TWI381007B - Non-halogen flame retardant resin composition - Google Patents
Non-halogen flame retardant resin composition Download PDFInfo
- Publication number
- TWI381007B TWI381007B TW94117088A TW94117088A TWI381007B TW I381007 B TWI381007 B TW I381007B TW 94117088 A TW94117088 A TW 94117088A TW 94117088 A TW94117088 A TW 94117088A TW I381007 B TWI381007 B TW I381007B
- Authority
- TW
- Taiwan
- Prior art keywords
- magnesium hydroxide
- flame retardant
- resin composition
- group
- halogen flame
- Prior art date
Links
- 239000003063 flame retardant Substances 0.000 title claims description 28
- 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 title claims description 24
- 229910052736 halogen Inorganic materials 0.000 title claims description 22
- 239000011342 resin composition Substances 0.000 title claims description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 64
- 239000000347 magnesium hydroxide Substances 0.000 claims description 63
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 63
- 239000002245 particle Substances 0.000 claims description 25
- 150000002367 halogens Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000013535 sea water Substances 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229920005672 polyolefin resin Polymers 0.000 claims description 5
- 239000012267 brine Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000011164 primary particle Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000011163 secondary particle Substances 0.000 claims 1
- -1 bromine compound Chemical class 0.000 description 16
- 239000013078 crystal Substances 0.000 description 14
- 229920005992 thermoplastic resin Polymers 0.000 description 14
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920002098 polyfluorene Polymers 0.000 description 6
