JP4672354B2 - Room temperature curable polyorganosiloxane composition - Google Patents
Room temperature curable polyorganosiloxane composition Download PDFInfo
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- JP4672354B2 JP4672354B2 JP2004356495A JP2004356495A JP4672354B2 JP 4672354 B2 JP4672354 B2 JP 4672354B2 JP 2004356495 A JP2004356495 A JP 2004356495A JP 2004356495 A JP2004356495 A JP 2004356495A JP 4672354 B2 JP4672354 B2 JP 4672354B2
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- 239000000203 mixture Substances 0.000 title claims description 56
- -1 silane compound Chemical class 0.000 claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- 229910000077 silane Inorganic materials 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- 239000011667 zinc carbonate Substances 0.000 claims description 10
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 10
- 235000004416 zinc carbonate Nutrition 0.000 claims description 10
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 9
- 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 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 150000003058 platinum compounds Chemical class 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003431 cross linking reagent Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 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 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 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 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- KFDGIFZCOIOUIL-UHFFFAOYSA-N CCCCO[Zr](OCCCC)OCCCC Chemical compound CCCCO[Zr](OCCCC)OCCCC KFDGIFZCOIOUIL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 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
- 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
- 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- IKHOZNOYZQPPCK-UHFFFAOYSA-K aluminum;4,4-diethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)(CC)C(=O)CC([O-])=O.CCC(CC)(CC)C(=O)CC([O-])=O.CCC(CC)(CC)C(=O)CC([O-])=O IKHOZNOYZQPPCK-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- HIPFLUHRNLYKES-UHFFFAOYSA-M butan-1-olate octadecanoate zirconium(4+) Chemical compound CCCCO[Zr+](OCCCC)OCCCC.CCCCCCCCCCCCCCCCCC([O-])=O HIPFLUHRNLYKES-UHFFFAOYSA-M 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 239000013013 elastic material Substances 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-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
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XTTBHNHORSDPPN-UHFFFAOYSA-J naphthalene-1-carboxylate;tin(4+) Chemical compound [Sn+4].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 XTTBHNHORSDPPN-UHFFFAOYSA-J 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 239000003921 oil Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、室温硬化性ポリオルガノシロキサン組成物に係り、さらに詳しくは、湿気の存在しない密封条件下では安定であって、空気中の水分と接触することにより、室温で硬化してゴム状弾性体を生じる室温硬化性ポリオルガノシロキサン組成物に関する。特に、本発明は、優れた難燃性を有する室温硬化性ポリオルガノシロキサン組成物に関する。 The present invention relates to a room temperature curable polyorganosiloxane composition. More specifically, the present invention is stable under a sealing condition in the absence of moisture, and is cured at room temperature by contact with moisture in the air, thereby forming a rubbery elastic material. The present invention relates to a room temperature curable polyorganosiloxane composition that produces a body. In particular, the present invention relates to a room temperature curable polyorganosiloxane composition having excellent flame retardancy.
室温で硬化してゴム状弾性体を生成するポリオルガノシロキサン組成物の中で、空気中の水分と接触することにより硬化反応が生起するタイプの室温硬化性ポリオルガノシロキサン組成物、それらのなかでもとりわけ１成分型のものは、使用直前に本体（ベースポリマー）や架橋剤、触媒等を秤量したり、混合したりする煩雑さがなく、配合上のミスを生じることがないうえに、接着性に優れているので、電気・電子工業用の弾性接着剤やコーティング材等として、また建築用シーリング材等として、広く用いられている。 Among the polyorganosiloxane compositions that are cured at room temperature to form rubbery elastic bodies, room temperature curable polyorganosiloxane compositions of the type in which a curing reaction occurs upon contact with moisture in the air, among these, In particular, the one-component type has no troublesome weighing and mixing of the main body (base polymer), crosslinking agent, catalyst, etc. immediately before use, and does not cause mistakes in blending. Therefore, it is widely used as an elastic adhesive and coating material for the electric / electronic industry and as a sealing material for construction.
一般に、このような組成物は、分子鎖末端が水酸基で閉塞されたシラノール基末端ポリジオルガノシロキサンに、アルコキシシランのような分子中に２個を超える加水分解性基を有する架橋剤等を配合したものであり、硬化の際に、架橋剤の種類に応じて酢酸等のカルボン酸、有機アミン、アミド、有機ヒドロキシルアミン、オキシム化合物、アルコール、アセトン等を放出する。特に、接着剤、コーティング材等の目的で室温硬化性ポリオルガノシロキサン組成物を硬化させてゴム状弾性体とする場合には、脱オキシム型、脱アセトン型、脱アルコール型のものが用いられることが多い。 In general, in such a composition, a silanol group-terminated polydiorganosiloxane whose molecular chain end is blocked with a hydroxyl group is blended with a crosslinking agent having more than two hydrolyzable groups in the molecule, such as alkoxysilane. Upon curing, carboxylic acid such as acetic acid, organic amine, amide, organic hydroxylamine, oxime compound, alcohol, acetone and the like are released according to the kind of the crosslinking agent. In particular, when a room temperature curable polyorganosiloxane composition is cured into a rubbery elastic body for the purpose of an adhesive, a coating material, etc., a deoxime type, a deacetone type, or a dealcohol type should be used. There are many.
