JP2023130798A - Addition-curable silicone composition, and flame-retardant silicone rubber - Google Patents
Addition-curable silicone composition, and flame-retardant silicone rubber Download PDFInfo
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- JP2023130798A JP2023130798A JP2022035297A JP2022035297A JP2023130798A JP 2023130798 A JP2023130798 A JP 2023130798A JP 2022035297 A JP2022035297 A JP 2022035297A JP 2022035297 A JP2022035297 A JP 2022035297A JP 2023130798 A JP2023130798 A JP 2023130798A
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 29
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 26
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 5
- 239000003063 flame retardant Substances 0.000 title claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- -1 triazole compound Chemical class 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 238000007259 addition reaction Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 17
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000013006 addition curing Methods 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 10
- 238000004438 BET method Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 abstract description 17
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 229910020485 SiO4/2 Inorganic materials 0.000 abstract 2
- 239000003431 cross linking reagent Substances 0.000 description 25
- 238000005259 measurement Methods 0.000 description 24
- 239000004205 dimethyl polysiloxane Substances 0.000 description 23
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 3
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 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 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 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 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IQSBKDJPSOMMRZ-UHFFFAOYSA-N ethenyl(methyl)silane Chemical compound C[SiH2]C=C IQSBKDJPSOMMRZ-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl 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])C([H])([H])[H] 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000000286 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
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
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- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 1
- QEASJVYPHMYPJM-UHFFFAOYSA-N 1,2-dihydrotriazol-5-one Chemical compound OC1=CNN=N1 QEASJVYPHMYPJM-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- WSPOQKCOERDWJQ-UHFFFAOYSA-N 2-methyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 WSPOQKCOERDWJQ-UHFFFAOYSA-N 0.000 description 1
- MOLKLIYWXFEEJM-UHFFFAOYSA-N 2h-triazole-4-carbaldehyde Chemical compound O=CC1=CNN=N1 MOLKLIYWXFEEJM-UHFFFAOYSA-N 0.000 description 1
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- QYXVDGZUXHFXTO-UHFFFAOYSA-L 3-oxobutanoate;platinum(2+) Chemical compound [Pt+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O QYXVDGZUXHFXTO-UHFFFAOYSA-L 0.000 description 1
- FJRZOOICEHBAED-UHFFFAOYSA-N 5-methyl-1h-1,2,4-triazol-3-amine Chemical compound CC1=NNC(N)=N1 FJRZOOICEHBAED-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
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Abstract
Description
本発明は、液状の付加硬化型シリコーン組成物、及び該組成物を硬化して成る難燃性シリコーンゴムに関する。 The present invention relates to a liquid addition-curing silicone composition and a flame-retardant silicone rubber obtained by curing the composition.
難燃性シリコーンゴムは、電気・電子部品、自動車部品、建材部品などに使用されている。シリコーンゴムに難燃性を付与するには、白金又は白金化合物の配合が不可欠であるが、白金又は白金化合物だけでは十分ではない。特許文献１には、液状シリコーンゴム組成物に、水酸化アルミニウム粉末と炭酸亜鉛粉末を配合することで、難燃性に優れたシリコーンゴム成形品を与えることが記載されている。また、特許文献２には、カーボンブラックと水酸化アルミニウムを含有する液状シリコーンゴム組成物が、難燃性を有するシリコーンゴムを与えることが記載されている。しかしながら、液状シリコーンゴム組成物に、水酸化アルミニウム、炭酸亜鉛等の塩基性無機フィラーを配合すると、材料の密度が上昇し、ゴム物性が低下する問題があった。 Flame-retardant silicone rubber is used in electrical and electronic parts, automobile parts, building material parts, etc. In order to impart flame retardancy to silicone rubber, it is essential to incorporate platinum or a platinum compound, but platinum or a platinum compound alone is not sufficient. Patent Document 1 describes that a silicone rubber molded article with excellent flame retardancy can be obtained by blending aluminum hydroxide powder and zinc carbonate powder into a liquid silicone rubber composition. Further, Patent Document 2 describes that a liquid silicone rubber composition containing carbon black and aluminum hydroxide provides a silicone rubber having flame retardancy. However, when a basic inorganic filler such as aluminum hydroxide or zinc carbonate is added to a liquid silicone rubber composition, there is a problem that the density of the material increases and the physical properties of the rubber deteriorate.
特許文献３には、液状付加硬化型シリコーンゴム組成物に酸化鉄微粉末を配合し、オルガノハイドロジェンポリシロキサンの加熱減量を制御して難燃性を向上する方法が記載されている。しかし、酸化鉄微粉末は比重が高いため、経時で沈降する問題があった。特許文献４と特許文献５には、シリコーンゴム組成物にトリアゾール化合物と亜リン酸エステルを配合することで、難燃性が高いシリコーンゴムを与えることが記載されている。しかし、これらのシリコーンゴム組成物では未だ十分な難燃性は得られていない。 Patent Document 3 describes a method for improving flame retardancy by blending iron oxide fine powder into a liquid addition-curing silicone rubber composition to control the heat loss of organohydrogenpolysiloxane. However, since iron oxide fine powder has a high specific gravity, it has a problem of settling over time. Patent Document 4 and Patent Document 5 describe that a silicone rubber with high flame retardancy can be obtained by blending a triazole compound and a phosphite ester into a silicone rubber composition. However, these silicone rubber compositions have not yet achieved sufficient flame retardancy.
