane mixture may further contain optional ingredients.
- Components used as necessary include, for example, a siloxane-based cross-linking agent, a siloxane-based cross-linking agent, and a siloxane oligomer having a terminal blocking group.
- organosiloxanes examples include chain organosiloxanes, alkoxysilane compounds, and cyclic organosiloxanes. Alkoxysilane compounds and cyclic organosiloxanes are preferred, and cyclic organosiloxanes are more preferred because of their high polymerization stability and high polymerization rate.
- a bifunctional alkoxysilane compound is preferable as the alkoxysilane compound.
- Examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane and methylphenyldiethoxysilane.
- An alkoxysilane compound can be used individually by 1 type or in combination of 2 or more types.
- the cyclic organosiloxane is preferably a 3- to 7-membered cyclic organosiloxane.
- Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane.
- Cyclic organosiloxane can be used individually by 1 type or in combination of 2 or more types. Octamethylcyclotetrasiloxane is preferred because the particle size distribution is easier to control.
- the organosiloxane is preferably at least one selected from the group consisting of cyclic dimethylsiloxane and bifunctional dialkylsilane compounds in order to obtain a polymer (C) capable of increasing the impact strength of the molded article.
- a cyclic dimethylsiloxane is a cyclic siloxane having two methyl groups on a silicon atom. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Cyclic dimethylsiloxane can be used individually by 1 type or in combination of 2 or more types.
- a bifunctional dialkylsilane compound is a silane compound having two alkoxy groups and two alkyl groups on a silicon atom. Examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and dipropoxydimethylsilane.
- a bifunctional dialkylsilane compound can be used individually by 1 type or in combination of 2 or more types.
- siloxane-based cross-linking agent one having a siloxy group is preferable.
- siloxane-based cross-linking agents include tri- or tetra-functional silane-based cross-linking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. agents. Tetrafunctional crosslinkers are preferred, and tetraethoxysilane is more preferred.
- the proportion of the siloxane-based cross-linking agent in 100% by mass of the organosiloxane mixture is not particularly limited, and is set to 10 to improve flame retardancy. % by mass or less is preferable, 3% by mass or less is more preferable, 0.5% by mass or less is even more preferable, and 0% by mass or less is possible. If the ratio of the siloxane-based cross-linking agent is equal to or less than the above upper limit, the impact strength of the resulting molded article can be easily improved.
- the siloxane-based crosslinker has a siloxy group (--Si--O--) and a functional group capable of polymerizing with a vinyl monomer.
- Examples of the siloxane-based crossing agent include siloxanes represented by the following formula (I). R—Si(R 1 ) n (OR 2 ) (3-n) (I)
- R 1 represents a methyl group, ethyl group, propyl group, or phenyl group.
- R2 represents an organic group such as a hydrocarbon group, preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.
- n 0, 1 or 2;
- R represents a functional group represented by any one of formulas (I-1) to (I-4) below.
- CH 2 C(R 3 )-COO-(CH 2 ) p - (I-1) CH 2 ⁇ C(R 4 )—C 6 H 4 ⁇ (I-2)
- CH 2 CH- (I-3) HS—(CH 2 ) p ⁇ (I-4)
- R 3 and R 4 each independently represent a hydrogen atom or a methyl group
- p represents an integer of 1-6.
- Examples of functional groups represented by formula (I-1) include methacryloyloxyalkyl groups.
- Examples of siloxanes having a group represented by formula (I-1) include ⁇ -methacryloyloxyethyldimethoxymethylsilane, ⁇ -methacryloyloxypropylmethoxydimethylsilane, ⁇ -methacryloyloxypropyldimethoxymethylsilane, ⁇ -methacryloyloxy propyltrimethoxysilane, ⁇ -methacryloyloxypropylethoxydiethylsilane, ⁇ -methacryloyloxypropyldiethoxymethylsilane, ⁇ -methacryloyloxybutyldiethoxymethylsilane.
- Examples of the functional group represented by formula (I-2) include a vinylphenyl group.
- Examples of siloxanes having a group represented by formula (I-2) include vinylphenylethyldimethoxysilane.
- Examples of siloxanes having functional groups represented by formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.
- the functional group represented by formula (I-4) includes a mercaptoalkyl group.
- Examples of siloxanes having a group represented by formula (I-4) include ⁇ -mercaptopropyldimethoxymethylsilane, ⁇ -mercaptopropylmethoxydimethylsilane, ⁇ -mercaptopropyldiethoxymethylsilane, ⁇ -mercaptopropylethoxydimethylsilane. Silanes such as ⁇ -mercaptopropyltrimethoxysilane can be mentioned.
- the siloxane-based crossing agent can be used singly or in combination of two or more.
- ⁇ -methacryloyloxypropylmethyldimethoxysilane is preferable because it easily forms a sea-island structure when the polyorganosiloxane (A1) and the vinyl polymer (A2) are combined.
- the proportion of the siloxane-based crossing agent in 100% by mass of the organosiloxane mixture is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 0.5% by mass. % or more is more preferable.
- the proportion of the siloxane crossing agent in 100% by mass of the organosiloxane mixture is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
- the above upper and lower limits can be combined arbitrarily. For example, 0.05 to 20% by mass is preferable, 0.1 to 10% by mass is more preferable, and 0.5 to 5% by mass is even more preferable.
- the ratio of the siloxane-based graft crossing agent is within the range of the upper limit and the lower limit, the covalent bond between the polyorganosiloxane (A1) and the vinyl polymer (A2) can be sufficiently formed, and the impact strength is good.
- a polymer (C) can be obtained.
- the mass average particle size of the polyorganosiloxane (A1) is preferably 100 nm or more, more preferably 200 nm or more, and even more preferably 300 nm or more.
- the mass average particle size of the polyorganosiloxane (A1) is preferably 1000 nm or less, more preferably 800 nm or less, even more preferably 600 nm or less.
- the above upper and lower limits can be combined arbitrarily. For example, 100 to 1000 nm is preferred, 200 to 800 nm is more preferred, and 300 to 600 nm is even more preferred. If the mass average particle size of the polyorganosiloxane (A1) is within the range of the upper limit and the lower limit, the mass average particle size of the polymer (C) is adjusted within the preferred upper limit and lower limit. It's easy to do.
- Method for producing polyorganosiloxane (A1) there are no particular restrictions on the method for producing the polyorganosiloxane (A1), for example, organosiloxane, optionally a siloxane-based cross-linking agent, optionally a siloxane-based cross-linking agent, and optionally a siloxane oligomer having a terminal blocking group. is emulsified with an emulsifier and water to prepare an emulsion, in this emulsion the organosiloxane mixture is polymerized at a high temperature in the presence of an acid catalyst, and then the acid catalyst is neutralized with an alkaline substance.
- organosiloxane optionally a siloxane-based cross-linking agent, optionally a siloxane-based cross-linking agent, and optionally a siloxane oligomer having a terminal blocking group.
- an "organosiloxane mixture” is used as a raw material for polymerization will be described.
- a similar manufacturing process can be applied to the case where "organosiloxane” is used as a raw material for polymerization.
- the method for preparing the emulsion includes, for example, microparticulation by shearing force due to high-speed rotation, for example, a method using a homomixer; a method of mixing by stirring; A method using a homogenizer is preferred because it facilitates narrowing the particle size distribution of the polyorganosiloxane latex.
- Methods for mixing the acid catalyst during polymerization include, for example, a method of adding the acid catalyst together with the organosiloxane mixture, the emulsifier and water all at once (Method 1); A method of adding them all at once (Method 2); and a method of dropping an emulsion of an organosiloxane mixture into a hot acid catalyst aqueous solution at a constant rate and mixing them (Method 3); Method 3 is preferred because it is easier to control the particle size of the polyorganosiloxane.
- the polymerization temperature is preferably 50°C or higher, more preferably 70°C or higher.
- the upper limit of the polymerization temperature is, for example, 100°C.
- the polymerization time is usually 2 hours or more, preferably 5 hours or more.
- the cross-linking reaction between silanols proceeds. Therefore, in order to increase the cross-linking density of the polyorganosiloxane, the resulting latex is heated at a temperature of 30° C. or lower after polymerization at a high temperature of 50° C. or higher. The temperature can be maintained for about 5 hours to 100 hours.
- the polymerization reaction of the organosiloxane mixture can be terminated by neutralizing the reaction system containing the latex to a pH of 6 or more and 8 or less with an alkaline substance such as sodium hydroxide, potassium hydroxide, or an aqueous ammonia solution.
- an alkaline substance such as sodium hydroxide, potassium hydroxide, or an aqueous ammonia solution.
- the emulsifier is not particularly limited as long as it can emulsify the organosiloxane mixture, and an anionic emulsifier or nonionic emulsifier is preferred.
- anionic emulsifiers include sodium alkylbenzenesulfonate, sodium alkyldiphenylether disulfonate, sodium alkylsulfate, sodium polyoxyethylene alkylsulfate, and sodium polyoxyethylene nonylphenyl ether sulfate.
- nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylene alkyl ethers, polyoxyethylene distyrenated phenyl ethers, polyoxyethylene tribenzylphenyl ethers, and polyoxyethylene polyoxypropylene glycols.
- An emulsifier can be used individually by 1 type or in combination of 2 or more types.
- the amount of emulsifier used is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the organosiloxane mixture.
- the amount of the emulsifier used is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the organosiloxane mixture.
- the above upper and lower limits can be combined arbitrarily. For example, 0.05 to 20 parts by mass is preferable, and 0.1 to 10 parts by mass is more preferable.
- the particle size of the polyorganosiloxane latex can be adjusted to a desired value by adjusting the amount of emulsifier used.
- the particle size can be reduced, and if the amount of emulsifier is decreased, the particle size can be increased.
- the amount of the emulsifier used is at least the lower limit, the emulsification stability of the emulsion of the organosiloxane mixture can be enhanced.
- the amount of the emulsifier used is not more than the above upper limit, the molded article has excellent heat discoloration resistance and surface appearance.
- Acid catalysts used in the polymerization of organosiloxane mixtures include, for example, sulfonic acids such as aliphatic sulfonic acids, aliphatic-substituted benzenesulfonic acids, and aliphatic-substituted naphthalenesulfonic acids; and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. mentioned.
- An acid catalyst can be used individually by 1 type or in combination of 2 or more types.
