JP5269405B2 - Flame retardant silicone rubber composition - Google Patents
Flame retardant silicone rubber composition Download PDFInfo
- Publication number
- JP5269405B2 JP5269405B2 JP2007321531A JP2007321531A JP5269405B2 JP 5269405 B2 JP5269405 B2 JP 5269405B2 JP 2007321531 A JP2007321531 A JP 2007321531A JP 2007321531 A JP2007321531 A JP 2007321531A JP 5269405 B2 JP5269405 B2 JP 5269405B2
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- JP
- Japan
- Prior art keywords
- platinum
- silicone rubber
- rubber composition
- flame retardant
- complex
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 22
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 21
- 239000003063 flame retardant Substances 0.000 title claims abstract description 17
- 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 abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 43
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229920005601 base polymer Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 239000013585 weight reducing agent Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- UIEXFJVOIMVETD-UHFFFAOYSA-N P([O-])([O-])[O-].[Pt+3] Chemical compound P([O-])([O-])[O-].[Pt+3] UIEXFJVOIMVETD-UHFFFAOYSA-N 0.000 claims description 2
- MGTPLVPKJIZKQE-UHFFFAOYSA-N [Pt]#P Chemical compound [Pt]#P MGTPLVPKJIZKQE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000004580 weight loss Effects 0.000 abstract description 4
- -1 methyl siloxane Chemical class 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 150000003058 platinum compounds Chemical class 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 3
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 2
- BTZXIUXKZZEBHY-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)OC1=CC=CC=C1.[Pt] Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)OC1=CC=CC=C1.[Pt] BTZXIUXKZZEBHY-UHFFFAOYSA-N 0.000 description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- WXWYJCSIHQKADM-ZNAKCYKMSA-N (e)-n-[bis[[(e)-butan-2-ylideneamino]oxy]-ethenylsilyl]oxybutan-2-imine Chemical compound CC\C(C)=N\O[Si](O\N=C(/C)CC)(O\N=C(/C)CC)C=C WXWYJCSIHQKADM-ZNAKCYKMSA-N 0.000 description 1
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- PKAUJJPTOIWMDM-UHFFFAOYSA-N 3h-dioxaphosphepine Chemical compound C=1C=CPOOC=1 PKAUJJPTOIWMDM-UHFFFAOYSA-N 0.000 description 1
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RBLNICCKPGGVJW-UHFFFAOYSA-N C(C)O[Si](O[Sn])(OCC)OCC Chemical compound C(C)O[Si](O[Sn])(OCC)OCC RBLNICCKPGGVJW-UHFFFAOYSA-N 0.000 description 1
- GIPWORJMJNBCBZ-UHFFFAOYSA-N C[Si]1(O[Si](O[Si](O[Si](O1)(ON(CC)CC)ON(CC)CC)(C)C)(CCCC)CCCC)C Chemical compound C[Si]1(O[Si](O[Si](O[Si](O1)(ON(CC)CC)ON(CC)CC)(C)C)(CCCC)CCCC)C GIPWORJMJNBCBZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- LFMUISBVPOHEBB-UHFFFAOYSA-N N-[[6,6-bis(diethylaminooxy)-4,4,8,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl]oxy]-N-methylethanamine Chemical compound C[Si]1(O[Si](O[Si](O[SiH](O1)ON(CC)C)(C)C)(ON(CC)CC)ON(CC)CC)C LFMUISBVPOHEBB-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- VXPYSZQGFPMWQU-UHFFFAOYSA-L [acetyloxy(diphenyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.C=1C=CC=CC=1[Sn+2]C1=CC=CC=C1 VXPYSZQGFPMWQU-UHFFFAOYSA-L 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- AWFFJJAOMMAGFE-BGSQTJHASA-L [dibutyl-[(z)-octadec-9-enoyl]oxystannyl] (z)-octadec-9-enoate Chemical compound CCCC[Sn+2]CCCC.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O AWFFJJAOMMAGFE-BGSQTJHASA-L 0.000 description 1
- PGQPMLCDSAVZNJ-BGSQTJHASA-L [dimethyl-[(z)-octadec-9-enoyl]oxystannyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCCC\C=C/CCCCCCCC PGQPMLCDSAVZNJ-BGSQTJHASA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 230000002411 adverse Effects 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
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- UKRVECBFDMVBPU-UHFFFAOYSA-N ethyl 3-oxoheptanoate Chemical compound CCCCC(=O)CC(=O)OCC UKRVECBFDMVBPU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QFWAHMAYYWUGTI-UHFFFAOYSA-N methyl-tris(prop-1-enoxy)silane Chemical compound CC=CO[Si](C)(OC=CC)OC=CC QFWAHMAYYWUGTI-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- LXUDRQBMFVSERF-UHFFFAOYSA-N n-[[2-(diethylaminooxy)-4,4,6,6,8,8-hexamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl]oxy]-n-ethylethanamine Chemical compound CCN(CC)O[Si]1(ON(CC)CC)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 LXUDRQBMFVSERF-UHFFFAOYSA-N 0.000 description 1
- DJCGPLIRELCAMC-UHFFFAOYSA-N n-[[4,4-bis(diethylaminooxy)-2,6,6,8,8-pentamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl]oxy]-n-ethylethanamine Chemical compound CCN(CC)O[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](ON(CC)CC)(ON(CC)CC)O1 DJCGPLIRELCAMC-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- UTNLQXOLUGCCEJ-UHFFFAOYSA-N n-ethyl-n-[(2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)oxy]ethanamine Chemical compound CCN(CC)O[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 UTNLQXOLUGCCEJ-UHFFFAOYSA-N 0.000 description 1
- XZZXKVYTWCYOQX-UHFFFAOYSA-J octanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O XZZXKVYTWCYOQX-UHFFFAOYSA-J 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- OLTVTFUBQOLTND-UHFFFAOYSA-N tris(2-methoxyethoxy)-methylsilane Chemical compound COCCO[Si](C)(OCCOC)OCCOC OLTVTFUBQOLTND-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は優れた難燃性を有するシリコーンゴム組成物に関する。 The present invention relates to a silicone rubber composition having excellent flame retardancy.