本発明は、上記問題に鑑みてなされたもので、優れた難燃性やゴム強度を有するシリコーンゴム硬化物を与える液状付加硬化型シリコーン組成物を提供することを目的とする。 The present invention was made in view of the above problems, and an object of the present invention is to provide a liquid addition-curable silicone composition that provides a cured silicone rubber product having excellent flame retardancy and rubber strength.
本発明者らは、上記目的を達成するために、液状付加硬化型シリコーン組成物において、架橋剤（硬化剤）であるオルガノハイドロジェンポリシロキサンの構造を特定した。さらに、前記組成物中のケイ素原子結合アルケニル基の総モル数に対して、ヒドロシリル基のモル数の比を、ある限られた範囲に限定した。そうすることにより、得られるシリコーンゴムは、優れた難燃性を安定して有することができ、且つ、良好なゴム強度を有することを見出し、本発明を完成させた。 In order to achieve the above object, the present inventors specified the structure of organohydrogenpolysiloxane, which is a crosslinking agent (curing agent), in a liquid addition-curing silicone composition. Furthermore, the ratio of the number of moles of hydrosilyl groups to the total number of moles of silicon-bonded alkenyl groups in the composition was limited to a certain limited range. It was discovered that by doing so, the obtained silicone rubber can stably have excellent flame retardancy and also have good rubber strength, and the present invention was completed.
即ち、本発明は、（Ａ）ケイ素原子と結合するアルケニル基を１分子中に２個以上有する、２３℃で液状のオルガノポリシロキサン：１００質量部、
（Ｂ）Ｒ１
３ＳｉＯ１／２単位（式中、Ｒ１は互いに独立に１価炭化水素基である）とＳｉＯ４／２単位を含有し、ＳｉＯ４／２単位に対するＲ１
３ＳｉＯ１／２単位のモル比［Ｒ１
３ＳｉＯ１／２／ＳｉＯ４／２］が０．５～１．５であり、アルケニル基含有量が１×１０－４～５×１０－３ｍｏｌ／ｇである三次元網状構造のオルガノポリシロキサンレジン：３～５０質量部
（Ｃ）下記式（１）で示される直鎖状のオルガノハイドロジェンポリシロキサン
：前記（Ａ）成分及び（Ｂ）成分中のケイ素原子結合アルケニル基の総数に対して（Ｃ）成分中のケイ素原子結合水素原子の個数の比が１．５～１．７となる量
（Ｄ）付加反応触媒：触媒量
（Ｅ）ＢＥＴ法による比表面積１００ｍ２／ｇ以上のヒュームドシリカ：１０～５０質量部、及び
（Ｆ）トリアゾール化合物：０．００１～０．５質量部
を含有する、付加硬化型シリコーン組成物を提供する。
That is, the present invention provides (A) 100 parts by mass of an organopolysiloxane that is liquid at 23°C and has two or more alkenyl groups in one molecule that bond to a silicon atom;
(B) Contains R 1 3 SiO 1/2 units (in the formula, R 1 is a monovalent hydrocarbon group independently of each other) and SiO 4/2 units, and R 1 3 SiO 1 to SiO 4/2 units /2 unit molar ratio [R 1 3 SiO 1/2 /SiO 4/2 ] is 0.5 to 1.5, and the alkenyl group content is 1×10 −4 to 5×10 −3 mol/g. Organopolysiloxane resin with a three-dimensional network structure: 3 to 50 parts by mass (C) A linear organohydrogenpolysiloxane represented by the following formula (1)
: An amount such that the ratio of the number of silicon-bonded hydrogen atoms in component (C) to the total number of silicon-bonded alkenyl groups in components (A) and (B) is 1.5 to 1.7. D) Addition reaction catalyst: catalyst amount
(E) An addition-curing silicone composition containing 10 to 50 parts by mass of fumed silica having a specific surface area of 100 m 2 /g or more by BET method, and (F) 0.001 to 0.5 parts by mass of a triazole compound. I will provide a.
本発明のシリコーン組成物は、優れた難燃性及びゴム強度を有する難燃性シリコーンゴムを提供することができる。 The silicone composition of the present invention can provide a flame-retardant silicone rubber having excellent flame retardancy and rubber strength.
以下、本発明について更に詳しく説明する。 The present invention will be explained in more detail below.
－（Ａ）アルケニル基含有オルガノポリシロキサン－
本発明の（Ａ）成分は、１分子中に２個以上のケイ素原子結合アルケニル基を有する、２３℃で液状のオルガノポリシロキサンである。前記（Ａ）成分の粘度は、ＪＩＳ Ｋ７１１７－１：１９９９記載の回転粘度計で測定した２３℃で１～１００Ｐａ・ｓの範囲であるのが好ましい。より好ましくは、５～１００Ｐａ・ｓ、更に好ましくは１０～１００Ｐａ・ｓである。
-(A) Alkenyl group-containing organopolysiloxane-
Component (A) of the present invention is an organopolysiloxane that is liquid at 23° C. and has two or more silicon-bonded alkenyl groups in one molecule. The viscosity of the component (A) is preferably in the range of 1 to 100 Pa·s at 23°C as measured with a rotational viscometer as described in JIS K7117-1:1999. More preferably, it is 5 to 100 Pa·s, and still more preferably 10 to 100 Pa·s.