- the particle size distribution of the polyorganosiloxane latex tends to be narrowed, and problems caused by the emulsifier component in the polyorganosiloxane latex (decrease in thermal decomposition resistance of the molded product, poor appearance, etc.) occur. easy to suppress.
- the amount of the acid catalyst used is preferably 0.005 parts by mass or more and 40 parts by mass or less per 100 parts by mass of the organosiloxane.
- the amount of the acid catalyst used is 0.005 parts by mass or more, the organosiloxane mixture can be polymerized in a short time.
- the amount of the acid catalyst used is 40 parts by mass or less, the molded article has excellent heat discoloration resistance and surface appearance.
- the amount of the acid catalyst used is a factor that determines the particle size of the polyorganosiloxane (A1), in order to obtain the polyorganosiloxane (A1) having a particle size described later, the amount of the acid catalyst used should be 100% of the organosiloxane. More preferably, the content is 1 part by mass or more and 30 parts by mass or less. In addition, when the amount of the acid catalyst used is small, the particle size tends to be large.
- an emulsifier may be added to the polyorganosiloxane latex obtained by the production method (M) for the purpose of improving mechanical stability.
- the emulsifier anionic emulsifiers and nonionic emulsifiers similar to those exemplified above are preferred.
- Polymer (A) may contain a vinyl polymer (A2).
- the polymer (A) may be a polymer in which the vinyl polymer (A2) and the polyorganosiloxane (A1) are crosslinked.
- it may be a composite polymer in which the polyorganosiloxane (A1) and the vinyl polymer (A2) are not crosslinked, and the vinyl polymer (A2) and the polyorganosiloxane (A1) are crosslinked. is preferred.
- the vinyl polymer (A2) is a polymer obtained by polymerizing the vinyl monomer component (a2). That is, the vinyl polymer (A2) contains vinyl monomer units derived from the vinyl monomer component (a2).
- the vinyl monomer component (a2) constituting the first vinyl polymer (A2) may be one kind of vinyl monomer or two or more kinds of vinyl monomers.
- the vinyl monomer component (a2) preferably contains a (meth)acrylate monomer (hereinafter also referred to as "monomer (a2-1)") from the viewpoint of the impact strength of the molded article.
- the monomer (a2-1) is not particularly limited, and preferably includes a (meth)acrylate having an alkyl group with 1 or more and 20 or less carbon atoms.
- alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i- alkyl methacrylates such as butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate;
- the (meth)acrylate is preferably an alkyl acrylate having 1 to 20 carbon atoms.
- the number of carbon atoms in the alkyl group of the alkyl acrylate is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 16 or less, and more preferably 12 or less, because the impact strength of the molded article is improved. 8 or less is more preferable.
- Particularly preferred is n-butyl acrylate.
- the monomer (a2-1) can be used singly or in combination of two or more.
- the vinyl monomer component (a2) may contain other monomers.
- Other monomers include polyfunctional monomers copolymerizable with the monomer (a2-1) (hereinafter also referred to as "monomer (a2-2)").
- the vinyl monomer component (a2) preferably contains the monomer (a2-1) and the monomer (a2-2) from the viewpoint of the impact strength of the molded article.
- the monomer (a2-2) is not particularly limited, and includes (meth)acrylate and cyanurate.
- (Meth)acrylates include, for example, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, and allyl methacrylate.
- Cyanurates include, for example, triallyl cyanurate and triallyl isocyanurate.
- the monomer (a2-2) can be used singly or in combination of two or more.
- the ratio of the monomer (a2-1) in 100% by mass of the vinyl monomer component (a2) is not particularly limited, and from the viewpoint of improving the impact strength of the molded article, it is preferably 60% by mass or more, and 70% by mass. 80% by mass or more is more preferable, and 90% by mass or more is particularly preferable.
- the ratio of the monomer (a2-1) to 100% by mass of the vinyl monomer component (a2) is 100% by mass or less, preferably 99.9% by mass or less.
- the above upper and lower limits can be combined arbitrarily. For example, 60 to 100% by mass is preferable, 70 to 100% by mass is more preferable, 80 to 99.9% by mass is even more preferable, and 90 to 99.9% by mass is particularly preferable.
- the ratio of the monomer (a2-2) in 100% by mass of the vinyl monomer component (a2) is not particularly limited, and is preferably 0.1% by mass or more and 2% by mass or less in order to improve impact strength. is more preferred.
- the vinyl monomer component (a2) may contain a monomer (a2-3) other than the monomer (a2-1) and the monomer (a2-2).
- Other monomers (a2-3) are not particularly limited and include, for example, aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylic group-modified silicones.
- the aromatic vinyl monomer is not particularly limited and includes styrene and ⁇ -methylstyrene.
- the vinyl cyanide monomer is not particularly limited and includes acrylonitrile and methacrylonitrile.
- Other monomers (a2-3) can be used singly or in combination of two or more.
- Polymer (A) Polymer (A) contains polyorganosiloxane (A1) and vinyl polymer (A2). Polymer (A) preferably functions as a composite rubber of polyorganosiloxane (A1) and vinyl polymer (A2). It is preferable that the polyorganosiloxane (A1) and the vinyl polymer (A2) each have a glass transition temperature (hereinafter sometimes referred to as Tg) of 0° C. or lower in order to function as a composite rubber.
- Tg glass transition temperature
- the mass ratio represented by polyorganosiloxane (A1)/vinyl polymer (A2) is preferably 50/50 or more, 70/ 98 or more is more preferable, 99/1 or less is preferable, and 95/5 or less is more preferable.
- the above upper and lower limits can be combined arbitrarily. For example, 50/50 to 99/1 is preferred, and 70/98 to 95/5 is more preferred.
- the method for producing the polymer (A) is not particularly limited, but since the molded article has excellent impact strength, in the presence of the latex containing the polyorganosiloxane (A1), the vinyl monomer constituting the vinyl polymer (A2) A method of polymerizing body component (a2) is preferred.
- the method of polymerizing the vinyl monomer component (a2) in the presence of the latex containing the polyorganosiloxane (A1) is not particularly limited, and the vinyl monomer component (a2) is added to the latex containing the polyorganosiloxane (A1).
- Method iii A method (method iii) in which the total amount of the vinyl monomer component (a2) is charged under conditions that do not initiate polymerization, particles of the polyorganosiloxane (A1) are impregnated, and then polymerized (method iii). Method iii is preferred because the molded article has excellent impact strength.
- the method for producing the vinyl polymer (A2) is not particularly limited. Polymerization methods are preferred.
- radical polymerization initiator used for polymerization of the vinyl monomer (a2) an azo initiator; a peroxide; and a redox initiator combining a peroxide and a reducing agent; are used.
- a radical polymerization initiator can be used individually by 1 type or in combination of 2 or more types. Azo initiators and redox initiators are preferred.
- azo initiators examples include 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2,4-dimethylvalero nitrile), oil-soluble azo initiators such as 2,2'-azobis (2-butyronitrile); 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis [N-(2- Carboxymethyl)-2-methylpropionamidine] hydrate, 2,2′-azobis-(N,N′-dimethyleneisobutylamidine) dihydrochloride, 2,2′-azobis[2-(2-imidazoline- 2-yl) propane] dihydrochloride and other water-soluble azo initiators; These can be used individually by 1 type or in combination of 2 or more types.
- peroxides examples include inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate; diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, succinic acid peroxide, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2- organic peroxides such as ethylhexanoate and t-butylperoxy-2-ethylhexanoate;
- a peroxide can be used individually by 1 type or in combination of 2 or more types.
- a redox initiator is obtained by combining a peroxide with a reducing agent, the above peroxide, a reducing agent such as sodium formaldehyde sulfoxylate, L-ascorbic acid, fructose, dextrose, sorbose, inositol, and sulfuric acid It is preferable to use monoiron/ethylenediaminetetraacetic acid disodium salt in combination. Redox initiators can be used singly or in combination of two or more.
- the radical polymerization initiator used for the polymerization of the vinyl monomer (a2) is a radical polymerization initiator having a solubility in water of 5% by mass or less at 20° C., since it is easy to obtain a graft copolymer having excellent impact resistance.
- a radical polymerization initiator of 2% by mass or less is preferred, and more preferred.
- radical polymerization initiator having a solubility in water at 20° C. of 5% by mass or less examples include cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate ate, 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′ -azobis(2-butyronitrile).
- the radical polymerization initiators having a solubility in water at 20° C. of 5% by mass or less can be used singly or in combination
- radical polymerization initiators in water at 20°C can be found from catalogs of various radical polymerization initiators.
- the amount of the azo initiator used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total monomers.
- the amount of peroxide to be used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total monomers.
- the amount of the reducing agent used is preferably 0.01 to 1 part by mass with respect to the total of 100 parts by mass of the monomers.
- the vinyl polymer (B) is a polymer obtained by polymerizing the vinyl monomer component (b), and is a polymer containing structural units derived from vinyl monomers.
- the vinyl monomer component (b) constituting the vinyl polymer (B) may be one or more vinyl monomers.
- the vinyl monomer that constitutes the vinyl monomer component (b) is not particularly limited, but preferably includes a (meth)acrylate monomer.
- (Meth)acrylate monomers are not particularly limited, and include alkyl (meth)acrylates.
- the obtained graft copolymer has excellent compatibility and dispersibility in a thermoplastic resin such as a polycarbonate resin. Tend.
- alkyl (meth)acrylates examples include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and i-butyl methacrylate; methyl acrylate, ethyl acrylate and n-butyl acrylate; (Meth)acrylate monomers may be used alone or in combination of two or more.
- the number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is not particularly limited, and is preferably 1 or more, preferably 12 or less, more preferably 6 or less, and even more preferably 4 or less.
- the above upper and lower limits can be combined arbitrarily. For example, 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 4 are even more preferred. Methyl methacrylate is particularly preferred.
- the vinyl monomer component (b) further contains one or more monomers selected from the group consisting of polyfunctional vinyl monomers, aromatic vinyl monomers, and vinyl cyanide monomers. It's okay.
- polyfunctional vinyl monomers examples include allyl (meth)acrylate, triallyl cyanurate, divinylbenzene, diallyl phthalate, and ethylene glycol di(meth)acrylate.
- Polyfunctional vinyl monomers may be used alone or in combination of two or more.
- the aromatic vinyl monomer is not particularly limited, and examples include styrene and ⁇ -methylstyrene.
- One aromatic vinyl monomer may be used alone, or two or more thereof may be used in combination.