- 150000001451 organic peroxides Chemical class 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VSCVYVRTQIRCTN-UHFFFAOYSA-N COC(CCCCCCCCC)(OC)OC.C=C Chemical compound COC(CCCCCCCCC)(OC)OC.C=C VSCVYVRTQIRCTN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000036284 oxygen consumption Effects 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- CYOQTWZWFHXPDM-UHFFFAOYSA-N (2-tridecylphenyl) dihydrogen phosphate Chemical compound CCCCCCCCCCCCCc1ccccc1OP(O)(O)=O CYOQTWZWFHXPDM-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- OTMBZPVYOQYPBE-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclododecane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCCCCCCCC1 OTMBZPVYOQYPBE-UHFFFAOYSA-N 0.000 description 1
- POBUJEBYLIZDCQ-UHFFFAOYSA-N 1,2,3-tributyl-4-propan-2-ylbenzene Chemical compound C(CCC)C1=C(C(=C(C=C1)C(C)C)CCCC)CCCC POBUJEBYLIZDCQ-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 1
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical compound OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
- UKWUOTZGXIZAJC-UHFFFAOYSA-N 4-nitrosalicylic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1O UKWUOTZGXIZAJC-UHFFFAOYSA-N 0.000 description 1
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 6-tert-butyl-m-cresol Natural products CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VCBKRBPXFOTPBQ-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC(CC(OC)(OC)OC)CCCCCCC Chemical compound C(C(=C)C)(=O)OCCCC(CC(OC)(OC)OC)CCCCCCC VCBKRBPXFOTPBQ-UHFFFAOYSA-N 0.000 description 1
- OMCNZPZIRSRDMR-UHFFFAOYSA-N C(C)OC(CCCCCCCCC)(OCC)OCC.C=C Chemical compound C(C)OC(CCCCCCCCC)(OCC)OCC.C=C OMCNZPZIRSRDMR-UHFFFAOYSA-N 0.000 description 1
- MZHBQLPGDMAMAI-UHFFFAOYSA-N C1(CC2C(CC1)O2)CCC(C(C)(C)C)CCCCCCC Chemical compound C1(CC2C(CC1)O2)CCC(C(C)(C)C)CCCCCCC MZHBQLPGDMAMAI-UHFFFAOYSA-N 0.000 description 1