該アルケニル基含有オルガノポリシロキサンとしては、通常、下記平均組成式（２）で示されるものが好適に使用される。
ＲａＳｉＯ（４－ａ）／２ （２）
（式中、Ｒは互いに独立に１価炭化水素基であり、ａは１．９～２．４の範囲の正数である。）
As the alkenyl group-containing organopolysiloxane, those represented by the following average composition formula (2) are usually suitably used.
R a SiO (4-a)/2 (2)
(In the formula, R is independently a monovalent hydrocarbon group, and a is a positive number in the range of 1.9 to 2.4.)
上記式（２）において、Ｒは、互いに独立に、炭素数１～１０の１価炭化水素基であり、炭素数１～８の１価炭化水素基が好ましい。例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ヘキシル基、シクロヘキシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基等のアルケニル基、フェニル基、トリル基、キシリル基等のアリール基、ベンジル基等のアラルキル基などが挙げられる。また、上記１価炭化水素基の水素原子の一部がハロゲン原子で置換されたものを用いてもよい。例えば、３，３，３－トリフルオロプロピル基、３，３，４，４，５，５，６，６，６－ノナフルオロヘキシル基などが挙げられる。前記Ｒのうち２個以上はアルケニル基であることが必要であり、好ましくは２～５０個、より好ましくは２～２０個のＲがアルケニル基である。ａは１．９～２．４、好ましくは１．９５～２．０５、より好ましくは１．９８～２．０１の範囲の数である。 In the above formula (2), R independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms. For example, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group Examples include alkenyl groups such as, phenyl groups, tolyl groups, aryl groups such as xylyl groups, and aralkyl groups such as benzyl groups. Furthermore, a monovalent hydrocarbon group in which some of the hydrogen atoms are replaced with halogen atoms may also be used. Examples include 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like. Two or more of the R's need to be alkenyl groups, preferably 2 to 50, more preferably 2 to 20 R's. a is a number ranging from 1.9 to 2.4, preferably from 1.95 to 2.05, more preferably from 1.98 to 2.01.
オルガノポリシロキサンは直鎖状であってもよいし、少量のＲ１ＳｉＯ３／２単位（Ｒ１は前記の通り、以下同じ）あるいはＳｉＯ４／２単位等の分岐単位を含んだ分岐鎖状であってもよい。中でも、主鎖がジオルガノシロキサン単位（Ｒ１ ２ＳｉＯ２／２）の繰り返し単位からなり、分子鎖両末端がトリオルガノシロキシ基（Ｒ１ ３ＳｉＯ１／２）で封鎖された、直鎖状のジオルガノポリシロキサンであることが好適である。前記アルケニル基としては、好ましくはビニル基が挙げられ、アルケニル基以外の１価炭化水素基としては、メチル基、フェニル基が好ましい。 The organopolysiloxane may be linear or branched containing a small amount of branching units such as R 1 SiO 3/2 units (R 1 is as described above, the same applies hereinafter) or SiO 4/2 units. It may be. Among these, straight-chain polymers have a main chain consisting of repeating diorganosiloxane units (R 1 2 SiO 2/2 ) and both ends of the molecular chain are blocked with triorganosiloxy groups (R 1 3 SiO 1/2 ). Diorganopolysiloxanes are preferred. The alkenyl group is preferably a vinyl group, and the monovalent hydrocarbon group other than the alkenyl group is preferably a methyl group or a phenyl group.
（Ａ）オルガノポリシロキサンは、好ましくは１．０×１０－５～２．０×１０－４モル／ｇのアルケニル基を含有する。特に１．３×１０－５～１．３×１０－４モル／ｇのアルケニル基を含有することが好ましい。アルケニル基含有量が少なすぎると架橋密度が低くなり、実用的なゴム強度が低下する場合があり、多すぎると架橋密度が高くなり、ゴム硬化物の切断時伸びが低下してしまう場合がある。なお、このアルケニル基の量は、１Ｈ－ＮＭＲスペクトルにより測定されたものである。 (A) Organopolysiloxane preferably contains 1.0×10 −5 to 2.0×10 −4 mol/g of alkenyl groups. In particular, it is preferable to contain 1.3×10 −5 to 1.3×10 −4 mol/g of alkenyl groups. If the alkenyl group content is too low, the crosslinking density will be low, which may reduce practical rubber strength. If it is too high, the crosslinking density will be high, and the elongation at break of the cured rubber product may decrease. . Note that the amount of this alkenyl group was measured by 1 H-NMR spectrum.