ところで、近年、電化製品をはじめあらゆる分野で、製品の安全性が重要視されており、難燃性をはじめとし耐熱性のさらなる向上が望まれている。このような状況の中で、難燃性を有するシール材およびコーティング材への要求が高まっており、難燃性を付与するための多種の材料が見出されている。すなわち、炭酸亜鉛、水酸化アルミニウム、炭酸マグネシウム、酸化チタン、二酸化ケイ素のような充填剤や白金化合物のような貴金属化合物、トリアゾール、カルボン酸アミド、塩化アンモニウム塩のような少量添加物等が、シリコーンゴムに難燃性を付与するための材料として報告されている（例えば、特許文献１参照。）。
しかしながら、前述したような室温硬化性シリコーンゴムにおいては、架橋剤や硬化触媒等の影響から未だ十分な難燃性を得るまでには至っていないのが実情である。すなわち、例えば、架橋剤として使用されているシランは揮発性が高いため、硬化物中に残存すると難燃性を低下させるという問題があった。また、硬化性が低いため、硬化時間が短いと十分な難燃性が得られない場合があった。 However, the room temperature curable silicone rubber as described above has not yet achieved sufficient flame retardancy due to the influence of a crosslinking agent, a curing catalyst and the like. That is, for example, since silane used as a cross-linking agent has high volatility, there is a problem that flame retardancy is reduced when it remains in a cured product. In addition, since the curability is low, if the curing time is short, sufficient flame retardancy may not be obtained.
本発明は、このような従来の問題を解消するためになされたもので、硬化性が良好で、従来に比べ高い難燃性を有する室温硬化性ポリオルガノシロキサン組成物を提供することを目的とする。 The present invention has been made to solve such conventional problems, and has an object to provide a room temperature curable polyorganosiloxane composition having good curability and high flame retardancy as compared with the prior art. To do.
本発明者は、前記した従来技術の問題を解決すべく鋭意研究を重ねた結果、難燃性を付与するための充填剤とともに、特定の２種のシラン化合物の部分加水分解縮合物を併用することにより、十分な難燃性を有する室温硬化性ポリオルガノシロキサン組成物が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the problems of the prior art described above, the present inventor uses a partial hydrolysis condensate of two specific silane compounds together with a filler for imparting flame retardancy. Thus, it was found that a room temperature-curable polyorganosiloxane composition having sufficient flame retardancy can be obtained, and the present invention has been completed.
すなわち、本発明は、
（Ａ）分子鎖両末端が水酸基で封鎖された２３℃における粘度が０．１〜１００Ｐａ・ｓであるポリオルガノシロキサン１００重量部に対して、
（Ｂ）難燃性付与充填剤１〜２００重量部、
（Ｃ）１分子中のＳｉ数が３〜２０であって、一般式（１）：
Ｒ１ ａＳｉ（ＯＲ２）４−ａ …（１）
（式中、Ｒ１およびＲ２は同一であっても異なっていてもよい置換または非置換の１価の炭化水素基、ａは平均値として０≦ａ≦０．２の数である。）で示されるシラン化合物の部分加水分解縮合物０．１〜１０重量部、
（Ｄ）１分子中のＳｉ数が３〜２０であって、一般式（２）：
Ｒ３ ｂＳｉ（ＯＲ４）４−ｂ …（２）
（式中、Ｒ３およびＲ４は同一であっても異なっていてもよい置換または非置換の１価の炭化水素基、ｂは平均値として０．８≦ｂ≦１．２の数である。）で示されるシラン化合物の部分加水分解縮合物０．１〜１０重量部、
（Ｅ）硬化触媒０．００１〜１０重量部、および
（Ｆ）白金化合物（白金元素として）１〜１０００ｐｐｍ
を含有することを特徴とする室温硬化性ポリオルガノシロキサン組成物である。
That is, the present invention
(A) For 100 parts by weight of a polyorganosiloxane having a viscosity of 0.1 to 100 Pa · s at 23 ° C. where both ends of the molecular chain are blocked with hydroxyl groups,
(B) 1 to 200 parts by weight of a flame retardant imparting filler,
(C) The number of Si in one molecule is 3 to 20, and the general formula (1):
R 1 a Si (OR 2 ) 4-a (1)
(In the formula, R 1 and R 2 may be the same or different substituted or unsubstituted monovalent hydrocarbon groups, and a is an average value of 0 ≦ a ≦ 0.2.) 0.1 to 10 parts by weight of a partially hydrolyzed condensate of the silane compound represented by
(D) The number of Si in one molecule is 3 to 20, and the general formula (2):
R 3 b Si (OR 4 ) 4-b (2)
Wherein R 3 and R 4 are the same or different substituted or unsubstituted monovalent hydrocarbon groups, and b is an average value of 0.8 ≦ b ≦ 1.2. .) 0.1 to 10 parts by weight of a partially hydrolyzed condensate of the silane compound represented by
(E) Curing catalyst 0.001 to 10 parts by weight, and (F) Platinum compound (as platinum element) 1 to 1000 ppm
Is a room temperature curable polyorganosiloxane composition.
本発明の室温硬化性ポリオルガノシロキサン組成物は、硬化性が良好で、かつ、配合成分が硬化物中に残存することがあっても揮発性が小さいため、十分な難燃性を備えることができる。 The room temperature curable polyorganosiloxane composition of the present invention has good curability, and even if the compounding component may remain in the cured product, the volatility is small, so that it may have sufficient flame retardancy. it can.