- ZGYWEAQYPZAYQF-UHFFFAOYSA-N COCCOC(CCCCCCCCC)(OCCOC)OCCOC.C=C Chemical compound COCCOC(CCCCCCCCC)(OCCOC)OCCOC.C=C ZGYWEAQYPZAYQF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004287 Dehydroacetic acid Substances 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N N-undecane Natural products CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- OLJCFOHFPIQGHO-UHFFFAOYSA-N NC1=NC(N)=NC(N)=N1.N=C=O.N=C=O.N=C=O Chemical compound NC1=NC(N)=NC(N)=N1.N=C=O.N=C=O.N=C=O OLJCFOHFPIQGHO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002675 Polyoxyl Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- AVRLEKKHTWOYOF-UHFFFAOYSA-N [Sr][Sr][Ba] Chemical compound [Sr][Sr][Ba] AVRLEKKHTWOYOF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 229940006612 barium citrate Drugs 0.000 description 1
- PAVWOHWZXOQYDB-UHFFFAOYSA-H barium(2+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PAVWOHWZXOQYDB-UHFFFAOYSA-H 0.000 description 1
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical compound NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
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Description
本發明係有關與先行技術品顯示同等以上高度難燃性,此外,材料費價廉,具良好張力強度,燃燒時未產生鹵素氣體,因此,對於環境具良好安定性之非鹵素難燃樹脂組成物。
近年來被揭示對於電線電纜之絕緣體、薄片所使用之聚烯烴系樹脂之難燃處方,使用氫氧化鎂等金屬氫氧化物之各種技術。
氫氧化鎂具有低毒性、發煙量少、低腐蝕性之優點、燃燒時藉由釋放結晶水後,發揮難燃作用,惟,其難燃性並不強,對於100重量份之低密度聚乙烯調配等量之100重量份其氧消耗指數仍僅接近25之值。於聚烯烴進行添加氫氧化鎂與聚矽氧時,出現難燃性之大幅提昇。
先行技術中做為熱塑性樹脂用難燃劑者所使用之氫氧化鎂係於海水或鹵水中所含之鎂鹽水溶液中加入NaOH、生石灰等鹼後,使置入核種之結晶成長、或直接藉由結晶成長之方法所合成者,特別是合成時於鹼溶液中進行加壓、加溫後取得六方晶系之結晶,於高溫條件下可製造板狀六方晶系之結晶。藉由此製法之氫氧化鎂粒徑細,其粒徑為2~10μm之氫氧化鎂與粒徑0.01~1.99μm之氫氧化鎂通常以20:80~0.1:99.9之比例存在之。
惟,此形態之氫氧化鎂其價格高,因此,調配此氫氧化鎂之聚烯烴混合物相較於氯化乙烯系混合物其價格太高之問題存在。又,倂用聚矽氧後雖可提昇難燃性,惟,藉由調配聚矽氧後其張力強度下降之問題存在之。
因此,最近開始使用廉價之粉碎天然岩石處理後之天然產品,惟,天然岩石出產時其不同的不純物影響所調配之組成物物性。且,含數十ppm之砷時其安全性出現問題,更常混入石棉類之纖維物,而使用上不理想。
合成品氫氧化鎂除上述結晶成長型之外,公知者有氧化鎂中反應未含二氧化碳水之方法,惟,此製造方法雖可做成0.1μm以下之微細粉末,惟,其成本極高,目前不大使用。
又,於海水或鹵水中所含之鎂鹽水溶液中加入NaOH等鹼後,藉由加壓、加溫等未經結晶成長直接使膠體狀沈澱進行洗淨、過濾之方法(以下,此方法所製造者記為非結晶成長型氫氧化鎂)例者。
此非結晶成長型氫氧化鎂其價格最為低廉,惟,用於樹脂時,藉由羥基之凝聚效果而變硬,轉矩變高而不易與樹脂混合,且,形成張力延伸低之組成物而不被使用之。目前專門做為廢水中和、排煙脫硫之用者。
做為非鹵素難燃樹脂組成物者,有關氫氧化鎂或氫氧化鎂與聚矽氧之倂用,目前為止如下例被揭示之。
使用表面處理之氫氧化鎂(專利文獻1~3)。樹脂中調配氫氧化鎂及有機聚矽氧烷(專利文獻4~6)。又,本發明