- the vinyl cyanide monomer is not particularly limited, and examples include acrylonitrile and methacrylonitrile. Vinyl cyanide monomers may be used alone or in combination of two or more.
- the ratio of the (meth)acrylate monomer in 100% by mass of the vinyl polymer (B) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. , 100% by mass.
- the Tg of the vinyl polymer (B) is preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and preferably 105°C or lower.
- the above upper and lower limits can be combined arbitrarily. For example, 70 to 105°C is preferred, 80 to 105°C is more preferred, and 90 to 105°C is even more preferred.
- the obtained powder of the polymer (C) has good fluidity and the like.
- the Tg of the vinyl polymer (B) can be adjusted by adjusting the type and ratio of the vinyl monomers constituting the vinyl monomer component (b).
- the Tg of the vinyl polymer (B) is obtained by the FOX formula.
- the Tg of the vinyl monomer homopolymer constituting the vinyl monomer component (b) for example, the value described in "Polymer Handbook” (Wiley Interscience/1999) can be used.
- the Tg of homopolymers of vinyl monomers not described in this document can be calculated using Bicerano's method "Prediction of Polymer Properties” (MARCEL DEKKER, 2002).
- the polymer (C) can be produced, for example, by polymerizing (graft polymerization) the vinyl monomer component (b) in the presence of the polymer (A). As a result, a polymer in which a part or all of the vinyl polymer (B) is grafted onto the polymer (A) is obtained.
- the method for producing the polymer (C) is not particularly limited. method is preferred.
- the latex of the polymer (A) is preferably produced by polymerizing the vinyl monomer component (a2) in the presence of the latex containing the polyorganosiloxane (A1).
- Conditions for polymerizing the vinyl monomer component (b) are not particularly limited, and conventional conditions can be applied, for example, conditions of 45 to 95° C. and 0.1 to 10 hours.
- the method of adding the vinyl monomer component (b) to the latex of the polymer (A) is not particularly limited, and it is preferable to add it dropwise since the generation of cullet can be suppressed.
- the total amount of the vinyl monomer component (b) may be dropped continuously, or the vinyl monomer component (b) may be dropped in multiple portions while providing a holding time during which the vinyl monomer component (b) is not dropped.
- the polymer (C) is recovered as a powder (or a powder group, or a powder group containing contaminants) from the resulting latex of the polymer (C). preferably.
- a direct drying method such as a spray drying method or a coagulation method can be used.
- the auxiliaries added at the time of polymerization can generally remain in the resulting powder.
- the coagulation method residual polymerization aids contained in the resulting powder, such as the emulsifier used during polymerization, its coagulation salt, and the initiator, can be reduced in the washing step after coagulation.
- the powder recovery method can be appropriately selected so that the polymer (C) remains in a desired state when added to the thermoplastic resin.
- the spray drying method which is a direct drying method, is a method in which the polymer (C) latex is sprayed into a dryer in the form of fine droplets, which are then dried by applying a heated gas for drying.
- Methods for generating fine droplets include, for example, a rotating disc type, a pressure nozzle type, a two-fluid nozzle type, and a pressurized two-fluid nozzle type.
- the capacity of the dryer can be from small capacity for laboratory use to large capacity for industrial use.
- the temperature of the heating gas for drying is preferably 200°C or less, more preferably 120 to 180°C. Latices of two or more graft copolymers made separately can also be spray dried together.
- optional components such as silica may be added to the latex of the polymer (C) and spray drying may be carried out.
- the coagulation method is a method of coagulating the latex of the polymer (C), separating the polymer (C), recovering it, and drying it.
- a latex of the polymer (C) is put into hot water in which a coagulant is dissolved, and the polymer (C) is separated by salting out and coagulating. Dehydration or the like is performed to recover the polymer (C) with a reduced water content.
- the recovered polymer (C) is dried using a press dehydrator or a hot air dryer.
- the coagulant includes, for example, inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate and calcium acetate; acids such as sulfuric acid; calcium acetate is preferred.
- a coagulant can be used individually by 1 type or in combination of 2 or more types.
- the concentration of the aqueous coagulant solution is preferably 0.1% by mass or more, more preferably 1% by mass or more, from the viewpoint of stably coagulating and recovering the polymer (C).
- the concentration of the coagulant aqueous solution is preferably 20% by mass or less, more preferably 15% by mass, from the viewpoint of reducing the amount of the coagulant remaining in the recovered polymer (C) and preventing deterioration of the molding appearance of the molded article.
- the above upper and lower limits can be combined arbitrarily. For example, 0.1 to 20% by mass is preferable, and 1 to 15% by mass is more preferable.
- the amount of the aqueous coagulant solution is not particularly limited, and is preferably 10 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the latex of the polymer (C).
- the method of bringing the latex of the polymer (C) into contact with the aqueous coagulant solution is not particularly limited, and the following methods may be mentioned.
- the temperature at which the latex is brought into contact with the aqueous coagulant solution is not particularly limited, and is preferably 30°C or higher and 100°C or lower. Contact time is not particularly limited.
- the coagulated polymer (C) is washed with about 1 to 100 times the weight of water of the polymer (C) and filtered.
- the filtered wet polymer (C) is dried using a fluidized dryer, a dehydrator, or the like.
- the drying temperature and drying time may be appropriately determined according to the polymer (C) to be obtained.
- the polymer (C) discharged from the press dehydrator or extruder may be directly sent to an extruder or molding machine for producing a resin composition without recovering it, and mixed with a thermoplastic resin to obtain a molded product. .
- a powder of the polymer (C) can be obtained by drying the obtained polymer (C), and an alkali metal atom in the powder of the polymer (C) can be removed by treating with an alkali metal salt solution. can be increased. Specifically, after adding deionized water to the powder of the polymer (C) and stirring, an aqueous alkali metal salt solution is added and stirred, followed by filtration, washing, dehydration and drying to remove the alkali metal atoms. A powder of the polymer (C) containing more can be obtained. Increasing the alkali metal salt concentration of the alkali metal salt solution tends to increase the atomic weight of the alkali metal contained in the powder of the polymer (C).
- the proportion of polyorganosiloxane (A1) in 100% by mass of polymer (C) is preferably less than 100% by mass, more preferably 98% by mass or less.
- the proportion of polyorganosiloxane (A1) in 100% by mass of polymer (C) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- the above upper and lower limits can be combined arbitrarily. For example, 50% by mass or more and less than 100% by mass is preferable, 70% by mass or more and less than 100% by mass is more preferable, 70 to 98% by mass is more preferable, 90 to 98% by mass or more is particularly preferable, and 95 to 98% by mass. The above are particularly preferred.
- the proportion of the polyorganosiloxane (A1) is at least the above lower limit, the impact strength of the molded article is excellent.
- the content is equal to or less than the above upper limit, the colored appearance of the molded product
- the proportion of polymer (A) in 100% by mass of polymer (C) is preferably 60% by mass or more, more preferably 70% by mass or more.
- the proportion of the polymer (A) in 100% by mass of the polymer (C) is preferably 95% by mass or less, more preferably 90% by mass or less.
- the above upper and lower limits can be combined arbitrarily. For example, 60 to 95% by mass is preferable, and 70 to 90% by mass is more preferable. If the content of the polymer (A) is at least the above lower limit, the impact strength and flame retardancy of the molded product will be excellent. If it is at most the above upper limit, the dispersibility of the polymer (C) in the thermoplastic resin is excellent, and the appearance of the resulting molded article is excellent.
- the proportion of the graft portion in 100% by mass of the polymer (C) is preferably 5% by mass or more, more preferably 7.5% by mass or more, and even more preferably 10% by mass or more.
- the proportion of the graft portion in 100% by mass of the polymer (C) is preferably 20% by mass or less, more preferably 17.5% by mass or less, and even more preferably 15% by mass or less.
- the above upper and lower limits can be combined arbitrarily. For example, 5 to 20% by mass is preferable, 7.5 to 17.5% by mass is more preferable, and 10 to 15% by mass is even more preferable.
- the content of the graft portion is at least the above lower limit, the dispersibility of the polymer (C) in the thermoplastic resin is excellent, and the appearance of the resulting molded article is excellent. If it is less than the above upper limit, the impact strength of the molded article is excellent.
- the proportion of the vinyl polymer (B) in 100% by mass of the polymer (C) is preferably 5% by mass or more, more preferably 10% by mass or more.
- the proportion of the vinyl polymer (B) in 100% by mass of the polymer (C) is preferably 40% by mass or less, more preferably 35% by mass or less.
- the above upper and lower limits can be combined arbitrarily. For example, 5 to 40% by mass is preferable, and 10 to 35% by mass is more preferable.
- the content of the vinyl polymer (B) is at least the above lower limit, the dispersibility of the polymer (C) in the thermoplastic resin is excellent, and the resulting molded article has an excellent appearance. If it is less than the above upper limit, the impact strength of the molded article is excellent.
- the resin composition according to one aspect of the present invention (hereinafter also referred to as “this resin composition”) comprises a polymer (C) and a thermoplastic resin (hereinafter also referred to as “thermoplastic resin (D)"). including.
- thermoplastic resin (D) is not particularly limited. system resins (vinyl chloride resin, etc.) and acrylic resins.
- thermoplastic engineering plastics various known thermoplastic engineering plastics can be used without particular limitation.
- engineering plastics include polyphenylene ether, polycarbonate, polyester polymers (polyethylene terephthalate, polybutylene terephthalate, etc.), syndiotactic polystyrene, nylon polymers (6-nylon, 6,6-nylon, etc.), and polyarylate.
- aromatic polycarbonate and polybutylene terephthalate are more preferable when higher strength development is required.
- aromatic polycarbonates include 4,4'-dioxydiarylalkane-based polycarbonates such as 4,4'-dihydroxydiphenyl-2,2-propane (bisphenol A)-based polycarbonates.
- olefin resins examples include high-density polyethylene; medium-density polyethylene; low-density polyethylene; copolymers of ethylene and other ⁇ -olefins; polypropylene; copolymers of propylene and other ⁇ -olefins; Poly-4-methylpentene-1;
- thermoplastic elastomers examples include styrene-based elastomers, urethane-based elastomers, polyolefin-based elastomers, polyamide-based elastomers, fluorine-based elastomers, chlorinated PE-based elastomers, and acrylic-based elastomers.
- Styrene-based elastomers include, for example, styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene/butene copolymer (SEB), styrene-ethylene/propylene copolymer.