以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
本発明の室温硬化性ポリオルガノシロキサン組成物の（Ａ）成分であるポリオルガノシロキサンは、分子鎖両末端が水酸基で封鎖されており、代表的には、下記一般式（３）で表される実質的に直鎖状のポリオルガノシロキサンである。
式（３）中、複数のＲ５は互いに同一であっても異なっていてもよい置換または非置換の１価の炭化水素基である。Ｒ５としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基のようなアルキル基；シクロヘキシル基のようなシクロアルキル基；ビニル基、アリル基のようなアルケニル基；フェニル基、トリル基、キシリル基のようなアリール基；ベンジル基、２−フェニルエチル基、２−フェニルプロピル基のようなアラルキル基、さらにこれらの炭化水素基の水素原子の一部がハロゲン原子等の他の原子または基で置換された、例えばクロロメチル基、３−クロロプロピル基、３，３，３−トリフルオロプロピル基のようなハロゲン化アルキル基；３−シアノプロピル基のようなシアノアルキル基等の置換炭化水素基が例示される。これらのうち、合成が容易で、（Ａ）成分が分子量の割に低い粘度を有し、硬化前の組成物に良好な押出し性を与えることと、硬化後の組成物に良好な物理的性質を与えることから、全有機基の８５％以上がメチル基であることが好ましく、実質的にすべての有機基がメチル基であることがより好ましい。 In the formula (3), a plurality of R 5 are substituted or unsubstituted monovalent hydrocarbon groups which may be the same as or different from each other. R 5 includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group; cycloalkyl group such as cyclohexyl group; vinyl group, allyl group An alkenyl group such as a group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; an aralkyl group such as a benzyl group, a 2-phenylethyl group and a 2-phenylpropyl group; and a hydrogen atom of these hydrocarbon groups A halogenated alkyl group such as a chloromethyl group, a 3-chloropropyl group, or a 3,3,3-trifluoropropyl group substituted by another atom or group such as a halogen atom; Examples thereof include substituted hydrocarbon groups such as a cyanoalkyl group such as a propyl group. Among these, the synthesis is easy, the component (A) has a low viscosity for the molecular weight, gives good extrudability to the composition before curing, and good physical properties to the composition after curing. Therefore, 85% or more of all organic groups are preferably methyl groups, and substantially all organic groups are more preferably methyl groups.
一方、特に、耐熱性、耐放射線性、耐寒性または透明性を付与する場合は、Ｒ５の一部として必要量のアリール基を、耐油性、耐溶剤性を付与する場合は、Ｒ５の一部として３，３，３−トリフルオロプロピル基や３−シアノプロピル基を、また塗装適性を有する表面を付与する場合は、Ｒ５の一部として長鎖アルキル基やアラルキル基を、それぞれメチル基と併用するなど、目的に応じて任意に選択することができる。 On the other hand, in particular, when imparting heat resistance, radiation resistance, cold resistance or transparency, a necessary amount of an aryl group as a part of R 5 , and when imparting oil resistance and solvent resistance, R 5 When a 3,3,3-trifluoropropyl group or a 3-cyanopropyl group is added as a part, or a surface having paintability is imparted, a long-chain alkyl group or an aralkyl group is a methyl group as a part of R 5. It can be arbitrarily selected depending on the purpose, for example, in combination with a group.
また、（Ａ）成分であるポリオルガノシロキサンは、２３℃における粘度が０．０２〜１０００Ｐａ・ｓであり、したがって、式（３）中のｎは、（Ａ）成分の２３℃における粘度が前記範囲になる数（整数）である。（Ａ）成分の２３℃における粘度が０．０２Ｐａ・ｓ未満では、硬化後のゴム状弾性体の伸びが不十分となり、逆に１０００Ｐａ・ｓを超えると、吐出性等の作業性および流動特性が低下する。（Ａ）成分の特に好ましい粘度は、硬化前および硬化後の組成物に要求される性質を調和させることから、０．１〜１００Ｐａ・ｓの範囲である。 In addition, the polyorganosiloxane as the component (A) has a viscosity at 23 ° C. of 0.02 to 1000 Pa · s. Therefore, n in the formula (3) is the viscosity of the component (A) at 23 ° C. A number (integer) in the range. If the viscosity of the component (A) at 23 ° C. is less than 0.02 Pa · s, the rubber-like elastic body after curing is insufficiently stretched, and conversely if it exceeds 1000 Pa · s, workability such as dischargeability and flow characteristics. Decreases. The particularly preferred viscosity of the component (A) is in the range of 0.1 to 100 Pa · s because the properties required for the composition before and after curing are harmonized.
このようなポリオルガノシロキサンは、例えば、オクタメチルシロキサンのような環状ジオルガノシロキサン低量体を、水の存在下に酸性触媒またはアルカリ性触媒によって開環重合または開環共重合させることにより得ることができる。 Such a polyorganosiloxane can be obtained, for example, by ring-opening polymerization or ring-opening copolymerization of a cyclic diorganosiloxane monomer such as octamethylsiloxane with an acidic catalyst or an alkaline catalyst in the presence of water. it can.
本発明の室温硬化性ポリオルガノシロキサン組成物の（Ｂ）成分である難燃性付与充填剤は、組成物および組成物の硬化により得られるゴム状弾性体に難燃性を付与するとともに、硬化物に対して高い機械的強度を付与する。このような難燃性付与充填剤としては、例えば、炭酸亜鉛、塩基性炭酸亜鉛、水酸化アルミニウム、炭酸マグネシウム、二酸化チタン、二酸化ケイ素（石英粉）、酸化セリウムおよびその表面が処理されたもの等が挙げられる。これらは１種を単独で使用してもよく、２種以上を混合して使用してもよい。難燃性を付与する効果の点からは、なかでも炭酸亜鉛、水酸化アルミニウム等が好ましく、流動特性の観点からは、炭酸亜鉛の使用が特に好ましい。 The flame retardant imparting filler which is the component (B) of the room temperature curable polyorganosiloxane composition of the present invention imparts flame retardancy to the rubber elastic body obtained by curing the composition and the composition and cures. Gives high mechanical strength to objects. Examples of such flame retardant imparting fillers include zinc carbonate, basic zinc carbonate, aluminum hydroxide, magnesium carbonate, titanium dioxide, silicon dioxide (quartz powder), cerium oxide and those whose surface has been treated. Is mentioned. These may be used individually by 1 type, and may mix and use 2 or more types. Of these, zinc carbonate and aluminum hydroxide are preferred from the viewpoint of imparting flame retardancy, and zinc carbonate is particularly preferred from the viewpoint of flow characteristics.