者加入熱塑性樹脂、氫氧化鎂、高聚合度之二甲基有機聚矽氧烷及含有乙烯基之油狀有機聚矽氧烷之混合物後,調配貴金屬觸媒時,顯示出現更高之難燃性(專利文獻7)。
[專利文獻1]特許第2825500號公報
[專利文獻2]特許第3019225號公報
[專利文獻3]特許第3072746號公報
[專利文獻4]特公平7-119324號公報
[專利文獻5]特許第3051211號公報
[專利文獻6]特許第3063759號公報
[專利文獻7]特願平2001-326197號公報
熱塑性樹脂為可燃性者,因此被提出難燃性對於必要用途之賦與各種難燃化之技術,先行技術中多半使用樹脂中調配具良好難燃性之溴化合物等鹵系難燃劑與氧化銻之難燃處方。鹵系難燃劑藉由自由基截留作用、不燃性氣體之產生等,發揮良好之難燃效果。惟,鹵系難燃劑於火災時產生大量有毒氣體,因此,最近被強烈期待出現一種非鹵素處方之難燃樹脂組成物。
因此,本發明之課題係為提供一種相較於先行技術者顯示同等以上之難燃性,同時為廉價,且具良好張力強度,燃燒時不會產生鹵素氣體,對於環境具良好安全性之非鹵素難燃樹脂組成物。
本發明者為了解決該課題,針對無混入砷、石棉危險
性、價格極廉,而,目前為止卻無法被利用之非結晶成長型氫氧化鎂著眼,進行研討熱塑性樹脂之使用。
其結果顯示,對於(A)熱塑性樹脂100質量份時,調配(B)非結晶成長型氫氧化鎂30~300質量份,(C)成份之有機聚矽氧烷以下記平均組成式(1)所示之平均聚合度為2000~30000之有機聚矽氧烷0.1~50質量份時,RaSiO4-a/2 (1)
(式中,R為碳數1~10之非取代或取代之一價烴基,a為1.9≦a≦2.1之數)。於先前技術之結晶成長型氫氧化鎂所見之凝聚,造成硬化、分散不良、張力延伸極端降低之缺點並未出現、顯示與調配結晶成長型氫氧化鎂之組成物為同等以上之難燃性。又,使高聚合度之二甲基有機聚矽氧烷與熱塑性樹脂與結晶成長型氫氧化鎂倂用時所出現之降低張力強度亦確定改善,而完成本發明。
本發明於燃燒時未產生鹵素氣體、比先前技術之無機難燃粉體量少、顯示充份高度之難燃性,可取得對於環境具良好安定性之非鹵素難燃樹脂組成物。
本發明之(A)成份之熱塑性樹脂例如有低密度聚乙烯、高密度聚乙烯、直鏈狀低密度聚乙烯、超低密度聚乙烯、超高分子量聚乙烯、聚丙烯、聚苯乙烯、ABS、聚醯胺
、聚碳酸酯、聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、乙烯醋酸乙烯酯共聚物、乙烯-乙烯醇共聚物等之乙烯醋酸乙烯酯共聚物皂化物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸醯胺共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-甲基丙烯酸縮水甘油酯共聚物、乙烯馬來酸酐共聚物、熱塑性彈性體之離子鍵聚合物、聚丙烯系彈性體、聚苯乙烯系彈性體等例,惟,並未受限於此。又特別以聚烯烴樹脂為最佳。
又,此等可單獨使用,亦可合倂2種以上使用。上述例之樹脂中又以低密度聚乙烯、高密度聚乙烯、直鏈狀低密度聚乙烯、超低密度聚乙烯、超高密度聚乙烯、聚丙烯、乙烯醋酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物等之聚烯烴樹脂最具與非結晶成長型氫氧化鎂及有機聚矽氧烷之難燃性的高度相乘效果。
本發明(B)成份之非結晶成長型氫氧化鎂例如有加入鹼於海水或鹵水中所含之鎂鹽水溶液後,不使結晶成長,製作膠體狀沈澱,使膠體沈澱進行洗淨、乾燥之氫氧化鎂等例,惟,本發明並未受限於此。該非結晶成長型氫氧化鎂係為合成品,未混入砷、石棉、價格為氫氧化鎂中最便宜,僅結晶成長型氫氧化鎂之一半以下。
又,非結晶成長型氫氧化鎂多半為2次凝聚者,因此,粒徑大,一般平均粒徑多半為3μm以上。以電子顯微鏡觀察此2次凝聚物時,發現粒徑為0.01~1.99μm之氫氧化
鎂1次粒子經凝聚所成者。
於熱塑性樹脂中添加氫氧化鎂進行使用時,通常,氫氧化鎂係使其表面以脂肪酸、矽烷偶合劑或、鈦酸酯系偶合劑進行表面處理者被使用之。此係為改善氫氧化鎂表面與熱塑性樹脂之互溶性不良者。惟,本發明非結晶成長型氫氧化鎂無須特別處理表面即可使用之。具體之理由不明,可解釋者係非結晶成長型氫氧化鎂形成粒徑為0.01~1.99μm之氫氧化鎂1次粒子凝聚之構造者。
此非結晶成長型氫氧化鎂含大量粒徑2~40μm之過大尺寸者導致對於樹脂之添加,分散不易,而,粒徑為2~40μm之氫氧化鎂與粒徑0.01~1.99μm之氫氧化鎂為25:75~99:1之比例時,藉由倂用聚矽氧後,證明可分散於樹脂。