- SBS styrene-butadiene-styrene copolymer
- SIS styrene-isoprene-styrene copolymer
- SEB styrene-ethylene/butene copolymer
- SEP styrene-ethylene-butene-styrene copolymer
- SEBS styrene-ethylene-propylene-styrene copolymer
- SEPS styrene-ethylene-ethylene-propylene-styrene copolymer
- SEEPS Styrene-butadiene-butylene-styrene copolymer
- SBBS partially hydrogenated SIS copolymer, part of styrene-isoprene-butadiene-styrene copolymer Hydrogenates are mentioned. "-" indicates that the monomers forming the units connected by "-" are copolymerized, and " ⁇ " is randomly modified by hydrogenation or the like after copolymerization. indicates that
- Urethane-based elastomers include, for example, reaction products of polymeric diols, organic diisocyanates, and chain extenders.
- polymeric diols include polyester diols, polyether diols, polyester ether diols, polycarbonate diols, and polyester polycarbonate diols.
- organic diisocyanates examples include 4,4′-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate (4,4′-dicyclohexylmethane diisocyanate), Examples include isophorone diisocyanate and hexamethylene diisocyanate, and 4,4'-diphenylmethane diisocyanate is preferred.
- chain extenders examples include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1 ,9-nonanediol, cyclohexanediol, 1,4-bis( ⁇ -hydroxyethoxy)benzene.
- polyolefin elastomers examples include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, and ethylene-acrylate copolymer.
- styrene resins include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene- ⁇ -methylstyrene copolymer, acrylonitrile-methyl methacrylate-styrene- ⁇ -methylstyrene copolymer, ABS resin, AS resin, MABS resin, MBS resin, AAS resin, AES resin, acrylonitrile-butadiene-styrene- ⁇ -methylstyrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene- ⁇ -methylstyrene copolymer, styrene-maleic anhydride copolymer Copolymers, styrene-maleimide copolymers, styrene-N-substituted maleimide copolymers, acrylonitrile-styrene-N-substituted
- the polyester resin is a polymer of a polybasic acid and a polyhydric alcohol, and is not particularly limited as long as it has thermoplasticity.
- Polybasic acids include, for example, terephthalic acid, naphthaldicarboxylic acid, cyclohexyldicarboxylic acid and esters thereof.
- Polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis(4-hydroxyethoxy phenyl)propane, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A bis(2-hydroxyethyl)ether (TBA-EO).
- the polyester resin may be a homopolymer, a copolymer, or a blend of two or more of these.
- a commercially available product such as "PETG” manufactured by Eastman Chemical Co. may be used.
- biodegradable resins include microbial polymers, chemical synthesis polymers, and natural product polymers.
- microbial polymers include biopolyesters such as polyhydroxybutyrate/valerate (PHB/V), bacterial cellulose, and microbial polysaccharides (pullulan, curdlan, etc.).
- chemically synthesized polymers include aliphatic polyesters (polycaprolactone, polybutylene succinate, polyethylene succinate, polyglycolic acid, polylactic acid, etc.), polyvinyl alcohol, and polyamino acids (PMLG, etc.).
- natural product-based polymers include chitosan, cellulose, starch, and cellulose acetate.
- halogen-based resins include vinyl chloride homopolymers, copolymers containing 80% by mass or more of vinyl chloride, and vinyl chloride resins such as highly chlorinated polyvinyl chloride.
- Copolymer components include, in addition to vinyl chloride, monovinylidene compounds such as ethylene, vinyl acetate, methyl methacrylate, and butyl acrylate. The proportion of structural units derived from these compounds in the copolymer may be 20% by mass or less.
- halogen-based resins include, in addition to vinyl chloride resins, fluorinated polymers, brominated polymers, and iodinated polymers.
- acrylic resins include copolymers obtained by polymerizing methyl methacrylate and copolymerizable vinyl monomers.
- copolymerizable vinyl monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate and the like.
- Aromatic vinyl compounds such as alkyl methacrylate, styrene, ⁇ -methylstyrene, and vinyl toluene are included.
- Polyester resins such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as syndiotactic polystyrene, 6-nylon and 6,6-nylon, polyarylate, polyphenylene sulfide, polyether ketone, polyether ether Polymer alloys of engineering plastics such as ketones, polysulfones, polyethersulfones, polyamideimides, polyetherimides and polyacetals and other thermoplastic resins are also included in the scope of the thermoplastic resin (D).
- the thermoplastic resin (D) can be used alone or in combination of two or more.
- the thermoplastic resin (D) is industrially readily available and has an excellent balance between the impact strength and colorability of the molded product. It preferably contains at least one selected from the group consisting of butylene terephthalate, polyvinyl chloride, polyphenylene sulfide and polyacetal, and at least one selected from the group consisting of polymethyl methacrylate and styrene-acrylonitrile copolymer. more preferred.
- the present resin composition may contain various well-known additives within a range that does not impair the object of the present invention.
- Additives include, for example, flame retardants (e.g., phosphorus-based, bromine-based, silicone-based, organometallic salt-based), anti-drip agents (e.g., fluorinated polyolefins, silicone and aramid fibers), lubricants (e.g., magnesium stearate long-chain fatty acid metal salts, etc.), release agents (e.g., pentaerythritol tetrastearate), nucleating agents, antistatic agents, stabilizers (e.g., phenol-based stabilizers, phosphorus-based stabilizers, ultraviolet absorbers, amines system light stabilizers), fillers (eg titanium oxide, talc, mica, kaolin, calcium carbonate, glass flakes), plasticizers, reinforcing agents (eg glass fibers, carbon fibers), dyes and pigment
- dyes or pigments include inorganic pigments such as iron oxide, ultramarine blue, titanium oxide, and carbon black.
- organic pigments include phthalocyanine-based and anthraquinone-based blue pigments, perylene-based and quinacridone-based red pigments, and isoindolinone-based yellow pigments.
- special pigments include fluorescent pigments, metal powder pigments, and pearl pigments.
- dyes include nigrosine, perinone, and anthraquinone dyes. Colorants and pigments are commercially available in various grades depending on the desired color, and they can be used either alone or in combination of two or more.
- the proportion of the polymer (C) in 100% by mass of the present resin composition is not particularly limited, preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more.
- the proportion of the polymer (C) in 100% by mass of the present resin composition is preferably 30% by mass or less, more preferably 20% by mass or less.
- the above upper and lower limits can be combined arbitrarily. For example, 0.5 to 30% by mass is preferable, 1 to 30% by mass is more preferable, and 2 to 20% by mass is even more preferable.
- the proportion of the polymer (C) is at least the above lower limit, the impact strength of the obtained molded article is excellent.
- the content is equal to or less than the upper limit, it is possible to suppress a decrease in fluidity and heat distortion temperature of the resin composition.
- the proportion of the thermoplastic resin (D) in 100% by mass of the present resin composition is not particularly limited, preferably 40% by mass or more, more preferably 50% by mass or more.
- the proportion of the thermoplastic resin (D) in 100% by mass of the present resin composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less.
- the above upper and lower limits can be combined arbitrarily. For example, 40 to 99.5% by mass is preferable, 40 to 99% by mass is more preferable, and 50 to 98% by mass is even more preferable.
- the proportion of the thermoplastic resin (D) is at least the above lower limit, it is possible to suppress a decrease in fluidity and heat distortion temperature of the resin composition. If it is not more than the above upper limit, the impact strength of the obtained molded article is excellent.
- the resin composition can be produced by mixing the polymer (C), the thermoplastic resin (D) and, if necessary, additives.
- a method for mixing each material includes a known blending method, and is not particularly limited. Examples thereof include a method of mixing and kneading with a tumbler, V-type blender, super mixer, Nauta mixer, Banbury mixer, kneading roll, extruder, or the like.
- the polymer (C), the thermoplastic resin (D) in pellet form, and optionally additives are mixed using an extruder, extruded into strands, A method of cutting into pellets with a rotary cutter or the like can be used. By this method, a pellet-shaped resin composition can be obtained.
- a molded article according to one aspect of the present invention (hereinafter also referred to as "main molded article”) contains a polymer (C) and a thermoplastic resin (D).
- the molded article may further contain other components.
- Other components include known components. It is preferable that the present molded article is made of the present resin composition.
- the present molded article can be produced, for example, by molding the present resin composition.
- the molding method include molding methods used for molding thermoplastic resin compositions, such as injection molding, extrusion molding, blow molding, and calendar molding.
- This molded product can be widely used industrially, for example, as various materials in the fields of automobiles, OA equipment, home appliances, electrical/electronics, construction, lifestyle/cosmetics, and medical products. More specifically, for example, it can be used as housings for electronic devices, various parts, covering materials, automobile structural members, automobile interior parts, light reflecting plates, building structural members, and fittings. More specifically, for example, personal computer housing, mobile phone housing, mobile information terminal housing, portable game machine housing, interior and exterior members such as printers and copiers, conductive coating materials, automobile interior and exterior members , building exterior materials, resin window frame members, flooring materials, and piping members.
- Solid content [%] w2/w1 x 100
- ⁇ Particle size> A sample obtained by diluting "polyorganosiloxane (A1) latex” or “polymer (C) latex” with deionized water to a solid content concentration of about 3% is measured using a CHDF2000 particle size distribution meter manufactured by MATEC in the United States. The number average particle size Dn and the mass average particle size Dw were measured using the following conditions.
- Cartridge Dedicated capillary cartridge for particle separation (trade name: C-202), Carrier liquid: Dedicated carrier liquid (trade name; 2XGR500), Liquid property of carrier liquid: Neutral, Carrier liquid flow rate: 1.4 mL/min, carrier liquid pressure: 4,000 psi (2,600 kPa); Measurement temperature: 35°C, Amount of sample used: 0.1 mL.
- ⁇ Amount of residual metal> Weigh about 0.25 g of the sample, add 8 mL of nitric acid and 2 mL of hydrogen fluoride water, perform decomposition treatment by microwave (wet decomposition), add distilled water to 50 mL, and use as a test solution an ICP emission spectrometer ( The amount of residual metal was quantified using iCAP7400 Duo manufactured by Thermo.
- Thermal decomposability was evaluated by the following method.
- the residual amount at each temperature when the sample temperature was raised to 550° C. at 10° C./min under the condition of a nitrogen flow rate of 200 mL/min was calculated by the following formula (1).
- the thermal decomposability was calculated by the following formula (2). The smaller the value calculated in (2), the shorter the time required from the start to the end of thermal decomposition, and the better the thermal decomposability.