この（Ｂ）成分の難燃性付与充填剤の配合量は、（Ａ）成分１００重量部に対して１〜２００重量部、より好ましくは５〜１００重量部である。１重量部未満では、難燃性が十分に付与されず、逆に２００重量部を超えると、硬化後の機械的特性や流動特性が低下する。 The blending amount of the flame retardant imparting filler of the component (B) is 1 to 200 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the component (A). If it is less than 1 part by weight, the flame retardancy is not sufficiently imparted. Conversely, if it exceeds 200 parts by weight, the mechanical properties and flow properties after curing are lowered.
本発明の室温硬化性ポリオルガノシロキサン組成物の（Ｃ）成分は、次述する（Ｄ）成分とともに、上記（Ａ）成分の架橋剤として作用する成分であり、一般式（１）：
Ｒ１ ａＳｉ（ＯＲ２）４−ａ …（１）
で示されるシラン化合物の部分加水分解縮合物である。
(C) component of the room temperature curable polyorganosiloxane composition of this invention is a component which acts as a crosslinking agent of said (A) component with (D) component described below, General formula (1):
R 1 a Si (OR 2 ) 4-a (1)
It is a partial hydrolysis-condensation product of the silane compound shown by these.
式（１）中、Ｒ１およびＲ２は互いに同一であっても異なっていてもよい置換または非置換の１価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、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基のようなアルキル基；シクロヘキシル基のようなシクロアルキル基；ビニル基、アリル基のようなアルケニル基；フェニル基、トリル基、キシリル基のようなアリール基；ベンジル基、２−フェニルエチル基、２−フェニルプロピル基のようなアラルキル基、さらにこれらの炭化水素基の水素原子の一部がハロゲン原子等の他の原子または基で置換された、例えばクロロメチル基、３−クロロプロピル基、３，３，３−トリフルオロプロピル基のようなハロゲン化アルキル基；３−シアノプロピル基のようなシアノアルキル基等の置換炭化水素基が例示される。また、ａは平均値として０≦ａ≦０．２の数であり、好ましくは０≦ａ≦０．１の数である。 In the formula (1), R 1 and R 2 are substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different from each other, and are methyl group, ethyl group, propyl group, butyl group, pentyl Group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group; cycloalkyl group such as cyclohexyl group; alkenyl group such as vinyl group, allyl group; phenyl group, tolyl group, xylyl group, etc. An aryl group; an aralkyl group such as a benzyl group, a 2-phenylethyl group, and a 2-phenylpropyl group, and a part of hydrogen atoms of these hydrocarbon groups is substituted with another atom or group such as a halogen atom, For example, a halogenated alkyl group such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group; Substituted hydrocarbon groups such as Noarukiru groups. Further, a is an average value of 0 ≦ a ≦ 0.2, and preferably 0 ≦ a ≦ 0.1.
この（Ｃ）成分の部分加水分解縮合物は、１分子中のＳｉ数が３〜２０であることが好ましく、４〜１５であるとより好ましい。Ｓｉ数が３未満では、十分な難燃性が得られず、また、２０を超えると、硬化性や硬化後の機械的特性が低下する。 In the partially hydrolyzed condensate of component (C), the number of Si in one molecule is preferably 3-20, and more preferably 4-15. When the number of Si is less than 3, sufficient flame retardancy cannot be obtained, and when it exceeds 20, curability and mechanical properties after curing are deteriorated.
（Ｃ）成分のシラン化合物の部分加水分解縮合物は、１種を単独で使用してもよく、２種以上を混合して使用してもよい。 (C) The partial hydrolysis-condensation product of the silane compound of a component may be used individually by 1 type, and 2 or more types may be mixed and used for it.
（Ｃ）成分の配合量は、（Ａ）成分１００重量部に対して０．１〜１０重量部であり、０．１重量部未満では、架橋が十分に行われず、硬度の低い硬化物しか得られないばかりでなく、架橋剤を配合した組成物の保存安定性が不良となる。逆に、１０重量部を超えると、硬化の際の収縮率が大きくなり、硬化後の弾性等の物性が低下する。さらに、硬化性の観点から、（Ｃ）成分の配合量は、（Ａ）成分であるポリオルガノシロキサンの水酸基１モルに対し、（Ｃ）成分中のＯＲ２基が２〜１５モルとなる範囲が好ましく、３〜１０モルとなる範囲がより好ましい。 Component (C) is blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of component (A). Not only can it be obtained, but the storage stability of the composition containing the crosslinking agent becomes poor. On the contrary, if it exceeds 10 parts by weight, the shrinkage rate at the time of curing increases, and the physical properties such as elasticity after curing decrease. Furthermore, from the viewpoint of curability, the blending amount of the component (C) is such that the OR 2 group in the component (C) is 2 to 15 moles with respect to 1 mole of the hydroxyl group of the polyorganosiloxane that is the component (A). Is preferable, and a range of 3 to 10 mol is more preferable.
本発明の室温硬化性ポリオルガノシロキサン組成物の（Ｄ）成分は、一般式（２）：
Ｒ３ ｂＳｉ（ＯＲ４）４−ｂ …（２）
で示されるシラン化合物の部分加水分解縮合物である。
The component (D) of the room temperature curable polyorganosiloxane composition of the present invention has the general formula (2):
R 3 b Si (OR 4 ) 4-b (2)
It is a partial hydrolysis-condensation product of the silane compound shown by these.
式（２）中、Ｒ３およびＲ４は互いに同一であっても異なっていてもよい置換または非置換の１価の炭化水素基であり、前記した（Ｃ）成分のＲ１およびＲ２と同様の基が例示される。また、ｂは平均値として０．８≦ｂ≦１．２の数であり、好ましくは０．９≦ｂ≦１．１の数である。 In the formula (2), R 3 and R 4 are substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different from each other, and R 1 and R 2 of the component (C) described above Similar groups are exemplified. Further, b is an average value of 0.8 ≦ b ≦ 1.2, and preferably 0.9 ≦ b ≦ 1.1.