従来から、硬化してシリコーンゴムとなるシリコーン組成物はよく知られており、その耐候性、耐熱性、電気絶縁性などの優れた性質を利用して、電気・電子部品のポッティング材、コーティング材、型取り用などの成形材料、電線用材料などに広く使用されている。また、このシリコーン組成物に各種添加剤を配合することによって、用途に応じた特性たとえば難燃性を付与して用いることも一般に行われている。上記シリコーンゴム組成物に対する難燃性付与の技術としては、従来より多数の報告がなされており、たとえば難燃性付与剤として白金系化合物を配合する方法(特許文献1参照)、また白金系化合物と金属酸化物等とを併用する方法(特許文献2参照)、さらに白金系化合物とカーボンブラック等とを併用する方法(特許文献3参照)などが知られている。また、白金系化合物を用いずに難燃性を付与する技術として、有機ハロゲン化合物を配合する方法(特許文献4参照)などが知られている。しかし、着色可能でUL94V0級の難燃性を得ようとすると、難燃助剤が持つ色調が影響することや、ベースに用いるメチルシロキサンの低分子シロキサン量を削減しなければならないなどの条件があった。また試験体の厚さに関わらず良好な難燃性を示すものがなかった。
本発明は斯かる従来技術の問題点に鑑み案出されたものであり、難燃性に優れ、且つシリコーンゴムの本来有する物性もそのまま維持している難燃性シリコーンゴム組成物を提供することを目的とする。 The present invention has been devised in view of such problems of the prior art, and provides a flame retardant silicone rubber composition which is excellent in flame retardancy and maintains the original physical properties of silicone rubber. With the goal.
本発明者等は上記目的を達成すべく鋭意検討した結果、熱硬化性ポリオルガノシロキサン組成物に対し、難燃性付与剤として常温常圧下で固体である白金錯体を一定量配合することで試験体の厚さに関わらず有効な難燃性を有することを見出し、本発明を完成するに至った。
即ち本発明は、
(A)熱硬化性ポリオルガノシロキサン組成物100重量部に対して、
(B)常温常圧下で固体であり、熱重量分析装置で重量減少率50重量%を超える時の温度が300℃以上である白金錯体を白金元素量として0.1〜1000ppm
添加してなる難燃性シリコーンゴム組成物である。
As a result of intensive studies to achieve the above-mentioned object, the present inventors have tested a thermosetting polyorganosiloxane composition by blending a certain amount of a platinum complex that is solid under normal temperature and pressure as a flame retardant imparting agent. It has been found that it has effective flame retardancy regardless of the thickness of the body, and has completed the present invention.
That is, the present invention
(A) With respect to 100 parts by weight of the thermosetting polyorganosiloxane composition,
(B) 0.1 to 1000 ppm as a platinum element amount of a platinum complex that is solid under normal temperature and normal pressure and has a temperature of 300 ° C. or higher when the weight loss rate exceeds 50 wt% in a thermogravimetric analyzer.
It is a flame retardant silicone rubber composition added.
本発明によれば、ベースに用いるメチルシロキサンの低分子シロキサン量を削減しなければならないなどの条件なく着色可能な難燃性シリコーンゴム組成物を提供することができる。本発明の難燃性シリコーンゴム組成物は、難燃性に優れると共にシリコーンゴムの本来有する優れた物性をそのまま維持しているので、ULの難燃認定を必要とするケーブル、パッキン、コネクター等に供される電気部品に好適に用いられ、また、熱や火炎に対して、本質的に難燃性が求められる建築部材(ガスケット、パッキング、シール材)にも好適に用いられる。 ADVANTAGE OF THE INVENTION According to this invention, the flame-retardant silicone rubber composition which can be colored without conditions, such as having to reduce the amount of low molecular siloxanes of the methylsiloxane used for a base, can be provided. The flame-retardant silicone rubber composition of the present invention is excellent in flame retardancy and maintains the excellent physical properties of silicone rubber as it is, so it can be used in cables, packings, connectors, etc. that require UL flame retardant certification. It is suitably used for electric parts to be provided, and is also suitably used for building members (gaskets, packing, sealing materials) that are essentially required to be flame retardant against heat and flame.