- Remaining amount (%) mass after retention (g)/mass of charge (g) Formula (1)
- Thermal decomposition (° C.) ((Temperature at 70% residual amount) - (Temperature at 1% residual amount) Equation (2)
- aqueous solution prepared by dissolving 1 part of sodium dodecylbenzenesulfonate (DBSNa) in 150 parts of deionized water was added to the organosiloxane mixture, and after stirring at 10,000 rpm for 5 minutes with a homomixer, a pressure of 20 MPa was applied to the homogenizer. to obtain a stable premixed emulsion.
- DBSNa sodium dodecylbenzenesulfonate
- the solid content of the polyorganosiloxane latex (S-1) was 30.2% by mass.
- the number average particle diameter (Dn) was 384 nm
- the mass average particle diameter (Dw) was 403 nm
- Dw/Dn was 1.05.
- Polyorganosiloxane latex (S-4) was obtained in the same manner as in Production Example 1-1, except that the composition of the organosiloxane mixture was changed to that shown in Table 1.
- the solid content of the polyorganosiloxane latex (S-4) was 30.8% by mass.
- the number average particle diameter (Dn) was 384 nm
- the mass average particle diameter (Dw) was 403 nm
- Dw/Dn was 1.05.
- aqueous solution prepared by dissolving 0.68 parts of sodium dodecylbenzenesulfonate (DBSNa) and 0.68 parts of dodecylbenzenesulfonic acid (DBSH) in 150 parts of deionized water was added to the organosiloxane mixture and mixed with a homomixer for 10 minutes. ,000 rpm for 5 minutes and then passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion.
- the solid content of the polyorganosiloxane latex (S-5) was 33.0% by mass.
- the number average particle diameter (Dn) was 64 nm
- the mass average particle diameter (Dw) was 248 nm
- Dw/Dn was 3.88.
- Production of polyorganosiloxane latex (S-6) The same procedure as in Production Example 1-1 was performed, except that the composition of the organosiloxane mixture was changed to that shown in Table 1 and the amount of sodium dodecylbenzenesulfonate (DBSNa) was increased to 1.5 parts. A siloxane latex (S-6) was obtained.
- the solid content of the polyorganosiloxane latex (S-6) was 30.8% by mass.
- the number average particle diameter (Dn) was 38 nm
- the mass average particle diameter (Dw) was 276 nm
- Dw/Dn 7.26.
- Table 1 shows the components of Production Examples 1-1 to 1-6. Abbreviations in Table 1 are as follows.
- TSF404 octamethylcyclotetrasiloxane
- DMC mixture of 3- to 6-membered cyclic organosiloxanes
- DSMA ⁇ -methacryloyloxypropyldimethoxymethylsilane
- TEOS tetraethoxysilane
- Example 1-1 80 parts of the polyorganosiloxane latex (S-1) obtained in Production Example 1-1 (10.0 parts in terms of polymer) was collected in a separable flask with a capacity of 5 liters, and 8.82 parts of butyl acrylate (BA). , 0.18 parts of allyl methacrylate (AMA) and 0.16 parts of cumene hydroperoxide (CB) were added and stirred at room temperature for 1 hour to impregnate the polyorganosiloxane.
- BA butyl acrylate
- BA butyl acrylate
- AMA allyl methacrylate
- CB cumene hydroperoxide
- the atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream, and the liquid temperature was raised to 50°C.
- the liquid temperature reached 50°C, 0.001 part of ferrous sulfate (Fe), 0.003 part of ethylenediaminetetraacetic acid disodium salt (EDTA), and 0.24 part of sodium formaldehyde sulfoxylate (SFS) were removed.
- An aqueous solution dissolved in 10 parts of ionized water was added to initiate radical polymerization.
- the liquid temperature was kept at 65° C. for 1 hour to complete the polymerization of the acrylate component to obtain a latex of composite rubber of polyorganosiloxane and poly-n-butyl acrylate.
- a liquid mixture of 11.0 parts of methyl methacrylate (MMA) and 0.24 parts of cumene hydroperoxide (CB) was added dropwise into the latex over 1 hour while the liquid temperature of the obtained composite rubber latex was adjusted to 65°C. , initiated the graft polymerization reaction. After completion of dropping, the temperature was maintained at 65° C. for 1 hour and then cooled to room temperature to obtain a latex of polyorganosiloxane-containing graft copolymer (G-1).
- MMA methyl methacrylate
- CB cumene hydroperoxide
- graft copolymer (G-1) 500 parts of an aqueous solution with a calcium acetate concentration of 1% by mass was heated to 85° C., and while stirring, 340 parts of the latex of the graft copolymer (G-1) was gradually dropped to solidify. The resulting graft copolymer (G-1) was filtered, washed, dehydrated, and dried to obtain a graft copolymer (G-1).
- graft copolymer (G-1) After 10 parts of the obtained graft copolymer (G-1) was added to 141 parts of deionized water and stirred for 3 minutes, 10 parts of a 10% by mass sodium chloride aqueous solution was added and stirred for 3 minutes.
- the graft copolymer (A-1) was filtered, washed, dehydrated, and dried to obtain a sodium-containing graft copolymer powder (A-1).
- the weight average particle size, alkali metal content and thermal decomposability of the resulting graft copolymer powder (A-1) were measured by the methods described above. Table 2 shows the results obtained.
- Example 2 Polyorganosiloxane-containing graft copolymers (G-2 to G-4) were prepared in the same manner as in Example 1-1, except that the raw material compositions used in Example 1-1 were changed to the conditions shown in Table 2. and obtained graft copolymer powders (A-2 to A-4) and subjected to similar measurements. Table 2 shows the results obtained.
- Example 1-5 A polyorganosiloxane-containing graft copolymer (G-1) was produced in the same manner as in Example 1-1, and the amount of the aqueous solution having a sodium chloride concentration of 10% by mass was changed to 20 parts. Graft copolymer powder (A-5) was obtained in the same manner as in 1-1, and the same measurement was performed. Table 2 shows the results obtained.
- Example 1-6 A polyorganosiloxane-containing graft copolymer (G-1) was produced in the same manner as in Example 1-1, and the amount of the aqueous solution having a sodium chloride concentration of 10% by mass was changed to 50 parts. Graft copolymer powder (A-6) was obtained in the same manner as in 1-1, and the same measurement was performed. Table 2 shows the results obtained.
- Example 1-5 A polyorganosiloxane-containing graft copolymer (G-5) was produced in the same manner as in Example 1-1 except that the raw material compositions used in Example 1-1 were changed to the conditions shown in Table 2, Further, a graft copolymer powder (A-11) was obtained and subjected to the same measurement. Table 2 shows the results obtained.
- nBA n-butyl acrylate
- AMA allyl methacrylate
- MMA methyl methacrylate
- the graft polymers according to Examples 1-1 to 1-6 had improved thermal decomposability compared to the graft copolymers according to Comparative Examples 1-1 to 1-7.
- Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-8 A polyorganosiloxane-containing polymer powder, an additive, and a thermoplastic resin were blended in the proportions shown in Table 3 to obtain a mixture. This mixture was supplied to a devolatilizing twin-screw extruder (manufactured by Ikegai Co., Ltd., PCM-30 (trade name)) and kneaded to prepare pellets of each resin composition.
- a devolatilizing twin-screw extruder manufactured by Ikegai Co., Ltd., PCM-30 (trade name)
- thermoplastic resin The following were used as the thermoplastic resin.
- PC Polycarbonate resin (Iupilon S-2000F, manufactured by Mitsubishi Engineering-Plastics, viscosity average molecular weight 24,000). The following additives were used.
- A-3750 Acrylic-modified PTFE (METABLEN A-3750, manufactured by Mitsubishi Chemical Corporation).
- Test piece A length 80 mm x width 10 mm x thickness 4 mm
- Test piece B length 100 mm x width 50 mm x thickness 2 mm
- Test piece C length 125 mm x width 13 mm x thickness 1.6 mm
- Extrusion conditions and injection molding conditions are as follows. Extrusion barrel temperature 280°C, Injection cylinder temperature: 280°C, Mold temperature: 60°C.
- Charpy impact strength was measured on test piece A by notching TYPE A notches conforming to ISO 179-1. The higher the Charpy impact strength, the higher the impact resistance. Table 3 shows the results obtained.
- test piece C the total burning time of five test pieces and the presence or absence of drip during ignition were measured by the vertical burning test method based on the UL94V test. It is preferable that the shorter the total burning time, the higher the flame retardancy and the absence of drip. Table 3 shows the evaluation results.
- the resin composition according to Comparative Example 2-1 did not contain a graft copolymer, its low-temperature impact strength and flame retardancy were low.
- the molded bodies according to Examples 2-1 to 2-9 which contain a polymer containing a specific particle size and a specific amount of alkali metal atoms, are compared with the molded bodies according to Comparative Examples 2-1 to 2-8. It had better flame retardancy.
- the graft copolymers of Comparative Examples 2-6 to 2-7 had a smaller particle size and were inferior in appearance.