針對此2種粒徑之比率更理想之比率為50:50~90:10,最理想之比率為60:40者。又,有關2種粒徑範圍中粒徑大之分佈,較理想之粒徑為2~20μm,更理想之粒徑為2~10μm者。
又,該非結晶成長型氫氧化鎂未經處理者,或以飽和脂肪酸,不飽和脂肪酸、鈦酸酯偶合劑、矽烷偶合劑、聚矽氧低聚物、反應性聚矽氧油、熱塑性樹脂等表面處理劑進行處理者均可。
做為用於非結晶成長型氫氧化鎂粉體表面處理之含不飽和官能基矽烷者如:乙烯三乙氧基矽烷、乙烯三甲氧基矽烷、乙烯三(β-甲氧基乙氧基)矽烷、γ-(甲基丙烯氧基
丙基)三甲氧基矽烷等。對於非結晶成長型氫氧化鎂粉體表面之該矽烷化合物處理量以粉體量之0.001~5質量%較佳,特別以0.01~3質量%為最佳。
本發明中,(B)成份之非結晶成長型氫氧化鎂之調配量對於100質量份之(A)成份時,(B)成份為30~300質量份較佳,更佳者為40~200質量份。當(B)成份不足30質量份時,則難燃效果將不足,反之,超出300質量份則硬度太大。
本發明之(C)成份有機聚矽氧烷係取下式(1)之構造者。
RaSiO4-a/2 (1)
(式中,R為羥基、或碳數1~10之非取代或取代之一價烴基,a為1.9≦a≦2.1之數)。
該(1)式中之R為羥基或碳原子數為1~10,較佳者為1~8之非取代或取代一價烴基,例如:甲基、乙基、丙基、丁基等烷基、乙烯基、烯丙基、丁烯基等脂烯基、苯基、甲苯基等芳基、結合於此等基之碳原子的部份或全部氫原子被氰基取代之2-氰乙基等之取代烴基例,惟,由對於粉體之計量機、輸送裝置之壁面的附著性及成型加工時的流動性觀點,其全部或大部份取代基為甲基者較佳。
又,此有機聚矽氧烷之分子構造為直鏈狀者為理想者,而,含部份支鏈狀之分子構造亦無妨。因此,a為1.9≦a≦2.1之數者較佳,更佳者為1.95≦a≦2.05之數。
該式(1)之矽氧烷單位重覆數之平均聚合度本發明所使用之有機聚矽氧烷為2500~30000較佳,更佳者為3000~1500。當平均聚度之值不足2500時,則樹脂成型物之機械性質降低,因此為不理想者。又,即使有機聚矽氧烷於成型加工時具良好流動性,而其平均聚合度卻超出30000,則組成物黏度太高,於製造時攪拌不易亦為不理想者。
該式(1)之例者,其具體例如下式所示例者。
其中,R1例如有選自碳數1~10之一價烴基、羥基之同種或不同種之取代基,例如:選自甲基、乙基、丙基、丁基等烷基、環己基等之環烷基、苯基芳基、或結合於此等基之碳原子之部份或全部氫原子被氰基等取代之三氟丙基、氰乙基等非取代或取代1價烴基等之基者。(C)成份之有機聚矽氧烷整體所含之R1至少80%為甲基者,其特性較佳。
此有機聚矽氧烷之性狀為油狀,生橡膠狀者均可。該式1之矽氧烷單位之重覆數之n值為未達2000時,有時難燃性降低,加工性變差,因此不理想。反之,n為超出30000則組成物黏度太高,製造時攪拌不易。本發明之(C)
成份亦可倂用2種以上者。
本發明(C)高聚合度有機聚矽氧烷之調配量對於100質量份之(A)熱塑性樹脂時,為0.1~50重量份較佳,較佳者為1~20重量份,更佳者為2~15重量份進行調配較佳。不足0.1重量份之調配量時,無法發揮足夠的難燃性,反之,超出50重量份則將降低張力強度,延伸等機械強度。
製造本發明組成物時,對於非結晶成長型氫氧化鎂粉末使該式(1)所示有機聚矽氧烷以1~30質量%比例預先藉由加壓混煉機等處理有機聚矽氧烷處理粉末者調配於熱塑性樹脂者亦可。
此時,分散非結晶成長型氫氧化鎂粉體之有機聚矽氧烷務必為1質量%~30質量%之金屬氫氧化物有機聚矽氧烷總重量。當不足1質量%時,則減少難燃性之提昇。超出30質量%則呈橡膠狀,而使得下一步驟之聚矽氧分散不易,出現降低難燃性。
本發明非鹵素難燃樹脂組成物在不阻擾其特性下,可依其目的調配添加劑。做為添加劑例者如:有機過氧化物、矽烷偶合劑、濕潤劑、抗氧化劑、紫外線吸收劑、安定劑、光安定劑、互溶化劑、他類之非鹵素難燃劑、潤滑劑、填充劑、黏著助劑、防銹劑例者。
做為本發明可使用之有機過氧化物例者如:二異丙苯過氧化物、第三-丁基過氧基-2-乙基己酸酯、2,5-二甲基-2,5-二(苯甲醯過氧基)己烷、第三-己基過氧基苯甲酸酯、1,1雙(第三-丁基過氧基)-3,3,5-三甲基環己烷、1
,1-雙(第三-己基過氧基)-環己烷、1,1-雙(第三-己基過氧基)-3,3,5-三甲基環己烷、1,1-雙(第三-丁己基過氧基)環己烷、1,1-雙(第三-丁基過氧基)-環十二烷、n-丁基-4,4-雙(第三-丁基過氧基)戊醯酸酯、2,5-二甲基-2,5-二(第三-丁基過氧基)己烷、α,α-雙(第三-丁基過氧基)二異丙基苯、第三-丁基異丙苯過氧化物、二-第三-丁基過氧化物、2,5-二甲基-2,5-二(第三-丁基過氧基)己烷-3、第三-丁基異丙苯過氧化物、1,1,3,3,-四甲基丁基過氧基-2-乙基己酸酯,苯甲醯過氧化物、第三-丁基丁基過氧基乙酸酯等例,惟並未受限於此。