上記(A)成分の熱硬化性ポリオルガノシロキサン組成物は、(a)ポリオルガノシロキサンベースポリマーと、(b)硬化剤と、必要に応じて各種添加剤等とを均一に分散させたものである。このような組成物に用いられる各種成分のうち、(a)シリコーンベースポリマーと(b)硬化剤とは、ゴム弾性体を得るための反応機構に応じて適宜選択されるものである。その反応機構としては、(1) 有機過酸化物加硫剤による架橋方法、(2) 縮合反応による方法、(3) 付加反応による方法等が知られており、その反応機構によって、(a)成分と(b)成分すなわち硬化用触媒もしくは架橋剤との好ましい組合せが決まることは周知である。先ず、上記(1) の架橋方法を適用する場合においては、通常、(a)成分のベースポリマーとしては、1分子中のケイ素原子に結合した有機基のうち、少なくとも2個がビニル、プロペニル、ブテニル、ヘキセニルなどのアルケニル基であるポリオルガノシロキサンが用いられる。特に合成の容易さ、原料の入手のし易さから、上記基の中でもビニル基が多用される。また、(b)成分の硬化剤としては、ベンゾイルペルオキシド、2,4−ジクロロベンゾイルペルオキシド、ジクミルペルオキシド、クミル−t−ブチルペルオキシド、2,5 −ジメチル−2,5 −ジ−t−ブチルペルオキシヘキサン、ジ−t−ブチルペルオキシド等の各種の有機過酸化物加硫剤が用いられ、特に低い圧縮永久歪みを与えることから、ジクミルペルオキシド、クミル−t−ブチルペルオキシド、2,5 −ジメチル−2,5 −ジ−t−ブチルペルオキシヘキサン、ジ−t−ブチルペルオキシドが好ましい。なお、これらの有機過酸化物加硫剤は、1種または2種以上の混合物として用いられる。(b)成分の硬化剤である有機過酸化物の配合量は、(a)成分のシリコーンベースポリマー 100重量部に対し0.05〜15重量部の範囲が好ましい。有機過酸化物の配合量が0.05重量部未満では加硫が十分に行われず、15重量部を超えて配合してもそれ以上の格別な効果がないばかりか、得られたシリコーンゴムの物性に悪影響を与えることがあるからである。 The thermosetting polyorganosiloxane composition of the component (A) is obtained by uniformly dispersing (a) a polyorganosiloxane base polymer, (b) a curing agent, and various additives as required. is there. Of the various components used in such a composition, (a) the silicone base polymer and (b) the curing agent are appropriately selected according to the reaction mechanism for obtaining a rubber elastic body. As the reaction mechanism, (1) a crosslinking method using an organic peroxide vulcanizing agent, (2) a condensation reaction method, (3) an addition reaction method, etc. are known. It is well known that the preferred combination of component and component (b), ie a curing catalyst or crosslinker, is determined. First, in the case of applying the crosslinking method of (1), usually, as the base polymer of the component (a), at least two of organic groups bonded to silicon atoms in one molecule are vinyl, propenyl, Polyorganosiloxanes that are alkenyl groups such as butenyl and hexenyl are used. Of these groups, vinyl groups are frequently used because of the ease of synthesis and the availability of raw materials. In addition, as the curing agent for component (b), benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dicumyl peroxide, cumyl-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxy Various organic peroxide vulcanizing agents such as hexane and di-t-butyl peroxide are used and give particularly low compression set. Therefore, dicumyl peroxide, cumyl-t-butyl peroxide, 2,5-dimethyl- 2,5-Di-t-butylperoxyhexane and di-t-butylperoxide are preferred. These organic peroxide vulcanizing agents are used as one kind or a mixture of two or more kinds. The blending amount of the organic peroxide which is the curing agent of the component (b) is preferably in the range of 0.05 to 15 parts by weight with respect to 100 parts by weight of the silicone base polymer of the component (a). If the amount of organic peroxide is less than 0.05 parts by weight, vulcanization will not be performed sufficiently, and if it exceeds 15 parts by weight, there will be no particular effect, and the physical properties of the resulting silicone rubber will be reduced. This is because it may have an adverse effect.
また、上記(2) の縮合反応を適用する場合においては、(a)成分のベースポリマーとしては両末端に水酸基を有するポリジオルガノシロキサンが用いられる。(b)成分の硬化剤としては、まず架橋剤として、エチルシリケート、プロピルシリケート、メチルトリメトキシシラン、ビニルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリエトキシシラン、メチルトリス(メトキシエトキシ)シラン、ビニルトリス(メトキシエトキシ)シラン、メチルトリプロペノキシシラン等のアルコキシ型;メチルトリアセトキシシラン、ビニルトリアセトキシシラン等のアセトキシ型;メチルトリ(アセトンオキシム)シラン、ビニルトリ(アセトンオキシム)シラン、メチルトリ(メチルエチルケトキシム)シラン、ビニルトリ(メチルエチルケトキシム)シラン等、およびその部分加水分解物が例示される。また、ヘキサメチル−ビス(ジエチルアミノキシ)シクロテトラシロキサン、テトラメチルジブチル- ビス(ジエチルアミノキシ)シクロテトラシロキサン、ヘプタメチル(ジエチルアミノキシ)シクロテトラシロキサン、ペンタメチル−トリス(ジエチルアミノキシ)シクロテトラシロキサン、ヘキサメチル−ビス(メチルエチルアミノキシ)シクロテトラシロキサン、テトラメチル−ビス(ジエチルアミノキシ)−モノ(メチルエチルアミノキシ)シクロテトラシロキサンのような環状シロキサン等も例示される。このように、架橋剤はシランやシロキサン構造のいずれでもよく、またそのシロキサン構造は直鎖状、分岐状および環状のいずれでもよい。さらに、これらを使用する際には、1種類に限定される必要はなく、2種類以上の併用も可能である。また、(b)成分の硬化剤のうち、硬化用触媒としては、鉄オクトエート、コバルトオクトエート、マンガンオクトエート、スズナフテネート、スズカプリレート、スズオレエートのようなカルボン酸金属塩;ジメチルスズジオレエート、ジメチルスズジラウレート、ジブチルスズジアセテート、ジブチルスズジオクトエート、ジブチルスズジラウレート、ジブチルスズジオレエート、ジフェニルスズジアセテート、酸化ジブチルスズ、ジブチルスズジメトキシド、ジブチルビス(トリエトキシシロキシ)スズ、ジオクチルスズジラウレートのような有機スズ化合物が用いられる。(b)成分の硬化剤のうち、上記架橋剤の配合量は(a)成分のベースポリマー 100重量部に対し 0.1〜20重量部が好ましい。架橋剤の使用量が 0.1重量部未満では、硬化後のゴムに充分な強度が得られず、また20重量部を超えると得られるゴムが脆くなり、いずれも実用に耐え難い。また、硬化用触媒の配合量は(a)成分のベースポリマー 100重量部に対し0.01〜5重量部が好ましい。これより少ない量では硬化用触媒として不十分であって、硬化に長時間を要し、また空気との接触面から遠い内部での硬化が不良となる。他方、これよりも多い場合には、保存安定性が低下してしまう。より好ましい配合量の範囲としては、 0.1〜3重量部の範囲である。 