上記（Ａ）オルガノポリシロキサンの平均重合度（又は、分子中のケイ素原子数）は、１００～１，５００、特に１５０～１，０００であることが好ましい。この平均重合度（又は平均分子量）は、トルエンを展開溶媒としたＧＰＣ（ゲルパーミエーションクロマトグラフィ）分析におけるポリスチレン換算の数平均重合度（又は数平均分子量）として求めることができる。 The average degree of polymerization (or number of silicon atoms in the molecule) of the organopolysiloxane (A) is preferably from 100 to 1,500, particularly from 150 to 1,000. This average degree of polymerization (or average molecular weight) can be determined as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in GPC (gel permeation chromatography) analysis using toluene as a developing solvent.
－（Ｂ）アルケニル基含有三次元網状構造オルガノポリシロキサンレジン－
（Ｂ）成分のアルケニル基含有オルガノポリシロキサンレジン（樹脂質共重合体）は、Ｒ１
３ＳｉＯ１／２単位及びＳｉＯ４／２単位を主成分として含有する三次元網状構造のオルガノポリシロキサンレジンである。前記（Ｂ）成分としては、２５℃で固体であることが好ましい。
-(B) Alkenyl group-containing three-dimensional network structure organopolysiloxane resin-
The alkenyl group-containing organopolysiloxane resin (resinous copolymer) of component (B) is an organopolysiloxane resin with a three-dimensional network structure containing R 1 3 SiO 1/2 units and SiO 4/2 units as main components. It is. The component (B) is preferably solid at 25°C.
Ｒ１は、互いに独立に、炭素数１～１０の１価炭化水素基であり、炭素数１～８が好ましい。例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基、シクロヘキセニル基、オクテニル基等のアルケニル基等が挙げられる。 R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. For example, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, Aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, Examples include alkenyl groups such as cyclohexenyl group and octenyl group.
（Ｂ）成分のアルケニル基含有三次元網状構造オルガノポリシロキサンレジン（樹脂質共重合体）は、上記Ｒ１ ３ＳｉＯ１／２単位及びＳｉＯ４／２単位からなるものであってもよく、また必要に応じ、Ｒ１ ２ＳｉＯ２／２単位やＲ１ＳｉＯ３／２単位（Ｒ１は上記の通り）を含んでもよい。 The alkenyl group-containing three-dimensional network structure organopolysiloxane resin (resinous copolymer) of component (B) may be composed of the above R 1 3 SiO 1/2 unit and SiO 4/2 unit, or If necessary, R 1 2 SiO 2/2 units or R 1 SiO 3/2 units (R 1 is as described above) may be included.
Ｒ１ ３ＳｉＯ１／２単位とＳｉＯ４／２単位とのモル比［Ｒ１ ３ＳｉＯ１／２／ＳｉＯ４／２］は０．５～１．５であることが特徴であり、好ましくは、０．５～１．３である。このモル比が０．５より小さいとゴムのタック力が大きくなり、１．５より大きいと相溶性が低下し、配合が困難になってしまう。 The molar ratio of R 1 3 SiO 1/2 units to SiO 4/2 units [R 1 3 SiO 1/2 /SiO 4/2 ] is characterized by being 0.5 to 1.5, preferably , 0.5 to 1.3. If this molar ratio is smaller than 0.5, the tack force of the rubber will increase, and if it is larger than 1.5, the compatibility will decrease and compounding will become difficult.
前記Ｒ１ ２ＳｉＯ２／２単位及び前記Ｒ１ＳｉＯ３／２単位は、これらの合計量として、共重合体全体に対して５０質量％以下（０～５０質量％）、好ましくは４０質量％以下（０～４０質量％）、より好ましくは３０質量％以下（０～３０質量％）の範囲で含んでよい。 The total amount of the R 1 2 SiO 2/2 units and the R 1 SiO 3/2 units is 50% by mass or less (0 to 50% by mass), preferably 40% by mass based on the entire copolymer. It may be contained in a range of 0 to 40% by mass or less, more preferably 30% by mass or less (0 to 30% by mass).
更に（Ｂ）成分のアルケニル基含有三次元網状構造オルガノポリシロキサンレジンは、アルケニル基の量が、１×１０－４～５×１０－３モル／ｇであることを特徴とし、好ましくは２×１０－４～３×１０－３モル／ｇ、より好ましくは３×１０－４～２×１０－３モル／ｇのビニル基を含有する。アルケニル基含有量が５×１０－３モル／ｇより多いとゴムが固くて脆くなり、１×１０－４モル／ｇより少ないとゴムが柔らかくなり、弱くなる。 Furthermore, the alkenyl group-containing three-dimensional network structure organopolysiloxane resin of component (B) is characterized in that the amount of alkenyl groups is 1×10 −4 to 5×10 −3 mol/g, preferably 2× It contains 10 −4 to 3×10 −3 mol/g, more preferably 3×10 −4 to 2×10 −3 mol/g of vinyl groups. When the alkenyl group content is more than 5×10 −3 mol/g, the rubber becomes hard and brittle, and when it is less than 1×10 −4 mol/g, the rubber becomes soft and weak.
なお、上記樹脂共重合体は、通常適当な（即ち、加水分解縮合してＲ１ ３ＳｉＯ１／２単位やＳｉＯ４／２単位を生成する）１官能性及び４官能性のクロロシランやアルコキシシランを当該技術において周知の方法で共加水分解縮合することによって製造することができる。 Note that the above resin copolymer is usually a monofunctional or tetrafunctional chlorosilane or alkoxysilane that can be hydrolyzed and condensed to produce R 1 3 SiO 1/2 units or SiO 4/2 units. can be prepared by cohydrolytic condensation using methods well known in the art.