この（Ｄ）成分の部分加水分解縮合物は、１分子中のＳｉ数が３〜２０であることが好ましく、４〜１５であるとより好ましい。Ｓｉ数が３未満では、十分な難燃性が得られず、また、２０を超えると、硬化性や硬化後の機械的特性が低下する。 In the partially hydrolyzed condensate of component (D), the number of Si in one molecule is preferably 3-20, and more preferably 4-15. When the number of Si is less than 3, sufficient flame retardancy cannot be obtained, and when it exceeds 20, curability and mechanical properties after curing are deteriorated.
（Ｄ）成分のシラン化合物の部分加水分解縮合物は、１種を単独で使用してもよく、２種以上を混合して使用してもよい。 (D) The partial hydrolysis-condensation product of the silane compound of a component may be used individually by 1 type, and 2 or more types may be mixed and used for it.
（Ｄ）成分の配合量は、（Ａ）成分１００重量部に対して０．１〜１０重量部であり、０．１重量部未満では、架橋が十分に行われず、硬度の低い硬化物しか得られない。逆に、１０重量部を超えると、硬化の際の収縮率が大きくなり、硬化後の弾性等の物性が低下する。さらに、硬化性の観点から、（Ｄ）成分の配合量は、（Ｃ）成分中のＯＲ２基１モルに対し、（Ｄ）成分中のＯＲ４基が０．１〜５モルとなる範囲が好ましく、０．２〜３モルとなる範囲がより好ましい。 The blending amount of component (D) is 0.1 to 10 parts by weight with respect to 100 parts by weight of component (A). I can't get it. On the contrary, if it exceeds 10 parts by weight, the shrinkage rate at the time of curing increases, and the physical properties such as elasticity after curing decrease. Further, from the viewpoint of curability, the blending amount of the component (D) is such that the OR 4 group in the component (D) is 0.1 to 5 mol with respect to 1 mol of the OR 2 group in the component (C). Is preferable, and a range of 0.2 to 3 mol is more preferable.
上記のような（Ｃ）成分および（Ｄ）成分を架橋剤として使用することにより、組成物の硬化性を高めることができるとともに、（Ｃ）成分および（Ｄ）成分自体、揮発性が非常に小さいために、硬化物中に残留することがあっても、組成物の難燃性を低下させることはなく、組成物の難燃性を十分に発現させることができる。 By using the components (C) and (D) as a crosslinking agent as described above, the curability of the composition can be improved, and the (C) component and the (D) component itself are very volatile. Since it is small, even if it remains in the cured product, the flame retardancy of the composition is not lowered, and the flame retardancy of the composition can be sufficiently exhibited.
本発明の室温硬化性ポリオルガノシロキサン組成物の（Ｅ）成分である硬化触媒は、（Ａ）成分の水酸基と（Ｃ）成分および（Ｄ）成分の加水分解性基、すなわち、ＯＲ２基およびＯＲ４基との縮合反応を促進する触媒である。このような（Ｅ）成分としては、鉄オクトエート、マンガンオクトエート、亜鉛オクトエート、スズナフテート、スズカプリレート、スズオレートのようなカルボン酸金属塩；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サイド、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；テトラエトキシチタン、テトラプロポキシチタン、テトラブトキシチタン、１、３−プロポキシチタンビス（エチルアセチルアセテート）のようなアルコキシチタン類；アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、ジイソプロポキシアルミニウムエチルアセトアセテート、トリエトキシアルミニウムのような有機アルミニウム；ジルコニウムテトラアセチルアセトナート、テトライソプロポキシジルコニウム、テトラブトキシジルコニウム、トリブトキシジルコニウムアセチルアセトネート、トリブトキシジルコニウムステアレートのような有機ジルコニウム化合物等が例示される。これらは１種を単独で使用してもよく、２種以上を混合して使用してもよい。微量の存在で大きな触媒能を持つことから、なかでも、有機スズ化合物、アルコキシチタン類が好ましく、特に有機スズ化合物が好ましい。 The curing catalyst which is the component (E) of the room temperature curable polyorganosiloxane composition of the present invention is a hydroxyl group of the component (A), a hydrolyzable group of the component (C) and (D), that is, an OR 2 group and It is a catalyst that promotes the condensation reaction with the OR 4 group. Examples of the component (E) include iron octoate, manganese octoate, zinc octoate, tin naphthate, tin caprylate, tin oleate, carboxylic acid metal salts; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate Organic tin compounds such as diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dioctyltin dilaurate; tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, 1,3-propoxytitaniumbis ( Alkoxytitanium such as ethyl acetylacetate; aluminum trisacetylacetonate, aluminum trisethylacetoacetate, dii Organic aluminum compounds such as propoxyaluminum ethyl acetoacetate and triethoxyaluminum; organic zirconium compounds such as zirconium tetraacetylacetonate, tetraisopropoxyzirconium, tetrabutoxyzirconium, tributoxyzirconium acetylacetonate, tributoxyzirconium stearate, etc. Illustrated. These may be used individually by 1 type, and may mix and use 2 or more types. Of these, organotin compounds and alkoxytitanium compounds are preferred, and organotin compounds are particularly preferred since they have a large catalytic ability in the presence of a trace amount.