When the condensation reaction (2) is applied, a polydiorganosiloxane having hydroxyl groups at both ends is used as the base polymer of the component (a). As the curing agent for component (b), first, as a crosslinking agent, ethyl silicate, propyl silicate, methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, methyltris (methoxyethoxy) silane, vinyltris ( Alkoxy type such as methoxyethoxy) silane and methyltripropenoxysilane; acetoxy type such as methyltriacetoxysilane and vinyltriacetoxysilane; methyltri (acetoneoxime) silane, vinyltri (acetoneoxime) silane, methyltri (methylethylketoxime) silane, Examples thereof include vinyltri (methylethylketoxime) silane and the like, and partial hydrolysates thereof. Hexamethyl-bis (diethylaminoxy) cyclotetrasiloxane, tetramethyldibutyl-bis (diethylaminoxy) cyclotetrasiloxane, heptamethyl (diethylaminoxy) cyclotetrasiloxane, pentamethyl-tris (diethylaminoxy) cyclotetrasiloxane, hexamethyl-bis ( Examples thereof include cyclic siloxanes such as methylethylaminoxy) cyclotetrasiloxane and tetramethyl-bis (diethylaminoxy) -mono (methylethylaminoxy) cyclotetrasiloxane. Thus, the cross-linking agent may be either a silane or siloxane structure, and the siloxane structure may be linear, branched or cyclic. Furthermore, when using these, it is not necessary to be limited to one type, and two or more types can be used together. Among the curing agents of component (b), examples of the curing catalyst include metal carboxylic acid salts such as iron octoate, cobalt octoate, manganese octoate, tin naphthenate, tin caprylate, and tin oleate; dimethyltin dioleate; Organotin compounds such as dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dioctyltin dilaurate Used. Of the curing agent (b), the amount of the crosslinking agent is preferably 0.1 to 20 parts by weight per 100 parts by weight of the base polymer (a). If the amount of the crosslinking agent used is less than 0.1 parts by weight, sufficient strength cannot be obtained in the rubber after curing, and if it exceeds 20 parts by weight, the resulting rubber becomes brittle, both of which are difficult to withstand practical use. Moreover, the compounding amount of the curing catalyst is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the component (a). If the amount is less than this, it is insufficient as a curing catalyst, and it takes a long time for curing, and curing in the interior far from the contact surface with air becomes poor. On the other hand, when it is more than this, the storage stability is lowered. A more preferable range of the blending amount is 0.1 to 3 parts by weight.
上記(3) の付加反応を適用する場合の(a)成分のベースポリマーとしては、上記(1) におけるベースポリマーと同様なものが用いられる。また、(b)成分の硬化剤としては、硬化用触媒として、塩化白金酸、白金オレフィン錯体、白金ビニルシロキサン錯体、白金黒、白金等の白金系触媒が用いられ、架橋剤として、ケイ素原子に結合した水素原子が1分子中に少なくとも平均2個を超える数を有するポリジオルガノシロキサンが用いられる。(b)成分の硬化剤のうち、硬化用触媒の配合量は、(a)成分のベースポリマーに対し白金元素量で1〜1000ppm の範囲となる量が好ましい。硬化用触媒の配合量が白金元素量として1ppm 未満では、充分に硬化が進行せず、また1000ppm を超えても特に硬化速度の向上等が期待できない。また、架橋剤の配合量は、(a)成分中のアルケニル基1個に対し、架橋剤中のケイ素原子に結合した水素原子が 0.5個〜4.0 個となるような量が好ましく、さらに好ましくは 1.0〜3.0個となるような量である。水素原子の量が0.5 個未満である場合は、組成物の硬化が充分に進行せずに、硬化後の組成物の硬さが低くなり、また水素原子の量が4.0 個を超えると硬化後の組成物の物理的性質と耐熱性が低下する。 As the base polymer of the component (a) in the case of applying the addition reaction of (3) above, the same base polymer as in the above (1) is used. In addition, as the curing agent of component (b), platinum catalysts such as chloroplatinic acid, platinum olefin complexes, platinum vinylsiloxane complexes, platinum black, platinum, etc. are used as curing catalysts. A polydiorganosiloxane having an average of more than at least two bonded hydrogen atoms per molecule is used. Of the curing agent of component (b), the blending amount of the curing catalyst is preferably in the range of 1 to 1000 ppm in terms of platinum element relative to the base polymer of component (a). If the amount of the curing catalyst is less than 1 ppm as the amount of platinum element, curing will not proceed sufficiently, and if it exceeds 1000 ppm, no improvement in the curing rate can be expected. The blending amount of the cross-linking agent is preferably such that 0.5 to 4.0 hydrogen atoms bonded to silicon atoms in the cross-linking agent per alkenyl group in component (a), more preferably The amount is 1.0 to 3.0. If the amount of hydrogen atoms is less than 0.5, curing of the composition does not proceed sufficiently, resulting in a low hardness of the composition after curing, and if the amount of hydrogen atoms exceeds 4.0, The physical properties and heat resistance of the composition are reduced.