これらアルケニル基含有三次元網状構造オルガノポリシロキサンレジンの配合量は、（Ａ）成分１００質量部に対し、３～５０質量部であり、特に４～４０質量部が好ましい。３質量部未満ではゴム補強の効果がなく、５０質量部を超えるとゴムが固くて脆くなる。 The amount of these alkenyl group-containing three-dimensional network structure organopolysiloxane resins is 3 to 50 parts by weight, particularly preferably 4 to 40 parts by weight, per 100 parts by weight of component (A). If it is less than 3 parts by mass, there is no rubber reinforcing effect, and if it exceeds 50 parts by mass, the rubber becomes hard and brittle.
－（Ｃ）オルガノハイドロジェンポリシロキサン－
（Ｃ）成分のオルガノハイドロジェンポリシロキサンは架橋剤（硬化剤）として作用する。（Ａ）成分中のアルケニル基及び（Ｂ）成分中のアルケニル基と、該（Ｃ）成分中のケイ素原子結合水素原子（ヒドロシリル基）とがヒドロシリル化付加反応することによって架橋構造を形成する。該オルガノハイドロジェンポリシロキサンは、下記式（１）で示される直鎖状のオルガノハイドロジェンポリシロキサンであることを特徴とする。
The organohydrogenpolysiloxane (C) component acts as a crosslinking agent (curing agent). A crosslinked structure is formed by a hydrosilylation addition reaction between the alkenyl group in component (A) and the alkenyl group in component (B) and the silicon-bonded hydrogen atom (hydrosilyl group) in component (C). The organohydrogenpolysiloxane is characterized by being a linear organohydrogenpolysiloxane represented by the following formula (1).
得られるシリコーンゴムが良好な難燃性を安定的に有するためには、好ましくは、ｙは４～９８であり、好ましくは４～８０であり、ｚは２～５０であり、好ましくは２～４５であり、かつ、ｙ＋ｚは６～１１０であり、好ましくは６～１００である。ｙ／ｚの比は２～４であり、２．５～３．５であることが好ましい。 In order for the obtained silicone rubber to stably have good flame retardancy, y is preferably 4 to 98, preferably 4 to 80, and z is 2 to 50, preferably 2 to 45, and y+z is 6 to 110, preferably 6 to 100. The y/z ratio is between 2 and 4, preferably between 2.5 and 3.5.
上記Ｒ２で示される炭素数１～１０の１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基が挙げられる。なお、これらの基の水素原子の一部又は全部をフッ素、臭素、塩素等のハロゲン原子で置換したものを用いてもよい。例えばクロロメチル基、クロロプロピル基、ブロモエチル基、トリフロロプロピル基等が挙げられる。また、Ｒ２はアルケニル基を含まない。全てのＲ２の９０モル％以上、特には全てのＲ２がメチル基であることが好ましい。また、Ｒ３は互いに独立に、炭素数１～１０の１価炭化水素基（アルケニル基を除く）又は水素原子である。炭素数１～１０の１価炭化水素基は、上記Ｒ２の定義ために例示した基が挙げられる。全てのＲ３の９０モル％以上、特には全てのＲ３がメチル基であることが好ましい。 Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 2 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, and neopentyl group. , alkyl groups such as hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, etc. can be mentioned. In addition, those in which part or all of the hydrogen atoms of these groups are replaced with halogen atoms such as fluorine, bromine, and chlorine may also be used. Examples include chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, and the like. Moreover, R 2 does not contain an alkenyl group. It is preferable that 90 mol% or more of all R 2 , particularly all R 2 , are methyl groups. Furthermore, R 3 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding alkenyl groups) or a hydrogen atom. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include the groups exemplified for the definition of R 2 above. It is preferred that 90 mol% or more of all R3s , particularly all R3s , be methyl groups.
直鎖状オルガノハイドロジェンポリシロキサンとしては、例えば、両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体等が挙げられる。（Ｃ）成分は１種単独で又は２種以上を組み合わせて使用してもよい。 Examples of the linear organohydrogenpolysiloxane include methylhydrogenpolysiloxane with trimethylsiloxy groups blocked at both ends, dimethylsiloxane/methylhydrogensiloxane copolymer with both ends blocked with trimethylsiloxy groups, and dimethylhydrogensiloxane copolymer with both ends blocked with trimethylsiloxy groups. Examples include dimethylsiloxane/methylhydrogensiloxane copolymer. Component (C) may be used alone or in combination of two or more.