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Abstract
Description
本願は、2021年3月30日に日本出願された、特願2021-056873号に基づき優先権を主張し、その内容をここに援用する。
特許文献2には、体積平均粒子径が300~2000nmであり、ポリオルガノシロキサンの含有量が70~98質量%のポリオルガノシロキサン含有グラフト共重合体が記載されている。
本発明は、樹脂に添加した際に、耐衝撃特性を大幅に低下させることなく優れた難燃性を示す成形体を得ることができるポリオルガノシロキサン含有重合体を提供することを目的とする。
[1]アルカリ金属原子を100質量ppm以上含有し、質量平均粒子径Dwが350nm以上である、ポリオルガノシロキサン含有重合体。
[2]質量平均粒子径Dwが1000nm以下である、[1]のポリオルガノシロキサン含有重合体。
[3]複合体とグラフト部とを有する重合体であり、
前記複合体は、ポリオルガノシロキサンと第1のビニル重合体とを含み、
前記グラフト部は、第2のビニル重合体を含む、[1]又は[2]のポリオルガノシロキサン含有重合体。
[4]ポリオルガノシロキサン含有重合体100質量%における前記グラフト部の割合が5質量%以上20質量%以下である、[3]のポリオルガノシロキサン含有重合体。
[5]前記第1のビニル重合体が(メタ)アクリレート単量体由来の構成単位を含有する、[3]又は[4]のポリオルガノシロキサン含有重合体。
[6]前記第2のビニル重合体が(メタ)アクリレート単量体由来の構成単位を含有する、[3]~[5]のいずれかのポリオルガノシロキサン含有重合体。
[7]前記ポリオルガノシロキサンがシロキサン系架橋剤由来の構成単位を含み、前記ポリオルガノシロキサン100質量%における前記シロキサン系架橋剤由来の構成単位の割合が3質量%以下である、[3]~[6]のいずれかのポリオルガノシロキサン含有重合体。
[8]ポリオルガノシロキサン含有重合体100質量%におけるポリオルガノシロキサンの割合が70質量%以上98質量%以下である、[1]~[7]のいずれかのポリオルガノシロキサン含有重合体。
[9]前記アルカリ金属原子がナトリウム原子である、[1]~[8]のいずれかのポリオルガノシロキサン含有重合体。
[10]粉体状である、[1]~[9]のいずれかのポリオルガノシロキサン含有重合体。
[11][1]~[10]のいずれかのポリオルガノシロキサン含有重合体と熱可塑性樹脂とを含有する組成物。
[12][1]~[10]のいずれかのポリオルガノシロキサン含有重合体と熱可塑性樹脂とを含有する成形体。
本発明において、ビニル単量体は、重合性二重結合を有する化合物を意味する。
本発明において、(メタ)アクリルは、アクリル及びメタクリルの一方又は両方を意味し、(メタ)アクリル酸エステルは、アクリル酸エステル及びメタクリル酸エステルの一方又は両方を意味する。
本明細書において、「~」は、その前後に記載される数値を下限値及び上限値として含む意味で使用される。即ち、「A~B」で表される数値は、A以上B以下を意味する。
本発明の一態様に係るポリオルガノシロキサン含有重合体(以下、「重合体(C)」とも記す。)は、重合体(A)と、第2のビニル重合体(B)(以下、「ビニル重合体(B)」とも記す。)とからなる。重合体(A)は、ポリオルガノシロキサン(A1)を少なくとも含み、第1のビニル重合体(A2)(以下、「ビニル重合体(A2)」とも記す。)をさらに含む複合体であることが好ましい。ポリオルガノシロキサン(A1)とビニル重合体(B)は、少なくとも一部が架橋していることが好ましい。ポリオルガノシロキサン含有重合体は、ポリオルガノシロキサン(A1)とビニル重合体(A2)との複合体(複合ゴム状重合体)と、ビニル重合体(B1)を含むグラフト部とを有するグラフト共重合体であることが好ましい。
本発明において、アルカリ金属原子量は、実施例に記載の測定方法に従って測定する。質量平均粒子径は実施例に記載の方法に従って測定する。
これにより、樹脂と配合して成形体を製造した際に、高い衝撃特性を有しつつ、高い難燃性を有し、外観性に優れた成形体を提供することができる。
ポリオルガノシロキサン(A1)は、オルガノシロキサン単位を含む重合体である。オルガノシロキサン単位とは、有機基が結合したSi-O単位を意味する。ポリオルガノシロキサンは、下記式(1)で表される構造を有する。
必要に応じて使用される成分としては、例えば、シロキサン系架橋剤、シロキサン系交叉剤、及び末端封鎖基を有するシロキサンオリゴマーが挙げられる。
R-Si(R1)n(OR2)(3-n) ・・・(I)
式(I)中、R1は、メチル基、エチル基、プロピル基、又はフェニル基を示す。R2は、炭化水素基等の有機基を示し、例えば、メチル基、エチル基、プロピル基、又はフェニル基が好ましい。nは、0、1又は2を示す。Rは、下記式(I-1)~(I-4)のいずれかで表される官能基を示す。
CH2=C(R3)-COO-(CH2)p- ・・・(I-1)
CH2=C(R4)-C6H4- ・・・(I-2)
CH2=CH- ・・・(I-3)
HS-(CH2)p- ・・・(I-4)
これらの式中、R3及びR4は、それぞれ独立に、水素原子又はメチル基を示し、pは1~6の整数を示す。
式(I-2)で表される官能基としては、例えば、ビニルフェニル基が挙げられる。式(I-2)で表される基を有するシロキサンとしては、例えば、ビニルフェニルエチルジメトキシシランが挙げられる。
式(I-3)で表される官能基を有するシロキサンとしては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシランが挙げられる。
式(I-4)で表される官能基としては、メルカプトアルキル基が挙げられる。式(I-4)で表される基を有するシロキサンとして、例えば、γ-メルカプトプロピルジメトキメチルシラン、γ-メルカプトプロピルメトキシジメチルシラン、γ-メルカプトプロピルジエトキシメチルシラン、γ-メルカプトプロピルエトキシジメチルシラン、γ-メルカプトプロピルトリメトキシシランが挙げられる。
シロキサン系交叉剤としては、ポリオルガノシロキサン(A1)とビニル重合体(A2)とが複合化した際に海島構造を形成しやすいことから、γ-メタクリロイルオキシプロピルメチルジメトキシシランが好ましい。
ポリオルガノシロキサン(A1)の製造方法に特に制限はなく、例えば、オルガノシロキサン、必要に応じてシロキサン系架橋剤、必要に応じてシロキサン系交叉剤、及び必要に応じて末端封鎖基を有するシロキサンオリゴマーを含むオルガノシロキサン混合物を、乳化剤と水によって乳化させてエマルションを調製し、このエマルション中で、酸触媒の存在下、オルガノシロキサン混合物を高温で重合させ、その後、アルカリ性物質により酸触媒を中和してポリオルガノシロキサンのラテックスを得る製造方法(M)を採用できる。
以下の説明においては、重合用の原料として「オルガノシロキサン混合物」を用いた場合について説明する。重合用の原料として「オルガノシロキサン」を用いた場合についても同様の製造プロセスを適用できる。
方法3を用いて重合する場合には、重合時間は、通常2時間以上、好ましくは5時間以上である。
アニオン系乳化剤としては、例えば、アルキルベンゼンスルホン酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、アルキル硫酸ナトリウム、ポリオキシエチレンアルキル硫酸ナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウムが挙げられる。
ノニオン系乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキレンアルキルエーテル、ポリオキシエチレンジスチレン化フェニルエーテル、ポリオキシエチレントリベンジルフェニルエーテル、ポリオキシエチレンポリオキシプロピレングリコールが挙げられる。
乳化剤は1種を単独で、又は2種以上を組み合わせて用いることができる。
重合体(A)は、ビニル重合体(A2)を含有していてもよい。重合体(A)がビニル重合体(A2)を含有する場合、重合体(A)は、ビニル重合体(A2)とポリオルガノシロキサン(A1)とが架橋している重合体であってもよいし、ポリオルガノシロキサン(A1)とビニル重合体(A2)とが架橋していない複合重合体であってもよく、ビニル重合体(A2)とポリオルガノシロキサン(A1)とが架橋していることが好ましい。
第1のビニル重合体(A2)を構成するビニル単量体成分(a2)は、1種のビニル単量体であってもよく、2種以上のビニル単量体であってもよい。
単量体(a2-1)は1種を単独で、又は2種以上を組み合わせて用いることができる。
単量体(a2-2)は1種を単独で、又は2種以上を組み合わせて用いることができる。
シアン化ビニル単量体としては、特段の制限はなく、アクリロニトリル、メタクリロニトリルが挙げられる。
その他の単量体(a2-3)は1種を単独で、又は2種以上を組み合わせて用いることができる。
重合体(A)は、ポリオルガノシロキサン(A1)とビニル重合体(A2)とを含む。重合体(A)はポリオルガノシロキサン(A1)とビニル重合体(A2)との複合ゴムとしての機能を有することが好ましい。複合ゴムとして機能するにはポリオルガノシロキサン(A1)とビニル重合体(A2)のガラス転移温度(以下、Tgと称す場合がある。)がそれぞれ0℃以下であることが好ましい。
重合体(A)の製造方法は特に限定されないが、成形体の衝撃強度が優れることから、ポリオルガノシロキサン(A1)を含むラテックスの存在下で、ビニル重合体(A2)を構成するビニル単量体成分(a2)を重合する方法が好ましい。
成形体の衝撃強度が優れることから、方法iiiが好ましい。
ラジカル重合開始剤としてレドックス系開始剤を用いる場合、過酸化物の使用量は、単量体の合計100質量部に対して0.01~1質量部が好ましい。ラジカル重合開始剤としてレドックス系開始剤を用いる場合、還元剤の使用量は、単量体の合計100質量部に対して0.01~1質量部が好ましい。
ビニル重合体(B)は、ビニル単量体成分(b)が重合された重合体であり、ビニル単量体由来の構成単位を含む重合体である。
ビニル重合体(B)を構成するビニル単量体成分(b)は、1種以上のビニル単量体であればよい。
(メタ)アクリレート単量体は1種を単独で用いてもよく、2種以上を併用してもよい。アルキル(メタ)アクリレートのアルキル基の炭素数は、特段の制限はなく、1以上が好ましく、12以下が好ましく、6以下がより好ましく、4以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、1~12が好ましく、1~6がより好ましく、1~4がさらに好ましい。メチルメタクリレートが特に好ましい。
ビニル重合体(B)のTgは、ビニル単量体成分(b)を構成するビニル単量体の種類と比率によって調整できる。
重合体(C)は、例えば、重合体(A)の存在下でビニル単量体成分(b)を重合(グラフト重合)することにより製造できる。これにより、重合体(A)にビニル重合体(B)の一部又は全部がグラフトされた重合体が得られる。