以上のような各種の反応機構において用いられる(a)成分のベースポリマーとしてのポリオルガノシロキサンにおける有機基は、1価の置換または非置換の炭化水素基であり、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、ドデシル基のようなアルキル基、フェニル基のようなアリール基、β−フェニルエチル基、β−フェニルプロピル基のようなアラルキル基等の非置換の炭化水素基や、クロロメチル基、3,3,3 −トリフルオロプロピル基等の置換炭化水素基が例示される。なお、一般的にはメチル基が合成のしやすさ等から多用される。 The organic group in the polyorganosiloxane as the base polymer of the component (a) used in the various reaction mechanisms as described above is a monovalent substituted or unsubstituted hydrocarbon group, such as a methyl group, an ethyl group, or a propyl group. An unsubstituted hydrocarbon group such as an alkyl group such as a butyl group, a hexyl group or a dodecyl group, an aryl group such as a phenyl group, an aralkyl group such as a β-phenylethyl group or a β-phenylpropyl group, Examples thereof include substituted hydrocarbon groups such as a methyl group and 3,3,3-trifluoropropyl group. In general, methyl groups are frequently used because of their ease of synthesis.
本発明に用いられる(B)成分の白金錯体は常温常圧下で固体であることが必須である。液状の白金錯体単独では十分な難燃性を付与することが困難である。また、熱重量分析装置で300℃以上で重量減少率50重量%を超えるものが特に好ましい。
(B)成分として好ましいものは、成分が白金−リン元素を含有する化合物錯体であり、特に白金−亜リン酸エステル錯体が好ましい。
ここで用いられるリン化合物については、たとえばトリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、6-[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2, 4, 8, 10-テトラ-tert-ブチルジベンズ[d, f,][1.3.2]ジオキサホスフェピンなどで例示される化合物であり、亜リン酸エステル化合物として常温常圧下で固体であるものが好ましい。
(B)白金錯体の配合量は、(A)成分の熱硬化性シリコーンゴム組成物100重量部に対し、白金の元素量に換算して0.01〜1000ppm となる範囲であり、好ましくは 0.5〜200ppmの範囲である。これらの白金元素としての配合量が0.01ppm 未満では難燃性付与効果が不十分となる。他方、白金系化合物は貴金属を含み一般に高価であることから多量の添加は経済的に不利であり、また1000ppm を超えても格別の意味がない上に耐熱性が悪くなるため、このような範囲が画定される。
The platinum complex of component (B) used in the present invention must be a solid at normal temperature and pressure. It is difficult to impart sufficient flame retardancy with a liquid platinum complex alone. Further, a thermogravimetric analyzer having a weight reduction rate exceeding 50% by weight at 300 ° C. or higher is particularly preferable.
A preferable component (B) is a compound complex containing a platinum-phosphorus element, and a platinum-phosphite complex is particularly preferable.
Examples of the phosphorus compound used here include tris (2,4-di-tert-butylphenyl) phosphite, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]- 2, 4, 8, 10-Tetra-tert-butyldibenz [d, f,] [1.3.2] A compound exemplified by dioxaphosphepine, etc., which is a solid phosphite compound at room temperature and normal pressure. Some are preferred.
The blending amount of the (B) platinum complex is within a range of 0.01 to 1000 ppm, preferably 0.5 to 200 ppm, in terms of the elemental amount of platinum with respect to 100 parts by weight of the thermosetting silicone rubber composition of the component (A). Range. If the compounding amount of these platinum elements is less than 0.01 ppm, the effect of imparting flame retardancy is insufficient. On the other hand, platinum compounds contain precious metals and are generally expensive, so adding a large amount is economically disadvantageous, and even if it exceeds 1000 ppm, there is no particular meaning and the heat resistance deteriorates. Is defined.
さらには本発明に用いられる固体の白金錯体に液体の白金錯体を併用することが好ましい。液体の白金錯体としては、前述したポリオルガノシロキサンの付加反応における硬化用触媒として用いられる白金系化合物と同様なものでよく、たとえばアルコール変性塩化白金酸、白金とオレフィンとの錯体、白金とケトン類との錯体、白金とビニルシロキサンとの錯体などで例示される白金系化合物が例示される。斯かる白金系化合物を前述の(B)成分と併用することにより、難燃性に優れ、且つシリコーンゴムの本来有する物性を阻害しないシリコーンゴムを得ることができる。併用する液体の白金系化合物の配合量は、(A)成分のシリコーンゴム組成物 100重量部に対し、白金金属の元素量に換算して0.01〜1000ppm となる範囲であり、好ましくは 0.5〜200ppmの範囲である。これらの白金化合物の配合量が0.01ppm 未満では難燃性付与効果が不十分となる。他方、白金化合物は一般に高価であることから多量の添加は経済的に不利であり、また1000ppm を超えても格別の意味がない上に耐熱性が悪くなるため、このような範囲が画定される。 Furthermore, it is preferable to use a liquid platinum complex in combination with the solid platinum complex used in the present invention. The liquid platinum complex may be the same as the platinum compound used as the curing catalyst in the polyorganosiloxane addition reaction described above. For example, alcohol-modified chloroplatinic acid, a complex of platinum and olefin, platinum and ketones And platinum-based compounds exemplified by complexes with platinum, complexes of platinum and vinylsiloxane, and the like. By using such a platinum compound in combination with the aforementioned component (B), it is possible to obtain a silicone rubber that is excellent in flame retardancy and does not hinder the inherent properties of the silicone rubber. The compounding amount of the liquid platinum compound used in combination is in the range of 0.01 to 1000 ppm, preferably 0.5 to 200 ppm, in terms of the amount of platinum metal element, per 100 parts by weight of the silicone rubber composition (A). Range. When the compounding amount of these platinum compounds is less than 0.01 ppm, the effect of imparting flame retardancy is insufficient. On the other hand, platinum compounds are generally expensive, so adding a large amount is economically disadvantageous, and there is no particular meaning even if the amount exceeds 1000 ppm, and the heat resistance deteriorates, so such a range is defined. .