この（Ｅ）成分の硬化触媒の配合量は、（Ａ）成分１００重量部に対して０．００１〜１０重量部、好ましくは０．０１〜５重量部である。０．００１重量部未満では、硬化触媒として十分に作用せず、硬化に長い時間がかかるばかりでなく、特に空気との接触面から遠いゴム層の深部における硬化が不十分となる。逆に１０重量部を超えると、その配合量に見合う効果がなく、無意味であるばかりか非経済的である。 The amount of the curing catalyst of component (E) is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of component (A). If it is less than 0.001 part by weight, it does not act sufficiently as a curing catalyst, and not only takes a long time for curing, but also the curing in the deep part of the rubber layer far from the contact surface with air becomes insufficient. On the other hand, if it exceeds 10 parts by weight, there is no effect commensurate with the blending amount, which is meaningless and uneconomical.
本発明の室温硬化性ポリオルガノシロキサン組成物の（Ｆ）成分である白金化合物は、組成物および組成物の硬化により得られるゴム状弾性体の難燃性をさらに向上させる。このような白金化合物としては、例えば、塩化白金酸、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、白金とニトリル化合物との錯体、リン酸もしくは亜リン酸化合物と白金との錯体等が例示される。これらの白金化合物は、１種を単独で使用してもよく、２種以上混合して使用してもよい。 The platinum compound which is the component (F) of the room temperature curable polyorganosiloxane composition of the present invention further improves the flame retardancy of the rubber elastic body obtained by curing the composition and the composition. Examples of such platinum compounds include chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of platinum and olefins, complexes of platinum and ketones, complexes of platinum and vinylsiloxane, and complexes of platinum and nitrile compounds. And a complex of phosphoric acid or phosphorous acid compound and platinum. These platinum compounds may be used individually by 1 type, and may be used in mixture of 2 or more types.
この（Ｆ）成分の白金化合物の配合量は、白金元素として（Ａ）成分１００重量部に対して１〜１０００ｐｐｍ、より好ましくは５〜１００ｐｐｍである。１ｐｐｍ未満では、難燃性を十分に向上させることができず、逆に１０００ｐｐｍを超えると、これ以上の効果が得られないばかりでなく不経済である。 The compounding amount of the platinum compound of component (F) is 1 to 1000 ppm, more preferably 5 to 100 ppm as platinum element with respect to 100 parts by weight of component (A). If it is less than 1 ppm, the flame retardancy cannot be sufficiently improved. Conversely, if it exceeds 1000 ppm, not only the effect can be obtained but also it is uneconomical.
本発明の室温硬化性ポリオルガノシロキサン組成物には、以上の各成分の他、本発明の効果を阻害しない範囲で、この種の組成物に一般に配合されている、乾式シリカ、湿式シリカ、石英粉末等の無機充填剤、顔料、チクソトロピー性付与剤、押出作業性を改良するための粘度調整剤、紫外線吸収剤、防かび剤、耐熱性向上剤、接着向上剤等の各種添加剤を、必要に応じて配合することができる。 The room temperature curable polyorganosiloxane composition of the present invention includes dry silica, wet silica, quartz, which are generally blended in this type of composition in addition to the above components, as long as the effects of the present invention are not impaired. Necessary various additives such as inorganic fillers such as powder, pigments, thixotropy imparting agents, viscosity modifiers to improve extrusion workability, UV absorbers, fungicides, heat resistance improvers, adhesion improvers, etc. It can be blended according to.
本発明の室温硬化性ポリオルガノシロキサン組成物は、上記（Ａ）〜（Ｆ）成分および必要に応じて配合される各種成分を、湿気を遮断した状態で混合することにより得られる。得られた組成物は、密閉容器中でそのまま保存し、使用時に空気中の水分に曝すことによってはじめて硬化する、いわゆる１包装型室温硬化性組成物として使用することができる。また、本発明の組成物を、例えば架橋剤と硬化触媒を分けた組成物として調製し、適宜２〜３個の別々の容器に分けて保存し、使用時にこれらを混合する、いわゆる多包装型室温硬化性組成物として使用することもできる。 The room temperature curable polyorganosiloxane composition of the present invention can be obtained by mixing the above components (A) to (F) and various components blended as necessary in a state where moisture is blocked. The obtained composition can be used as a so-called one-packaging room temperature curable composition that is stored as it is in a closed container and cured only by exposure to moisture in the air during use. In addition, the composition of the present invention is prepared as a composition in which, for example, a crosslinking agent and a curing catalyst are separated, and is stored in two or three separate containers as appropriate, and these are mixed at the time of use. It can also be used as a room temperature curable composition.
本発明により得られる室温硬化性ポリオルガノシロキサン組成物は、湿気の存在しない密封条件下では安定であり、空気中の水分と接触することにより、室温で硬化してゴム状弾性体を生じる。特に本発明によれば、従来品より優れた難燃性を有する室温硬化性ポリオルガノシロキサン組成物を得ることができる。 The room temperature curable polyorganosiloxane composition obtained according to the present invention is stable under sealed conditions where moisture is not present, and is cured at room temperature upon contact with moisture in the air to produce a rubber-like elastic body. In particular, according to the present invention, a room temperature-curable polyorganosiloxane composition having flame retardancy superior to that of conventional products can be obtained.
以下、本発明を実施例によりさらに具体的に説明するが、これらの実施例は本発明の範囲を何ら限定するものではない。なお、実施例中、「部」とあるのはいずれも「重量部」を表し、粘度等の物性値は全て２３℃、相対湿度５０％での値を示す。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the scope of the present invention. In the examples, “part” means “part by weight”, and all physical properties such as viscosity are values at 23 ° C. and relative humidity 50%.