（Ｃ）成分のオルガノハイドロジェンポリシロキサンの配合比は（Ａ）成分及び（Ｂ）成分中に含まれるアルケニル基の合計個数に対して（Ｃ）成分中のヒドロシリル基の個数の比（ヒドロシリル基／アルケニル基）が１．５～１．７であることを特徴とする。好ましくは、１．５～１．６である。上記範囲内であれば、得られるシリコーンゴムに安定的に難燃性を付与できるため好ましい。また、（Ｃ）成分の配合量は、前記式（１）で示されるオルガノハイドロジェンポリシロキサンの構造や、ヒドロシリル基量にもよるが、（Ａ）成分１００質量部に対して０．５～２５質量部、好ましくは０．５～２０質量部、より好ましくは１～１５質量部である。（Ｃ）成分の量が少なすぎると架橋密度が低くなりすぎて、ゴム成形品の物性に悪影響を与える。また多すぎると、脱水素反応による発泡の問題が生じる上、同様に物性に悪影響を与える。 The blending ratio of the organohydrogenpolysiloxane of component (C) is the ratio of the number of hydrosilyl groups in component (C) to the total number of alkenyl groups contained in components (A) and (B). /alkenyl group) is 1.5 to 1.7. Preferably it is 1.5 to 1.6. If it is within the above range, flame retardancy can be stably imparted to the resulting silicone rubber, which is preferable. The amount of component (C) to be blended varies from 0.5 to 100 parts by mass of component (A), although it depends on the structure of the organohydrogenpolysiloxane represented by formula (1) and the amount of hydrosilyl groups. The amount is 25 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight. If the amount of component (C) is too small, the crosslinking density will be too low, which will adversely affect the physical properties of the rubber molded product. On the other hand, if the amount is too large, the problem of foaming due to dehydrogenation reaction will occur, and the physical properties will also be adversely affected.
－（Ｄ）付加反応触媒－
（Ｄ）付加反応触媒としては、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と１価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系触媒、パラジウム系触媒、ロジウム系触媒などが挙げられる。付加反応触媒の量は触媒量であればよいが、通常、（Ａ）成分の質量に対する白金族金属の質量換算で、０．５～１，０００ｐｐｍ、特に１～２００ｐｐｍ程度である。
-(D) Addition reaction catalyst-
(D) Addition reaction catalysts include platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Examples include catalysts based on catalysts, palladium-based catalysts, rhodium-based catalysts, and the like. The amount of the addition reaction catalyst may be any catalytic amount, but it is usually about 0.5 to 1,000 ppm, particularly about 1 to 200 ppm, calculated as the mass of platinum group metal relative to the mass of component (A).
なお、保存安定性の向上などを目的として、上記付加反応触媒の反応制御剤を添加してもよい。反応制御剤としては、アセチレン化合物、アルケニル基含有低分子シロキサン、窒素含有化合物、リン化合物、ニトリル化合物、カルボキシレート、錫化合物、水銀化合物、及び硫黄化合物等が挙げられる。中でも、エチニルシクロヘキサノール、２－メチル－３－プロピン－１－オール、３－メチル－１－トリデシン－３－オールなどのアセチレン化合物や１，３，５，７－テトラビニルテトラメチルシクロテトラシロキサン、１，３－ジビニル－１，１，３，３－テトラメチルジシロキサンなどのアルケニル基含有低分子シロキサンが好ましい。これらの反応制御剤は、１種単独でも２種以上併用して用いてもよい。 In addition, for the purpose of improving storage stability, etc., a reaction control agent for the above-mentioned addition reaction catalyst may be added. Examples of the reaction control agent include acetylene compounds, alkenyl group-containing low-molecular siloxanes, nitrogen-containing compounds, phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, and sulfur compounds. Among them, acetylene compounds such as ethynylcyclohexanol, 2-methyl-3-propyn-1-ol, 3-methyl-1-tridecyn-3-ol, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, Alkenyl group-containing low molecular weight siloxanes such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are preferred. These reaction control agents may be used alone or in combination of two or more.
上記反応制御剤の配合量としては、所望する保存安定性や反応制御剤の分子量などによって任意に設定可能だが、上記（Ａ）成分１００質量部に対して０．０１～１質量部が好ましい。 The amount of the reaction control agent can be arbitrarily set depending on the desired storage stability, the molecular weight of the reaction control agent, etc., but it is preferably 0.01 to 1 part by weight per 100 parts by weight of component (A).
－（Ｅ）ＢＥＴ法による比表面積１００ｍ２／ｇ以上のヒュームドシリカ－
（Ｅ）成分の補強性シリカ微粉末は、通常ゴムの補強剤として使用されるものであればよい。その補強性シリカ微粉末としては、従来のシリコーンゴム組成物に使用されているものを使用できるが、ＢＥＴ法による比表面積が１００ｍ２／ｇ以上である補強性シリカ微粉末を用いる。特にＢＥＴ法による比表面積が１００～４００ｍ２／ｇ、とりわけ１００～３５０ｍ２／ｇの、沈澱シリカ（湿式シリカ）、ヒュームドシリカ（乾式シリカ）、焼成シリカ等が好適に使用され、ゴム強度を向上することからヒュームドシリカが好適である。また、上記補強性シリカ微粉末は、例えば、クロロシラン、アルコキシシラン、オルガノシラザン等の（通常、加水分解性の）有機ケイ素化合物などの表面処理剤で、表面が疎水化処理されたシリカ微粉末であってもよい。その場合、これらのシリカ微粉末は、予め粉体の状態で、表面処理剤により直接、表面疎水化処理されたものでもよいし、シリコーンオイル（例えば、上記（Ａ）成分のアルケニル基含有オルガノポリシロキサン）との混練時に表面処理剤を添加して、表面疎水化処理したものでもよい。
- (E) Fumed silica with a specific surface area of 100 m 2 /g or more by BET method -
The fine reinforcing silica powder of component (E) may be of any kind as long as it is normally used as a reinforcing agent for rubber. As the reinforcing fine silica powder, those used in conventional silicone rubber compositions can be used, but the reinforcing fine silica powder having a specific surface area of 100 m 2 /g or more by the BET method is used. In particular, precipitated silica (wet silica), fumed silica (dry silica), calcined silica, etc. with a specific surface area of 100 to 400 m 2 /g, especially 100 to 350 m 2 /g by BET method are preferably used to improve rubber strength. Fumed silica is preferred because of its improved performance. The reinforcing silica fine powder is, for example, silica fine powder whose surface has been hydrophobized with a surface treatment agent such as a (usually hydrolyzable) organosilicon compound such as chlorosilane, alkoxysilane, or organosilazane. There may be. In that case, these silica fine powders may be directly surface-hydrophobized with a surface treatment agent in the powder state, or may be treated with silicone oil (for example, alkenyl group-containing organopolymer of component (A) above). A surface treatment agent may be added during kneading with siloxane) to make the surface hydrophobic.