上述中又以過氧化縮酮類、二烷基過氧化物類所屬有機過氧化物所產生高游離自由基量者多,因此適於交聯。
有機過氧化物之種類一般依加工時之溫度,考量10小時半衰期溫度後進行選取之。加工溫度依其樹脂種類而變更,一般,聚烯烴樹脂時以80~250℃較佳。有機過氧化物之調配量以0.01~5重量份較佳。
做為本發明可使用之矽烷偶合劑例者如:β-(3,4-環氧基環己基)乙基三甲基矽烷、γ環氧丙氧基丙基三甲氧基矽烷、γ甲基丙烯氧基丙基甲氧基矽烷、N-β(胺基乙基)γ胺基丙基三甲氧基矽烷、γ胺基丙基三乙氧基矽烷、γ氫硫基丙基三甲氧基矽烷、乙烯三甲氧基矽烷、乙烯三甲氧基矽烷、乙烯三(β甲氧基乙氧基)矽烷等例。
做為本發明可使用之濕潤劑者,如黏度為10000mm/s以下之各種聚矽氧油例。具體例如:二甲基聚矽氧油、乙
烯聚矽氧油、苯基聚矽氧油、含羥基之聚矽氧油、含烷氧基之聚矽氧油、環氧基改性聚矽氧油、羧基改性聚矽氧油、胺基改性聚矽氧油、苯酚改性聚矽氧油、卡必醇改性聚矽氧油等例。
做為本發明可使用之抗氧化劑例者如:2,6-二-第三-丁基-4-甲基苯酚、n-辛癸基-3-(3’,5’-二-第三-丁基-4-羥苯基)丙酸酯、四[亞甲基-3-(3,5-二-第三-丁基-4-羥苯基)丙酸酯]甲烷、三(3,5-二-第三-丁基-4-羥基苄基)三異氰酸酯、4,4’-亞丁基雙-(3-甲基-6-第三-丁基苯酚)、三乙二醇-雙[3-(3-第三-丁基-4-羥基-5-甲基苯基)丙酸酯]、3,9-雙{2-[3-(3-第三-丁基-4-羥基-5-甲基苯基)丙醯氧基]-1,1-二甲基乙基}-2,4,8,10-四噁螺旋[5,5]十一烷、4-4-硫代雙-(2-第三-丁基-5-甲基苯酚)、2,2-亞甲基雙-(6-第三-丁基-甲基苯酚)、4,4-亞甲基雙(2,6-二-第三-丁基苯酚)、1,3,5,-三甲基-2,4,6-三(3,5-二-第三-丁基-4-羥基苄基)苯、三壬基苯基磷酸酯、三(2,4-二-第三-丁基苯基)磷酸酯、二硬脂烯基季戊四醇磷酸酯、雙(2,4-二-第三-丁基苯基)季戊四醇磷酸酯、雙(2,6-二-第三-丁基-4-甲基苯基)季戊四醇磷酸酯、2,2-亞甲基雙(4,6-二-第三-丁基苯基)辛基磷酸酯、四(2,4-二-第三-丁基苯基)-4,4’-聯苯-二磷酸酯、二月桂基-3,3’-硫代二丙酸酯、二肉豆蔻-3,3’-硫代二丙酸酯、季戊四醇四(3-月桂硫代丙酸酯)、2,5,7,8-四甲基-2(4,8,12-三甲基癸基)香豆酮-2-醇、5,7-二-第三-丁基-3-(3,4-二
甲基苯基)-3H-苯並呋喃-2-酮、2-[1-(2-羥基-3,5-二-第三-戊基苯基)乙基]-4,6-二戊基苯基丙烯酸酯、2-第三-丁基-6-(3-第三-丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、四(亞甲基)-3-(月桂基硫代丙酸酯)甲烷等例。
做為本發明可使用之安定劑例者如:硬脂酸鋰、硬脂酸鎂、月桂酸鈣、萞麻醇酸鈣、硬脂酸鈣、月桂酸鋇、萞麻醇酸鋇、硬脂酸鋇、月桂酸鋅、萞麻醇酸鋅、硬脂酸鋅等各種金屬皂系安定劑、月桂酸酯系、馬來酸酯系、氫硫系各種有機錫系安定劑、硬脂酸鉛、三鹼性硫酸鉛等各種鉛系安定劑、環氧化植物油等環氧化合物、烷基烯丙基磷酸酯、三烷基酸酯等磷酸酯化合物、二苯甲醯甲烷、脫氫醋酸等β-二酮化合物、山梨糖醇、甘露醇、季戊四醇系聚醇、水滑石類、沸石類例者。
做為本發明可使用之光安定劑例者如:苯並三唑系紫外線吸收劑、二苯甲酮系紫外線吸收劑、水楊酸酯系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑、草酸醯替苯胺系紫外線吸收劑、受阻胺系光安定劑等例。
做為本發明可使用之互溶化劑例如:丙烯基有機聚矽氧烷共聚物、二氧化矽與有機聚矽氧烷之部份交聯物,聚矽氧粉末、MQ樹脂、無水馬來化接枝改性聚烯烴、羧酸化接枝改性聚烯烴、聚烯烴接枝改性有機聚矽氧烷等例。
做為本發明可使用之其他非鹵素難燃劑例者如:硼酸鋅、錫酸鋅,各種磷系難燃劑、膨脹性石墨、三異氰酸蜜胺、胺基磺酸脈、光氧化鈦等例。又,做為填充劑例者如
:矽酸、碳酸鈣、氧化鈦、碳黑、陶土黏土、燒成黏土、矽酸鋁、矽酸鎂、矽酸鈣、氧化鋇等例。