なお、本発明の難燃性シリコーンゴム組成物には、補強性充填剤、耐熱性向上剤、上記以外の難燃剤等の各種添加剤を随時付加的に配合してもよい。このようなものとしては、通常、煙霧質シリカ、沈澱法シリカ、けいそう土等の補強性充填剤、グラファイト、酸化アルミニウム、二酸化チタン、水酸化セリウム、マイカ、クレイ、ガラスビーズ、ポリジメチルシロキサン、アルケニル基含有ポリシロキサン等の耐熱向上剤が例示される。 The flame retardant silicone rubber composition of the present invention may additionally contain various additives such as reinforcing fillers, heat resistance improvers and flame retardants other than those described above. As such, usually, fumed silica, precipitated silica, diatomaceous earth and other reinforcing fillers, graphite, aluminum oxide, titanium dioxide, cerium hydroxide, mica, clay, glass beads, polydimethylsiloxane, Examples thereof include heat resistance improvers such as alkenyl group-containing polysiloxane.
以下、本発明の実施例について説明する。尚、実施例中の部は重量部を示す。 Examples of the present invention will be described below. In addition, the part in an Example shows a weight part.
錯体調製例1
5gの塩化白金酸(H2PtCl6)(白金含有量37wt%)、90gのTHF(テトラヒドロフラン)、12.3gのトリス(2,4,-ジ-tert-ブチルフェニル)ホスファイトを混合し、窒素雰囲気下6時間加熱還流させた。次に減圧下濃縮した。200gのエタノールを加え白色沈殿物を得た。得られた沈殿物を濾過によって取り分けた後、エタノールで洗浄した。このものの、熱重量分析装置(air雰囲気下、10℃/minの昇温条件下)で50%の重量減少率を超えた温度は395℃であった。粘度10Pa・sの両末端ビニルジメチルシロキシ基封鎖直鎖状ジメチルポリシロキサンで25℃において希釈し、ペースト1(白金含有量1wt%)を調製した。
Complex preparation example 1
5 g of chloroplatinic acid (H 2 PtCl 6 ) (platinum content 37 wt%), 90 g of THF (tetrahydrofuran), 12.3 g of tris (2,4, -di-tert-butylphenyl) phosphite were mixed, The mixture was heated to reflux for 6 hours under a nitrogen atmosphere. Then, it was concentrated under reduced pressure. 200 g of ethanol was added to obtain a white precipitate. The resulting precipitate was filtered off and washed with ethanol. However, the temperature exceeding the 50% weight reduction rate in a thermogravimetric analyzer (in the air atmosphere, at a temperature rising rate of 10 ° C./min) was 395 ° C. A paste 1 (platinum content 1 wt%) was prepared by diluting at 25 ° C. with a vinyldimethylsiloxy group-blocked linear dimethylpolysiloxane having a viscosity of 10 Pa · s at both ends.
錯体調製例2
5gの塩化白金酸(H2PtCl6)(白金含有量37wt%)、90gのTHF、12.2gの6-[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2, 4, 8, 10-テトラ-tert-ブチルジベンズ[d, f,][1.3.2]ジオキサホスフェピンを混合し、窒素雰囲気下6時間加熱還流させた。次に減圧下濃縮した。200gのエタノールを加え白色沈殿物を得た。得られた沈殿物を濾過によって取り分けた後、多量のエタノールで洗浄した。このものの、熱重量分析装置(air雰囲気下、10℃/minの昇温条件下)で50%の重量減少率を超えた温度は436℃であった。粘度10Pa・sの両末端ビニルジメチルシロキシ基封鎖直鎖状ジメチルポリシロキサンで25℃において希釈し、ペースト2(白金含有量1wt%)を調製した。
Complex preparation example 2
5 g chloroplatinic acid (H 2 PtCl 6 ) (platinum content 37 wt%), 90 g THF, 12.2 g 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2, 4, 8, 10-Tetra-tert-butyldibenz [d, f,] [1.3.2] dioxaphosphine was mixed and heated to reflux in a nitrogen atmosphere for 6 hours. Then, it was concentrated under reduced pressure. 200 g of ethanol was added to obtain a white precipitate. The obtained precipitate was separated by filtration and then washed with a large amount of ethanol. However, the temperature at which the weight loss rate exceeded 50% was 436 ° C. in a thermogravimetric analyzer (in the air atmosphere, at a temperature rising rate of 10 ° C./min). A paste 2 (platinum content 1 wt%) was prepared by diluting with a linear dimethylpolysiloxane blocked with vinyldimethylsiloxy group-blocked linear dimethylpolysiloxane having a viscosity of 10 Pa · s.
比較錯体調製例1
5gの塩化白金酸(H2PtCl6)(白金含有量37wt%)、80gのエタノール、13gのトリスノニルフェニルホスファイト、34gの炭酸水素ナトリウムを混合し、4時間加熱還流させた。次に生成した塩を濾過し更に20gのエタノールで洗浄して、白金錯体のエタノール溶液を得た。過剰のエタノールを減圧下で除去した。このものの、熱重量分析装置(air雰囲気下、10℃/minの昇温条件下)で50%の重量減少率を超えた温度は286℃であった。次いで、白金含有量が1%になるように粘度10Pa・sの両末端ビニルジメチルシロキシ基封鎖直鎖状ジメチルポリシロキサンで25℃において希釈し、ペースト3を調整した。
Comparative complex preparation example 1
5 g of chloroplatinic acid (H 2 PtCl 6 ) (platinum content 37 wt%), 80 g of ethanol, 13 g of trisnonylphenyl phosphite and 34 g of sodium hydrogen carbonate were mixed and heated to reflux for 4 hours. Next, the produced salt was filtered and further washed with 20 g of ethanol to obtain an ethanol solution of a platinum complex. Excess ethanol was removed under reduced pressure. However, the temperature at which the weight loss rate exceeded 50% was 286 ° C. in a thermogravimetric analyzer (in the air atmosphere, at a temperature rising rate of 10 ° C./min). Next, the paste 3 was prepared by diluting with a linear dimethylpolysiloxane blocked at both ends with a vinyldimethylsiloxy group having a viscosity of 10 Pa · s so that the platinum content was 1% at 25 ° C.