実施例１
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン（粘度：１Ｐａ・ｓ、水酸基量０．０８ｍｍｏｌ／ｇ）１００部に、炭酸亜鉛５０部、塩化白金酸（白金元素として）５０ｐｐｍ、ジ−ｎ−ブチルスズジラウレート０．１部、式：Ｓｉ（ＯＣ２Ｈ５）４で示されるシランの部分加水分解縮合物（Ｓｉ数５）４部および式：ＣＨ３Ｓｉ（ＯＣ２Ｈ５）３で示されるシランの部分加水分解縮合物（Ｓｉ数５）６部を添加し、湿気遮断下で均一に混合し、ポリオルガノシロキサン組成物を得た。
Example 1
100 parts of polydimethylsiloxane (viscosity: 1 Pa · s, hydroxyl amount 0.08 mmol / g) blocked at both ends of the molecular chain with hydroxyl groups, 50 parts of zinc carbonate, 50 ppm of chloroplatinic acid (as platinum element), di-n -0.1 part of butyltin dilaurate, 4 parts of partially hydrolyzed condensate (Si number 5) of silane represented by formula: Si (OC 2 H 5 ) 4 and represented by formula: CH 3 Si (OC 2 H 5 ) 3 6 parts of a partially hydrolyzed silane condensate (Si number 5) was added and mixed uniformly while blocking moisture to obtain a polyorganosiloxane composition.
実施例２
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン（粘度：１Ｐａ・ｓ、水酸基量０．０８ｍｍｏｌ／ｇ）１００部に、炭酸亜鉛５０部、塩化白金酸（白金元素として）５０ｐｐｍ、ジ−ｎ−ブチルスズジラウレート０．１部、式：Ｓｉ（ＯＣ２Ｈ５）４で示されるシランの部分加水分解縮合物（Ｓｉ数７）６部および式：ＣＨ３Ｓｉ（ＯＣ２Ｈ５）３で示されるシランの部分加水分解縮合物（Ｓｉ数８）３部を添加し、湿気遮断下で均一に混合し、ポリオルガノシロキサン組成物を得た。
Example 2
100 parts of polydimethylsiloxane (viscosity: 1 Pa · s, hydroxyl amount 0.08 mmol / g) blocked at both ends of the molecular chain with hydroxyl groups, 50 parts of zinc carbonate, 50 ppm of chloroplatinic acid (as platinum element), di-n -0.1 part of butyltin dilaurate, 6 parts of partially hydrolyzed condensate (Si number 7) of silane represented by formula: Si (OC 2 H 5 ) 4 and represented by formula: CH 3 Si (OC 2 H 5 ) 3 3 parts of a partially hydrolyzed silane condensate (Si number 8) was added and mixed uniformly while blocking moisture to obtain a polyorganosiloxane composition.
比較例１
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン（粘度：１Ｐａ・ｓ、水酸基量０．０８ｍｍｏｌ／ｇ）１００部に、炭酸亜鉛５０部、塩化白金酸（白金元素として）５０ｐｐｍ、ジ−ｎ−ブチルスズジラウレート０．１部、式：Ｓｉ（ＯＣ２Ｈ５）４で示されるシラン６部および式：ＣＨ３Ｓｉ（ＯＣ２Ｈ５）３で示されるシラン３部を添加し、湿気遮断下で均一に混合し、ポリオルガノシロキサン組成物を得た。
Comparative Example 1
100 parts of polydimethylsiloxane (viscosity: 1 Pa · s, hydroxyl amount 0.08 mmol / g) blocked at both ends of the molecular chain with hydroxyl groups, 50 parts of zinc carbonate, 50 ppm of chloroplatinic acid (as platinum element), di-n -0.1 part of butyltin dilaurate, 6 parts of silane represented by the formula: Si (OC 2 H 5 ) 4 and 3 parts of silane represented by the formula: CH 3 Si (OC 2 H 5 ) 3 were added, and moisture was blocked. To obtain a polyorganosiloxane composition.
比較例２
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン（粘度：１Ｐａ・ｓ、水酸基量０．０８ｍｍｏｌ／ｇ）１００部に、炭酸亜鉛５０部、塩化白金酸（白金元素として）５０ｐｐｍ、ジ−ｎ−ブチルスズジラウレート０．１部、式：Ｓｉ（ＯＣ２Ｈ５）４で示されるシランの部分加水分解縮合物（Ｓｉ数５）４部および式：ＣＨ３Ｓｉ（ＯＣ２Ｈ５）３で示されるシラン６部を添加し、湿気遮断下で均一に混合し、ポリオルガノシロキサン組成物を得た。
Comparative Example 2
100 parts of polydimethylsiloxane (viscosity: 1 Pa · s, hydroxyl amount 0.08 mmol / g) blocked at both ends of the molecular chain with hydroxyl groups, 50 parts of zinc carbonate, 50 ppm of chloroplatinic acid (as platinum element), di-n -0.1 part of butyltin dilaurate, 4 parts of partially hydrolyzed condensate (Si number 5) of silane represented by formula: Si (OC 2 H 5 ) 4 and represented by formula: CH 3 Si (OC 2 H 5 ) 3 6 parts of silane to be added was added and mixed uniformly under moisture blocking to obtain a polyorganosiloxane composition.
比較例３
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン（粘度：１Ｐａ・ｓ、水酸基量０．０８ｍｍｏｌ／ｇ）１００部に、炭酸亜鉛５０部、塩化白金酸（白金元素として）５０ｐｐｍ、ジ−ｎ−ブチルスズジラウレート０．１部および式：Ｓｉ（ＯＣ２Ｈ５）４で示されるシランの部分加水分解縮合物（Ｓｉ数５）１０部を添加し、湿気遮断下で均一に混合し、ポリオルガノシロキサン組成物を得た。
Comparative Example 3
100 parts of polydimethylsiloxane (viscosity: 1 Pa · s, hydroxyl amount 0.08 mmol / g) blocked at both ends of the molecular chain with hydroxyl groups, 50 parts of zinc carbonate, 50 ppm of chloroplatinic acid (as platinum element), di-n -0.1 part of butyltin dilaurate and 10 parts of a partially hydrolyzed condensate of silane represented by the formula: Si (OC 2 H 5 ) 4 (Si number 5) are added and mixed uniformly under moisture blocking, A siloxane composition was obtained.