表面処理法は特に制限されず公知技術により処理すればよい。例えば、常圧で密閉された機械混練装置又は流動層に上記未処理のシリカ微粉末と処理剤を入れ、必要に応じて不活性ガス存在下において室温あるいは熱処理（加熱下）にて混合処理する。場合により、触媒（加水分解促進剤等）を使用して処理を促進してもよい。混練後、乾燥することにより処理シリカ微粉末を製造し得る。処理剤の配合量は、その処理剤の被覆面積から計算される量以上であればよい。 The surface treatment method is not particularly limited, and any known technique may be used. For example, the untreated fine silica powder and the treatment agent are placed in a mechanical kneading device or fluidized bed sealed at normal pressure, and mixed at room temperature or heat treatment (under heating) in the presence of an inert gas, if necessary. . Optionally, catalysts (such as hydrolysis promoters) may be used to accelerate the process. After kneading, a treated silica fine powder can be produced by drying. The amount of the treatment agent to be blended may be at least the amount calculated from the area covered by the treatment agent.
表面処理剤としては、例えば、へキサメチルジシラザン等のシラザン類、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、ブチルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、トリメチルメトキシシラン、トリエチルメトキシシラン、ビニルトリス（メトキシエトキシ）シラン、トリメチルクロロシラン、ジメチルジクロロシラン、ジビニルジメトキシシラン及びクロロプロピルトリメトキシシラン等のシランカップリング剤、ポリメチルシロキサン、オルガノハイドロジェンポリシロキサン等の有機ケイ素化合物が挙げられ、これらで表面処理し、疎水性シリカ微粉末として用いる。処理剤としては、特にシラン系カップリング剤又はシラザン類が好ましい。 Examples of surface treatment agents include silazane such as hexamethyldisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, and vinyltriethoxysilane. , silane coupling agents such as vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris(methoxyethoxy)silane, trimethylchlorosilane, dimethyldichlorosilane, divinyldimethoxysilane and chloropropyltrimethoxysilane, polymethylsiloxane, organohydro Examples include organosilicon compounds such as genpolysiloxane, which are surface-treated and used as hydrophobic silica fine powder. As the treatment agent, silane coupling agents or silazane are particularly preferred.
（Ｅ）成分の配合量は、（Ａ）成分１００質量部に対して１０～５０質量部、好ましくは１０～４５質量部、より好ましくは１０～４０質量部である。１０質量部より少ないと十分な補強効果が得られず、５０質量部を超えるとシリコーンゴム組成物の粘度が高くなりすぎて作業性、加工性が悪くなる。
また、上記（Ｅ）成分以外に、必要に応じて、沈降シリカ、石英粉、珪藻土、炭酸カルシウムなどの充填材を配合してもよい。これらの充填材の配合量は、本発明の効果を損なわない範囲で任意だが、（Ａ）成分１００質量部に対して、５０質量部以下であることが好ましい。
The blending amount of component (E) is 10 to 50 parts by weight, preferably 10 to 45 parts by weight, and more preferably 10 to 40 parts by weight per 100 parts by weight of component (A). If it is less than 10 parts by mass, a sufficient reinforcing effect cannot be obtained, and if it exceeds 50 parts by mass, the viscosity of the silicone rubber composition becomes too high, resulting in poor workability and processability.
In addition to the above component (E), fillers such as precipitated silica, quartz powder, diatomaceous earth, and calcium carbonate may be added as necessary. The blending amount of these fillers is arbitrary within a range that does not impair the effects of the present invention, but it is preferably 50 parts by mass or less with respect to 100 parts by mass of component (A).