比較錯体調製例2
5gの塩化白金酸(H2PtCl6)(白金含有量37wt%)、80gのエタノール、13gの2−エチルヘキシルアシッドホスフェート、34gの炭酸水素ナトリウムを混合し4時間加熱還流させた。次に生成した塩を濾過し更に20gのエタノールで洗浄して、白金錯体のエタノール溶液を得た。過剰のエタノールを減圧下で除去し、析出してきた塩を更に濾過した。このものの、熱重量分析装置(air雰囲気下、10℃/minの昇温条件下)で50%の重量減少率を超えた温度は207℃であった。次いで、白金含有量が1%になるように粘度10Pa・sの両末端ビニルジメチルシロキシ基封鎖直鎖状ジメチルポリシロキサンで25℃において希釈し、ペースト4を調整した。
Comparative complex preparation example 2
5 g of chloroplatinic acid (H 2 PtCl 6 ) (platinum content 37 wt%), 80 g of ethanol, 13 g of 2-ethylhexyl acid phosphate and 34 g of sodium hydrogen carbonate were mixed and heated to reflux for 4 hours. Next, the produced salt was filtered and further washed with 20 g of ethanol to obtain an ethanol solution of a platinum complex. Excess ethanol was removed under reduced pressure, and the precipitated salt was further filtered. However, the temperature exceeding the 50% weight reduction rate by a thermogravimetric analyzer (under an air atmosphere at a temperature rising rate of 10 ° C./min) was 207 ° C. Next, the paste 4 was prepared by diluting with a linear dimethylpolysiloxane blocked at both ends with a vinyldimethylsiloxy group having a viscosity of 10 Pa · s so that the platinum content was 1% at 25 ° C.
実施例1
メチルビニルシロキサン単位を0.13モル%含有するポリジメチルシロキサン(重合度約5500)100 部、及び煙霧質シリカ(Aerosil 130 、日本アエロジル(株)製)30部を、ニーダーを用いて均一に混練した後、これを150℃の温度で2時間処理した。室温まで冷却した後、結晶性シリカ(Crystalite VX-S、龍森(株)製)60部、酸化チタン(P-25 、日本アエロジル(株)製)5部、水酸化セリウム(第一稀元素化学工業(株)製)10部、錯体調製例1で調製したペースト(白金含有量1wt%)を混合、撹拌してコンパウンドを得た。
このコンパウンドに加硫剤(2,5−ジメチル−2,5 −ジ−t−ブチルパーオキシヘキサン)を添加後、170℃×10分でプレス後、200℃×4時間で熱空気加硫を行い、3種類の厚さ(0.5, 1.0, 2.0 mm)のゴムシートを作成した。
Example 1
After uniformly kneading 100 parts of polydimethylsiloxane (degree of polymerization about 5500) containing 0.13 mol% of methylvinylsiloxane unit and 30 parts of fumed silica (Aerosil 130, Nippon Aerosil Co., Ltd.) using a kneader This was treated at a temperature of 150 ° C. for 2 hours. After cooling to room temperature, 60 parts of crystalline silica (Crystalite VX-S, manufactured by Tatsumori Co., Ltd.), 5 parts of titanium oxide (P-25, manufactured by Nippon Aerosil Co., Ltd.), cerium hydroxide (first rare element) 10 parts by Chemical Industry Co., Ltd. and the paste prepared in Complex Preparation Example 1 (platinum content 1 wt%) were mixed and stirred to obtain a compound.
After adding a vulcanizing agent (2,5-dimethyl-2,5-di-t-butylperoxyhexane) to this compound, press it at 170 ° C for 10 minutes, and then perform hot air vulcanization at 200 ° C for 4 hours. The rubber sheet of 3 types (0.5, 1.0, 2.0 mm) was produced.
実施例2〜4、比較例1〜4
表1に示すように、錯体調製例1〜2、比較錯体調製例1〜2で調製したペースト1〜4、並びにこれらと白金−トリフェニルホスファイト錯体(白金含有量6.3wt%)を表1に示す量添加した以外は実施例1と同様にしてゴムシートを作成した。
Examples 2-4, Comparative Examples 1-4
As shown in Table 1, Table 1 shows pastes 1 to 4 prepared in Complex Preparation Examples 1 and 2, Comparative Complex Preparation Examples 1 and 2, and platinum-triphenylphosphite complex (platinum content: 6.3 wt%). A rubber sheet was prepared in the same manner as in Example 1 except that the amount shown in (1) was added.
比較例5〜7
表1に示すように、ペースト1に代えてビニル錯体とホスフィンの混合物を表1に示す量添加した以外は実施例1と同様にしてゴムシートを作成した。
Comparative Examples 5-7
As shown in Table 1, a rubber sheet was prepared in the same manner as in Example 1 except that instead of paste 1, a mixture of vinyl complex and phosphine was added in the amount shown in Table 1.