上記各実施例および各比較例で調製し密封して保存したポリオルガノシロキサン組成物について、下記に示す方法で各種特性を評価した。結果を表１に示す。
［硬化性］
２３℃、５０％ＲＨの雰囲気下、組成物を金型に厚さ６ｍｍに流し込み、２時間、４時間および８時間後の性状（硬化状態）を調べた。
［難燃性］
組成物を金型に流し込み、２３℃、５０％ＲＨの雰囲気中に３日間放置して厚さ２ｍｍの硬化物を得、ＵＬ９４Ｖに基づく燃焼試験を行った。
Various characteristics of the polyorganosiloxane compositions prepared and sealed in the above Examples and Comparative Examples were evaluated by the methods described below. The results are shown in Table 1.
[Curing property]
Under an atmosphere of 23 ° C. and 50% RH, the composition was poured into a mold to a thickness of 6 mm, and properties (cured state) after 2 hours, 4 hours and 8 hours were examined.
[Flame retardance]
The composition was poured into a mold, left in an atmosphere of 23 ° C. and 50% RH for 3 days to obtain a cured product having a thickness of 2 mm, and a combustion test based on UL94V was performed.
表１から明らかなように、実施例１および２で調製されたポリオルガノシロキサン組成物は、比較例１〜３で得られたポリオルガノシロキサン組成物に比べ、硬化性に優れるとともに、高い難燃性を有している。 As is apparent from Table 1, the polyorganosiloxane compositions prepared in Examples 1 and 2 have excellent curability and high flame retardancy as compared with the polyorganosiloxane compositions obtained in Comparative Examples 1 to 3. It has sex.
Claims (4)
（Ｂ）難燃性付与充填剤１〜２００重量部、
（Ｃ）１分子中のＳｉ数が３〜２０であって、一般式（１）：
Ｒ１ ａＳｉ（ＯＲ２）４−ａ …（１）
（式中、Ｒ１およびＲ２は同一であっても異なっていてもよい置換または非置換の１価の炭化水素基、ａは平均値として０≦ａ≦０．２の数である。）で示されるシラン化合物の部分加水分解縮合物０．１〜１０重量部、
（Ｄ）１分子中のＳｉ数が３〜２０であって、一般式（２）：
Ｒ３ ｂＳｉ（ＯＲ４）４−ｂ …（２）
（式中、Ｒ３およびＲ４は同一であっても異なっていてもよい置換または非置換の１価の炭化水素基、ｂは平均値として０．８≦ｂ≦１．２の数である。）で示されるシラン化合物の部分加水分解縮合物０．１〜１０重量部、
（Ｅ）硬化触媒０．００１〜１０重量部、および
（Ｆ）白金化合物（白金元素として）１〜１０００ｐｐｍ
を含有することを特徴とする室温硬化性ポリオルガノシロキサン組成物。 (A) For 100 parts by weight of a polyorganosiloxane having a viscosity of 0.1 to 100 Pa · s at 23 ° C. where both ends of the molecular chain are blocked with hydroxyl groups,
(B) 1 to 200 parts by weight of a flame retardant imparting filler,
(C) The number of Si in one molecule is 3 to 20, and the general formula (1):
R 1 a Si (OR 2 ) 4-a (1)
(In the formula, R 1 and R 2 may be the same or different substituted or unsubstituted monovalent hydrocarbon groups, and a is an average value of 0 ≦ a ≦ 0.2.) 0.1 to 10 parts by weight of a partially hydrolyzed condensate of the silane compound represented by
(D) The number of Si in one molecule is 3 to 20, and the general formula (2):
R 3 b Si (OR 4 ) 4-b (2)
Wherein R 3 and R 4 are the same or different substituted or unsubstituted monovalent hydrocarbon groups, and b is an average value of 0.8 ≦ b ≦ 1.2. .) 0.1 to 10 parts by weight of a partially hydrolyzed condensate of the silane compound represented by
(E) Curing catalyst 0.001 to 10 parts by weight, and (F) Platinum compound (as platinum element) 1 to 1000 ppm
A room temperature-curable polyorganosiloxane composition comprising:
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| JP2007321122A (en) * | 2006-06-05 | 2007-12-13 | Shin Etsu Chem Co Ltd | Room temperature-curable organopolysiloxane composition |
| KR101357530B1 (en) * | 2007-12-19 | 2014-01-29 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | Room-temperature-curable polyorganosiloxane composition |
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| JP5888779B2 (en) * | 2012-03-29 | 2016-03-22 | 日本タングステン株式会社 | Method for producing light reflecting coating film |
| JP7372033B2 (en) * | 2018-12-10 | 2023-10-31 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Room temperature curable polyorganosiloxane composition, cured product and laminate thereof |
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| JPH07133430A (en) * | 1993-11-09 | 1995-05-23 | Toshiba Silicone Co Ltd | Cold-setting polyorganosiloxane composition |
| JPH0940869A (en) * | 1995-07-31 | 1997-02-10 | Toray Dow Corning Silicone Co Ltd | Curable silicon composition |
| JP2000129130A (en) * | 1998-07-13 | 2000-05-09 | Shin Etsu Chem Co Ltd | Production of room temperature-curable organopolysiloxane composition |
| JP2003012925A (en) * | 2001-06-26 | 2003-01-15 | Ge Toshiba Silicones Co Ltd | Heat-conductive silicone rubber composition and heater roll prepared therefrom |
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| JP2004315561A (en) * | 2003-04-11 | 2004-11-11 | Shin Etsu Chem Co Ltd | Room temperature curing silicone rubber composition |
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