重合体(C)を粉体として回収する場合には、噴霧乾燥法等の直接乾燥法又は凝固法を用いることができる。直接乾燥法では、重合時に添加した助剤類を概ね得られる粉体中に残存させることができる。凝固法では、凝析後の洗浄工程にて、重合時に使用した乳化剤及びその凝析塩、開始剤等、得られる粉体中に含まれる重合助剤残存物を低減できる。粉体回収法は、重合体(C)を熱可塑性樹脂に添加した際に、望む残存状態となるように適宜選択することができる。
凝固剤水溶液の量は特に限定されず、重合体(C)のラテックス100質量部に対して10質量部以上、500質量部以下であることが好ましい。
(1)凝固剤水溶液を攪拌しながら、その中にラテックスを連続的に添加して一定時間保持する方法、
(2)凝固剤水溶液とラテックスとを、一定の比率で攪拌機付きの容器内に連続的に注入しながら接触させ、凝析された重合体と水とを含む混合物を容器から連続的に抜き出す方法。
ラテックスを凝固剤水溶液に接触させるときの温度は特に限定されず、30℃以上、100℃以下であることが好ましい。接触時間は特に限定されない。
圧搾脱水機や押出機から排出された重合体(C)を回収せず、直接、樹脂組成物を製造する押出機や成形機に送り、熱可塑性樹脂と混合して成形体を得てもよい。
本発明の一態様に係る樹脂組成物(以下、「本樹脂組成物」とも記す。)は、重合体(C)と熱可塑性樹脂(以下、「熱可塑性樹脂(D)」とも記す。)とを含む。
エンジニアリングプラスチックとしては、例えば、ポリフェニレンエーテル、ポリカーボネート、ポリエステル系重合体(ポリエチレンテレフタレート、ポリブチレンテレフタレート等)、シンジオタクチックポリスチレン、ナイロン系重合体(6-ナイロン、6,6-ナイロン等)、ポリアリレート、ポリフェニレンスルフィド、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリスルホン、ポリエーテルスルホン、ポリアミドイミド、ポリエーテルイミド、ポリアセタールが挙げられる。
芳香族ポリカーボネートとしては、例えば、4,4’-ジヒドロキシジフェニル-2,2-プロパン(ビスフェノールA)系ポリカーボネート等の4,4’-ジオキシジアリールアルカン系ポリカーボネートが挙げられる。
高分子ジオールとしては、例えば、ポリエステルジオール、ポリエーテルジオール、ポリエステルエーテルジオール、ポリカーボネートジオール、ポリエステルポリカーボネートジオールが挙げられる。
有機ジイソシアネートとしては、例えば、4,4’-ジフェニルメタンジイソシアネート、トルエンジイソシアネート、p-フェニレンジイソシアネート、キシリレンジイソシアネート、ナフタレンジイソシアネート、水素化4,4’-ジフェニルメタンジイソシアネート(4,4’-ジシクロヘキシルメタンジイソシアネート)、イソホロンジイソシアネート、ヘキサメチレンジイソシアネートが挙げられ、4,4’-ジフェニルメタンジイソシアネートが好ましい。
鎖伸張剤としては、例えば、エチレングリコール、ジエチレングリコール、1,4-ブタンジオール、1,5-ペンタンジオール、2-メチル-1,3-プロパンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、1,9-ノナンジオール、シクロヘキサンジオール、1,4-ビス(β-ヒドロキシエトキシ)ベンゼンが挙げられる。
ポリエステル樹脂は、単独重合体、共重合体又はこれら2種以上のブレンド物であってもよい。
ポリエステル樹脂としては、イーストマンケミカル社製の商品名「PETG」等の市販品を用いてもよい。
微生物系ポリマーとしては、例えば、ポリヒドロキシブチレート/バリレート(PHB/V)等のバイオポリエステル、バクテリアセルロース、微生物多糖(プルラン、カードラン等)が挙げられる。
化学合成系ポリマーとしては、例えば、脂肪族ポリエステル(ポリカプロラクトン、ポリブチレンサクシネート、ポリエチレンサクシネート、ポリグリコール酸、ポリ乳酸等)、ポリビニルアルコール、ポリアミノ酸類(PMLG等)が挙げられる。
天然物系ポリマーとしては、例えば、キトサン、セルロース、澱粉、酢酸セルロースが挙げられる。
ハロゲン系樹脂としては、塩化ビニル樹脂のほか、例えば、フッ素化重合体、臭素化重合体、ヨウ素化重合体が挙げられる。
熱可塑性樹脂(D)は、工業的に入手しやすいこと、成形体の衝撃強度と着色性のバランスに優れることから、芳香族ポリカーボネート、ポリメチルメタクリレート、スチレン-アクリロニトリル共重合体、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリ塩化ビニル、ポリフェニレンスルファイド及びポリアセタールからなる群より選ばれる少なくとも1種を含むことが好ましく、ポリメチルメタクリレート及びスチレン-アクリロニトリル共重合体からなる群より選ばれる少なくとも1種を含むことがより好ましい。
添加剤としては、例えば、難燃剤(例えば、燐系、ブロム系、シリコーン系、有機金属塩系)、ドリップ防止剤(例えば、フッ素化ポリオレフィン、シリコーン及びアラミド繊維)、滑剤(例えば、ステアリン酸マグネシウム等の長鎖脂肪酸金属塩)、離型剤(例えば、ペンタエリスリトールテトラステアレート)、成核剤、帯電防止剤、安定剤(例えば、フェノール系安定剤、燐系安定剤、紫外線吸収剤、アミン系光安定剤)、充填材(例えば、酸化チタン、タルク、マイカ、カオリン、炭酸カルシウム、ガラスフレーク)、可塑剤、強化剤(例えば、ガラス繊維、炭素繊維)、色素、顔料が挙げられる。本発明においては、重合体(C)の存在により、樹脂組成物の難燃性が向上する傾向があるため、難燃剤を添加しない、又は少量の添加でも高い難燃性が得られる。
樹脂組成物は、重合体(C)と、熱可塑性樹脂(D)と、必要により添加剤とを混合することにより製造できる。
各材料の混合方法としては、公知のブレンド方法が挙げられ、特に限定されない。例えば、タンブラー、V型ブレンダー、スーパーミキサー、ナウターミキサー、バンバリーミキサー、混練ロール、押出機等で混合、混練する方法が挙げられる。
本発明の樹脂組成物の製造方法の一例として、重合体(C)と、ペレット状の熱可塑性樹脂(D)と、必要により添加剤とを押出機を用いて混合し、ストランド状に押出し、回転式カッター等でペレット状にカットする方法が挙げられる。この方法により、ペレット状の樹脂組成物を得ることができる。
本発明の一態様に係る成形体(以下、「本成形体」とも記す。)は、重合体(C)と熱可塑性樹脂(D)とを含む。
本成形体は、その他の成分をさらに含んでいてもよい。その他の成分としては公知の成分が挙げられる。
本成形体は、本樹脂組成物からなることが好ましい。
成形方法としては、熱可塑性樹脂組成物の成形に用いられる成形法、例えば、射出成形法、押出成形法、ブロー成形法、カレンダー成形法が挙げられる。
質量w1のポリオルガノシロキサンのラテックスを180℃の熱風乾燥機で30分間乾燥し、乾燥後の残渣の質量w2を測定し、下記式により固形分[%]を算出する。
固形分[%]=w2/w1×100
「ポリオルガノシロキサン(A1)ラテックス」又は「重合体(C)ラテックス」を脱イオン水で固形分濃度約3%に希釈したものを試料とし、米国MATEC社製CHDF2000型粒度分布計を用いて、下記条件を用いて、数平均粒子径Dn及び質量平均粒子径Dwを測定した。
カートリッジ:専用の粒子分離用キャピラリー式カートリッジ(商品名;C-202)、
キャリア液:専用キャリア液(商品名;2XGR500)、
キャリア液の液性:中性、
キャリア液の流速:1.4mL/分、
キャリア液の圧力:4,000psi(2,600kPa)、
測定温度:35℃、
試料使用量:0.1mL。
試料約0.25gを計量し、硝酸8mLとフッ化水素水2mLを加えマイクロウェーブ(湿式分解)により分解処理を行い、蒸留水で50mLにメスアップしたものを試験溶液として、ICP発光分析装置(Thermo社製 iCAP7400 Duo)により残存金属量を定量した。
グラフト共重合体に対してTG/DTA6200(セイコーインスツルメンツ社製)を用いて熱重量分析を行い、下記方法で熱分解性を評価した。
残存量(%)=保持後の質量(g)/仕込みの質量(g) ・・・式(1)
熱分解性(℃)=((残存量70%時点の温度)-(残存量1%時点の温度) ・・・式(2)
[製造例1-1:ポリオルガノシロキサンラテックス(S-1)の製造]
γ-メタクリロイルオキシプロピルジメトキシメチルシラン(DSMA)2部、及びオクタメチルシクロテトラシロキサン(モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製、製品名:TSF404)98部を混合してオルガノシロキサン混合物100部を得た。脱イオン水150部中にドデシルベンゼンスルホン酸ナトリウム(DBSNa)1部を溶解した水溶液を、オルガノシロキサン混合物中に添加し、ホモミキサーにて10,000rpmで5分間攪拌した後、ホモジナイザーに20MPaの圧力で2回通し、安定な予備混合エマルションを得た。
オルガノシロキサン混合物の組成を表1に示す組成に変更した以外は、製造例1-1と同様の操作を行い、ポリオルガノシロキサンラテックス(S-2)を得た。
ポリオルガノシロキサンラテックス(S-2)の固形分は30.4質量%であった。数平均粒子径(Dn)は384nm、質量平均粒子径(Dw)は403nmであり、Dw/Dnは1.05であった。
オルガノシロキサン混合物の組成を表1に示す組成に変更した以外は、製造例1-1と同様の操作を行い、ポリオルガノシロキサンラテックス(S-3)を得た。
ポリオルガノシロキサンラテックス(S-3)の固形分は30.6質量%であった。数平均粒子径(Dn)は384nm、質量平均粒子径(Dw)は403nmであり、Dw/Dnは1.05であった。
オルガノシロキサン混合物の組成を表1に示す組成に変更した以外は、製造例1-1と同様の操作を行い、ポリオルガノシロキサンラテックス(S-4)を得た。
ポリオルガノシロキサンラテックス(S-4)の固形分は30.8質量%であった。数平均粒子径(Dn)は384nm、質量平均粒子径(Dw)は403nmであり、Dw/Dnは1.05であった。
γ-メタクリロイルオキシプロピルジメトキシメチルシラン(DSMA)0.5部、テトラエトキシシラン(TEOS)2部、及びオクタメチルシクロテトラシロキサン(信越シリコーン社製、製品名:DMC、3~6員環の環状オルガノシロキサンの混合物)97.5部を混合してオルガノシロキサン混合物100部を得た。脱イオン水150部中にドデシルベンゼンスルホン酸ナトリウム(DBSNa)0.68部、ドデシルベンゼンスルホン酸(DBSH)0.68部を溶解した水溶液を、オルガノシロキサン混合物中に添加し、ホモミキサーにて10,000rpmで5分間攪拌した後、ホモジナイザーに20MPaの圧力で2回通し、安定な予備混合エマルションを得た。
オルガノシロキサン混合物の組成を表1に示す組成に変更し、ドデシルベンゼンスルホン酸ナトリウム(DBSNa)の量を1.5部に増やした以外は、製造例1-1と同様の操作を行い、ポリオルガノシロキサンラテックス(S-6)を得た。