実施例5
粘度が10Pa・sである分子鎖両末端がビニルジメチルシロキシ基で封鎖されたジメチルポリシロキサン100部、及び煙霧質シリカ(Aerosil 130 、日本アエロジル(株)製)27部、ヘキサメチルシラザン4部を、万能混練機を用いて均一に混練した後、これを150℃の温度で2時間減圧処理した。室温まで冷却した後、結晶性シリカ(Crystalite VX-S、龍森(株)製)60部、酸化チタン(P-25 、日本アエロジル(株)製)60部、錯体調整例1で調整したペースト(白金含有量1wt%)、白金−亜リン酸トリフェニル錯体(白金含有量6.3wt%)を混合撹拌してコンパウンドを得た。そこに粘度が0.04Pa・sであるメチルハイドロジェンポリシロキサン5部加え、均一に混合し、難燃性シリコーン組成物を得た。
この組成物を170℃×10 分でプレス後、200℃×4時間で熱空気加硫を行い、3種類の厚さ(0.5, 1.0, 2.0 mm)のゴムシートを作成した。
Example 5
100 parts of dimethylpolysiloxane having both ends of a molecular chain with a viscosity of 10 Pa · s blocked with vinyldimethylsiloxy groups, 27 parts of fumed silica (Aerosil 130, manufactured by Nippon Aerosil Co., Ltd.), 4 parts of hexamethylsilazane The mixture was uniformly kneaded using a universal kneader, and then subjected to reduced pressure treatment at a temperature of 150 ° C. for 2 hours. After cooling to room temperature, 60 parts of crystalline silica (Crystalite VX-S, manufactured by Tatsumori Co., Ltd.), 60 parts of titanium oxide (P-25, manufactured by Nippon Aerosil Co., Ltd.), paste prepared in Complex Preparation Example 1 (Platinum content 1 wt%) and platinum-phosphorous triphenyl complex (platinum content 6.3 wt%) were mixed and stirred to obtain a compound. Thereto was added 5 parts of methyl hydrogen polysiloxane having a viscosity of 0.04 Pa · s and mixed uniformly to obtain a flame retardant silicone composition.
This composition was pressed at 170 ° C. × 10 minutes and then hot-air vulcanized at 200 ° C. × 4 hours to prepare rubber sheets having three thicknesses (0.5, 1.0, 2.0 mm).
実施例6〜8、比較例8〜10
表2に示すように、錯体調製例1〜2、比較錯体調製例1〜2で調製したペースト1〜4、並びにこれらと白金−トリフェニルホスファイト錯体(白金含有量6.3wt%)を表2に示す量添加した以外は実施例1と同様にしてゴムシートを作成した。
比較例11〜13
表2に示すように、ペースト1に代えてビニル錯体とホスフィンの混合物を表2に示す量添加した以外は実施例5と同様にしてゴムシートを作成した。
Examples 6-8, Comparative Examples 8-10
As shown in Table 2, pastes 1 to 4 prepared in Complex Preparation Examples 1 and 2 and Comparative Complex Preparation Examples 1 to 2, and these and a platinum-triphenylphosphite complex (platinum content 6.3 wt%) are shown in Table 2. A rubber sheet was prepared in the same manner as in Example 1 except that the amount shown in (1) was added.
Comparative Examples 11-13
As shown in Table 2, a rubber sheet was prepared in the same manner as in Example 5 except that instead of paste 1, a mixture of a vinyl complex and a phosphine was added in the amount shown in Table 2.
(難燃性の評価)
該硬化物の難燃性の評価を、UL−94の難燃性の試験方法に準じて、以下のようにして行った。ブンゼンバーナー(内径9.5mm)の頂部から上方に発生している高さ20mmの開放青色炎中において、試験片の末端がブンゼンバーナーの頂部から10mmの高さの位置になるように、前記試験片を垂直に固定した。そして、開放青色炎中に10秒間暴露した。その後、該試験片を開放青色炎中から取り出し、該試験片が完全に消炎するまでの時間(秒)を測定した(操作1)。この操作1を、同一の試料について、2回繰返した。以上の操作を5個の試料について行い、操作1の最大燃焼時間、合計10回の測定値(離炎後、試料が完全に消炎するまでの時間)の合計値を求めた。またそれぞれの厚さの合計値も求めた。その結果を、表1、表2の難燃性の欄に示す。
(Evaluation of flame retardancy)
The flame retardancy of the cured product was evaluated according to the flame retardancy test method of UL-94 as follows. In the open blue flame with a height of 20 mm that is generated upward from the top of the Bunsen burner (inner diameter 9.5 mm), the test piece is positioned so that the end of the test piece is at a height of 10 mm from the top of the Bunsen burner. Was fixed vertically. They were then exposed for 10 seconds in an open blue flame. Thereafter, the test piece was taken out from the open blue flame, and the time (seconds) until the test piece was completely extinguished was measured (operation 1). This operation 1 was repeated twice for the same sample. The above operation was performed on five samples, and the total value of the maximum burning time of operation 1 and a total of 10 measurement values (time until the sample was completely extinguished after flame release) was obtained. The total value of each thickness was also obtained. The results are shown in the flame retardancy column of Tables 1 and 2.
Claims (3)
(B)常温常圧下で固体であり、熱重量分析装置で重量減少率50重量%を超える時の温度が300℃以上である白金錯体を白金元素量として0.1〜1000ppm、
添加してなる難燃性シリコーンゴム組成物。 (A) (a) Thermosetting poly , comprising a polyorganosiloxane base polymer in which at least two of the organic groups bonded to silicon atoms in one molecule are vinyl groups, and (b) an organic peroxide vulcanizing agent. For 100 parts by weight of the organosiloxane composition,
(B) 0.1 to 1000 ppm as a platinum element amount of platinum complex that is solid under normal temperature and normal pressure, and the temperature when the weight reduction rate exceeds 50% by weight in a thermogravimetric analyzer is 300 ° C. or more.
A flame retardant silicone rubber composition added.
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