本發明非鹵素難燃樹脂組成物亦可將非結晶成長型氫氧化鎂、高聚合度有機聚矽氧烷加入熱塑性樹脂時,直接以雙軸擠壓器、單軸擠壓器、超高速攪拌式混合器、或於加壓揑合器中進行加熱混合者,而,作成調配高聚合度有機聚矽氧烷與非結晶成長型氫氧化鎂之主膠料,將主膠料以所定濃度調配於熱塑性樹脂者較具良好使用性及分散性者。
本發明非鹵素難燃樹脂組成物做為難燃管或難燃薄片成型用材料特別理想。
以下,以實施例、比較例為基準,進行本發明更具體之說明,惟,本發明在不超越該主旨下,並未受限於以下實施例。另外,表1之原材料欄之數字代表質量份。
對於100質量份之(A)成份之EVA樹脂(ebaflec 460、三井Deupon chemical股份公司製)時,以表2及表3之比例調配(B)成份之表1所示各種氫氧化鎂原材料,(C)成份之下式所示高聚合度二甲基聚矽氧烷後,置入Laboplastmil R250混合器(東洋精機公司製),於150℃、30rpm、10分鐘之條件下進行混合後,做成顆粒進行擠壓之後,於150℃
,1分鐘,成1mm厚度下藉由加壓成型後,作成試驗用薄片。將此薄片以JIS-K7113之1號啞鈴型試驗片作成穿孔試驗片,依JIS-K7113為基準測定張力強度及延伸度。又,將試驗用薄片切取長度150mm、寬20mm,依JIS-K7201為基準求取耗氧指數。(測定結果載於表2、表3)。
高聚合度二甲基聚矽氧烷
氫氧化鎂之價格與粒徑尺寸之分佈
所使用氫氧化鎂之種類如下。
(1)kisma 8:結晶成長型氫氧化鎂(協和化學工業股份公司製) 平均粒徑1.7μm
(2)kisma 5A:結晶成長型氫氧化鎂(協和化學工業股份公司製) 平均粒徑0.8μm
(3)magnifin H-5GV:結晶成長型氫氧化鎂(Albemall股份公司製) 平均粒徑0.8μm
(4)magsiez N-4:結晶成長型氫氧化鎂(神島化學工業股份公司製) 平均粒徑0.9μm
(5)MGZ-3:於微細之氧化鎂反應未含二氧化碳之水者(堺化學工業股份公司製) 平均粒徑0.1μm
(6)UD-650:非結晶成長型氫氧化鎂(宇部materials股份公司製) 平均粒徑3.2μm
(7)日本海水加工公司製氫氧化鎂:非結晶成長型氫氧化鎂(日本海水加工股份公司製) 平均粒徑5.0μm
(8)UD-650分級物A:UD-650以分級機TTSP分離器(細川micron股份公司製)分級之第2畫分 平均粒徑0.4μm
(9)UD-650分級物B:UD-650以分級機TTSP分離器(細川micron股份公司製)分級之第1畫分 平均粒徑7.0μm
表2~表3所載之物性的測定方法如以下所示。
張力強度:依JIS-K 7113為基準進行測定之。
延伸度:依JIS-K 7113為基準進行測定之。
耗氧指數:依JIS-K 7201為基準進行測定之。
表2~表3所載之價格的評定基準如下述。
將調配比例依上述方法進行調配(A)EVA 100質量份、(B)氫氧化鎂94質量份、(C)高聚合度二甲基聚矽氧烷6質量份時之價格依下述基準進行評定之。
評價判定
○:使用kisma 5A組成物未達3/4之價格
△:使用kisma 5A組成物為3/4~同額價格
×:高於所使用kisma 5A組成物之價格
Claims (5)
- 一種非鹵素難燃樹脂組成物,其特徵係對於(A)聚烯烴樹脂100質量份時,配合(B)非結晶成長型氫氧化鎂30~300質量份、(C)成份之有機聚矽氧烷為以下述平均組成式(1)所示平均聚合度為2000~30000之有機聚矽氧烷0.1~50質量份所成者,RaSiO4-a/2 (1)(式中,R為選自羥基或碳數1~10之非取代或取代之一價烴基之基團,a為1.9≦a≦2.1之數)。
- 如申請專利範圍第1項之非鹵素難燃樹脂組成物,其中(B)成份之非結晶成長型氫氧化鎂係於海水或鹵水中所含之鎂鹽水溶液中添加入鹼後,不使結晶成長而製作膠體狀沈澱,膠體沈澱經洗淨乾燥後之氫氧化鎂構成者。
- 如申請專利範圍第1或2項之非鹵素難燃樹脂組成物,其中(B)成份之非結晶成長型氫氧化鎂係由含有粒徑為2~40μm之氫氧化鎂與粒徑為0.01~1.99μm之氫氧化鎂,其兩者之比例為25:75~99:1所成之氫氧化鎂者。
- 如申請專利範圍第1或2項之非鹵素難燃樹脂組成物,其中(B)成份之非結晶成長型氫氧化鎂為粒徑2~40μm之氫氧化鎂、粒徑0.01~1.99μm之氫氧化鎂1次粒子凝聚所成的2次粒子。
- 如申請專利範圍第1或2項之非鹵素難燃樹脂組成物 ,其中(C)成份之有機聚矽氧烷係具有下式(2)構造之高聚合度有機聚矽氧烷,
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