表1中の略号は以下の通りである。
TSF404:オクタメチルシクロテトラシロキサン
DMC:3~6員環の環状オルガノシロキサンの混合物
DSMA:γ-メタクリロイルオキシプロピルジメトキシメチルシラン
TEOS:テトラエトキシシラン
製造例1-1において得たポリオルガノシロキサンラテックス(S-1)80部(ポリマー換算で10.0部)を容量5リットルのセパラブルフラスコ内に採取し、ブチルアクリレート(BA)8.82部、アリルメタクリレート(AMA)0.18部、クメンハイドロパーオキサイド(CB)0.16部の混合物を添加し、室温で1時間撹拌を続けポリオルガノシロキサンに含浸させた。
得られたグラフト共重合体の粉体(A-1)の質量平均粒子径、アルカリ金属量及び熱分解性を上述の方法により測定した。得られた結果を表2に示す。
実施例1-1において用いた各原料組成を表2に示す条件に変更したこと以外は実施例1-1と同様にして、ポリオルガノシロキサン含有グラフト共重合体(G-2~G-4)を製造し、さらにグラフト共重合体の粉体(A-2~A-4)を得て、同様の測定を行った。得られた結果を表2に示す。
実施例1-1と同様にして、ポリオルガノシロキサン含有グラフト共重合体(G-1)を製造し、さらに塩化ナトリウムの濃度が10質量%の水溶液の量を20部に変更した以外は実施例1-1と同様の手法でグラフト共重合体の粉体(A-5)を得て、同様の測定を行った。得られた結果を表2に示す。
実施例1-1と同様にして、ポリオルガノシロキサン含有グラフト共重合体(G-1)を製造し、さらに塩化ナトリウムの濃度が10質量%の水溶液の量を50部に変更した以外は実施例1-1と同様の手法でグラフト共重合体の粉体(A-6)を得て、同様の測定を行った。得られた結果を表2に示す。
ポリオルガノシロキサン含有グラフト共重合体(G-1)を得た後に塩化ナトリウム溶液による処理を行わなかった以外は実施例1-1と同様の方法によりポリオルガノシロキサン含有グラフト共重合体粉体(A-7)を得て、同様の測定を行った。得られた結果を表2に示す。
ポリオルガノシロキサン含有グラフト共重合体(G-2)を得た後に塩化ナトリウム溶液による処理を行わなかった以外は実施例1-2と同様の方法によりポリオルガノシロキサン含有グラフト共重合体粉体(A-8)を得て、同様の測定を行った。得られた結果を表2に示す。
ポリオルガノシロキサン含有グラフト共重合体(G-3)を得た後に塩化ナトリウム溶液による処理を行わなかった以外は実施例1-3と同様の方法によりポリオルガノシロキサン含有グラフト共重合体粉体(A-9)を得て、同様の測定を行った。得られた結果を表2に示す。
ポリオルガノシロキサン含有グラフト共重合体(G-4)を得た後に塩化ナトリウム溶液による処理を行わなかった以外は実施例1-4と同様の方法によりポリオルガノシロキサン含有グラフト共重合体粉体(A-10)を得て、同様の測定を行った。得られた結果を表2に示す。
実施例1-1において用いた各原料組成を表2に示す条件に変更したこと以外は実施例1-1と同様にして、ポリオルガノシロキサン含有グラフト共重合体(G-5)を製造し、さらにグラフト共重合体の粉体(A-11)を得て、同様の測定を行った。得られた結果を表2に示す。
比較例1-5に記載された方法によりポリオルガノシロキサン含有グラフト共重合体(G-5)を得た後に、得られたグラフト共重合体(G-5)10部を脱イオン水141部に投入して3分間攪拌した後で塩化ナトリウムの濃度が10質量%の水溶液10部を投入し3分間攪拌し、ろ過、洗浄、脱水した後、乾燥させてナトリウムを含むグラフト共重合体の粉体(A-12)を得て、同様の測定を行った。得られた結果を表2に示す。
実施例1-1において用いた各原料組成を表2に示す条件に変更したこと以外は実施例1-1と同様にして、ポリオルガノシロキサン含有グラフト共重合体(G-6)を得た後に、得られたグラフト共重合体(G-6)10部を脱イオン水141部に投入して3分間攪拌した後で塩化ナトリウムの濃度が10質量%の水溶液10部を投入し3分間攪拌し、ろ過、洗浄、脱水した後、乾燥させてナトリウムを含むグラフト共重合体の粉体(A-13)を得て、同様の測定を行った。得られた結果を表2に示す。
nBA:n-ブチルアクリレート
AMA:アリルメタクリレート
MMA:メチルメタクリレート
Na:ナトリウム
K:カリウム
ポリオルガノシロキサン含有重合体粉体、添加剤、及び熱可塑性樹脂を表3の比率で配合し、混合物を得た。この混合物を脱揮式二軸押出機(池貝社製、PCM-30(商品名))に供給して混練し、各樹脂組成物のペレットを作製した。
PC:ポリカーボネート樹脂(ユーピロンS-2000F、三菱エンジニアリングプラスチックス社製、粘度平均分子量24,000)。
添加剤としては、以下のものを用いた。
A-3750:アクリル変性PTFE(メタブレンA-3750、三菱ケミカル社製)。
試験片の仕様:
試験片A:長さ80mm×幅10mm×厚み4mm
試験片B:長さ100mm×幅50mm×厚み2mm
試験片C:長さ125mm×幅13mm×厚み1.6mm
押出条件、射出成形条件は以下の通りである。
押出バレル温度280℃、
射出シリンダー温度:280℃、
金型温度:60℃。
「判定方法」ゲート部の外観を目視にて判定する(A:フローマークが目立たない、B:フローマークが目立つ)。評価結果を表3に示す。
特定の粒子径とともに特定量のアルカリ金属原子を含む重合体を含有する実施例2-1~2-9に係る成形体は、比較例2-1~2-8に係る成形体と比較してより良好な難燃性を備えていた。
実施例2-1~2-9に係るグラフト共重合体と比べ、比較例2-6~2-7に係るグラフト共重合体は粒子径が小さいため、外観性に劣っていた。
Claims (12)
- アルカリ金属原子を100質量ppm以上含有し、質量平均粒子径Dwが350nm以上である、ポリオルガノシロキサン含有重合体。
- 質量平均粒子径Dwが1000nm以下である、請求項1に記載のポリオルガノシロキサン含有重合体。
- 複合体とグラフト部とを有する重合体であり、
前記複合体は、ポリオルガノシロキサンと第1のビニル重合体とを含み、
前記グラフト部は、第2のビニル重合体を含む、請求項1又は2に記載のポリオルガノシロキサン含有重合体。 - ポリオルガノシロキサン含有重合体100質量%における前記グラフト部の割合が5質量%以上20質量%以下である、請求項3に記載のポリオルガノシロキサン含有重合体。
- 前記第1のビニル重合体が(メタ)アクリレート単量体由来の構成単位を含有する、請求項3又は4に記載のポリオルガノシロキサン含有重合体。
- 前記第2のビニル重合体が(メタ)アクリレート単量体由来の構成単位を含有する、請求項3~5のいずれか1項に記載のポリオルガノシロキサン含有重合体。
- 前記ポリオルガノシロキサンがシロキサン系架橋剤由来の構成単位を含み、前記ポリオルガノシロキサン100質量%における前記シロキサン系架橋剤由来の構成単位の割合が3質量%以下である、請求項3~6のいずれか1項に記載のポリオルガノシロキサン含有重合体。
- ポリオルガノシロキサン含有重合体100質量%におけるポリオルガノシロキサンの割合が70質量%以上98質量%以下である、請求項1~7のいずれか1項に記載のポリオルガノシロキサン含有重合体。
- 前記アルカリ金属原子がナトリウム原子である、請求項1~8のいずれか1項に記載のポリオルガノシロキサン含有重合体。
- 粉体状である、請求項1~9のいずれか1項に記載のポリオルガノシロキサン含有重合体。
- 請求項1~10のいずれか1項に記載のポリオルガノシロキサン含有重合体と熱可塑性樹脂とを含有する組成物。
- 請求項1~10のいずれか1項に記載のポリオルガノシロキサン含有重合体と熱可塑性樹脂とを含有する成形体。
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KR1020237024912A KR20230122135A (ko) | 2021-03-30 | 2022-03-28 | 폴리오르가노실록산 함유 중합체, 조성물 및 성형체 |
CN202280019755.9A CN116997583A (zh) | 2021-03-30 | 2022-03-28 | 含聚有机硅氧烷的聚合物、组合物和成型体 |
EP22780703.9A EP4317229A1 (en) | 2021-03-30 | 2022-03-28 | Polyorganosiloxane-containing polymer, composition, and molded article |
US18/464,531 US20230416441A1 (en) | 2021-03-30 | 2023-09-11 | Polyorganosiloxane-containing polymer, composition, and molded article |
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WO2013162080A2 (ja) | 2013-08-13 | 2013-10-31 | 三菱レイヨン株式会社 | ポリオルガノシロキサン含有グラフト共重合体、樹脂組成物、成形体、摺動性改良剤及び摺動部材 |
WO2018225582A1 (ja) | 2017-06-06 | 2018-12-13 | 三菱ケミカル株式会社 | ポリオルガノシロキサン含有グラフト共重合体、熱可塑性樹脂組成物及び成形体 |
JP2020041067A (ja) * | 2018-09-12 | 2020-03-19 | 三菱ケミカル株式会社 | ポリオルガノシロキサン含有グラフト共重合体、熱可塑性樹脂組成物及び成形体 |
JP2021056873A (ja) | 2019-09-30 | 2021-04-08 | 本田技研工業株式会社 | 走行支援システム、走行支援方法およびプログラム |
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JP3865295B2 (ja) * | 2001-10-11 | 2007-01-10 | 旭化成ケミカルズ株式会社 | 難燃性樹脂組成物 |
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2022
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CN116997583A (zh) | 2023-11-03 |
US20230416441A1 (en) | 2023-12-28 |
KR20230122135A (ko) | 2023-08-22 |
TW202237678A (zh) | 2022-10-01 |
TWI831169B (zh) | 2024-02-01 |
EP4317229A1 (en) | 2024-02-07 |
JPWO2022210492A1 (ja) | 2022-10-06 |
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