－（Ｆ）トリアゾール化合物－
（Ｆ）成分はトリアゾール化合物である。（Ｆ）成分の配合量は、前記（Ａ）成分１００質量部に対して、０．００１～０．５質量部であり、０．００５～０．１質量部が好ましい。（Ｆ）成分は、シリコーンゴム硬化物の機械的強度、切断時伸び等の物理特性（ゴム物性）を損なうことなく、難燃性を付与するための、難燃性付与剤である。
-(F) Triazole compound-
Component (F) is a triazole compound. The blending amount of component (F) is 0.001 to 0.5 parts by mass, preferably 0.005 to 0.1 parts by mass, per 100 parts by mass of component (A). Component (F) is a flame retardant agent that imparts flame retardancy to the cured silicone rubber without impairing physical properties (rubber properties) such as mechanical strength and elongation at cutting.
トリアゾール化合物としては、例えば、１，２，３－トリアゾール、１，２，４－トリアゾール及びこれらの誘導体が挙げられる。例えば、１，２，３－トリアゾールの誘導体としては、ベンゾトリアゾール、４－ヒドロキシ－１，２，３－トリアゾール、１，２，３－トリアゾール－４－アルデヒド、４－シアノ－１，２，３－トリアゾールなどが挙げられる。１，２，４－トリアゾールの誘導体としては、５－アミノ－３－メチル－１，２，４－トリアゾール、３－メルカプト－１，２，４－トリアゾールなどが挙げられる。これらのうち最も好適なものは、ベンゾトリアゾール、１，２，３－トリアゾール、１，２，４－トリアゾールである。これらは単独で使用しても２種以上を併用してもよい。 Examples of triazole compounds include 1,2,3-triazole, 1,2,4-triazole, and derivatives thereof. For example, derivatives of 1,2,3-triazole include benzotriazole, 4-hydroxy-1,2,3-triazole, 1,2,3-triazole-4-aldehyde, 4-cyano-1,2,3 - Triazoles, etc. Examples of derivatives of 1,2,4-triazole include 5-amino-3-methyl-1,2,4-triazole and 3-mercapto-1,2,4-triazole. The most preferred among these are benzotriazole, 1,2,3-triazole, and 1,2,4-triazole. These may be used alone or in combination of two or more.
－その他の成分－
本発明の付加硬化型シリコーン組成物において、その他の成分として、必要に応じて、導電性亜鉛華、金属粉等の導電性付与剤、酸化鉄、酸化セリウムのような耐熱性付与剤、カーボンブラック、酸化チタンの着色剤、ジメチルシリコーンオイル等の内部離型剤、接着性付与剤（特には、分子中にアルケニル基、エポキシ基、アミノ基、（メタ）アクリロキシ基、メルカプト基等から選ばれる少なくとも１種の官能性基を含有すると共に、分子中にヒドロシリル基を含有しないアルコキシシラン等の有機ケイ素化合物など）、チクソ性付与剤等を配合することができる。
これらの配合量としては、ゴム成形品の外観を損ねたり、本発明の効果である難燃性を低下させたりしない範囲で任意とされる。例えば、上記導電性付与剤であれば、（Ａ）成分１００質量部に対して０．１～２０質量部が好ましく、上記耐熱性付与剤であれば、（Ａ）成分１００質量部に対して０．０１～２０質量部が好ましい。上記着色剤であれば、（Ａ）成分１００質量部に対して０．０１～１０質量部が好ましい。
-Other ingredients-
In the addition-curing silicone composition of the present invention, other components may include conductive zinc white, a conductivity imparting agent such as metal powder, a heat resistance imparting agent such as iron oxide or cerium oxide, and carbon black. , titanium oxide colorant, internal mold release agent such as dimethyl silicone oil, adhesion imparting agent (particularly at least one selected from alkenyl group, epoxy group, amino group, (meth)acryloxy group, mercapto group, etc. in the molecule) An organosilicon compound such as an alkoxysilane containing one kind of functional group and no hydrosilyl group in the molecule), a thixotropy imparting agent, etc. can be blended.
The amount of these compounds to be blended is arbitrary within a range that does not impair the appearance of the rubber molded product or reduce the flame retardancy, which is an effect of the present invention. For example, the above conductivity imparting agent is preferably 0.1 to 20 parts by mass per 100 parts by mass of component (A), and the above heat resistance imparting agent is preferably 0.1 to 20 parts by mass per 100 parts by mass of component (A). 0.01 to 20 parts by mass is preferred. The above coloring agent is preferably used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of component (A).
本発明の付加硬化型シリコーン組成物は、ニーダー、プラネタリーミキサーなどの通常の混合攪拌器、混練器等を用いて上記各成分を均一に混合することにより製造することができる。 The addition-curable silicone composition of the present invention can be produced by uniformly mixing the above-mentioned components using a conventional mixing agitator, kneader, etc. such as a kneader or a planetary mixer.
本発明の付加硬化型シリコーン組成物は２３℃で液状である。好ましくは、粘度・粘弾性測定装置（ＨＡＫＫＥＭＡＲＳ４０、サーモフィッシャーサイエンティフィック株式会社製）で測定した２３℃における粘度が、１，０００ｍＰａ・ｓ～５，０００，０００ｍＰａ・ｓであることが好ましい。また（Ｆ）成分を含有する場合には、２３℃における粘度の好ましい範囲は、１０，０００ｍＰａ・ｓ～１０，０００，０００ｍＰａ・ｓ、好ましくは１０，０００ｍＰａ・ｓ～５，０００，０００ｍＰａ・ｓとなる。 The addition-curing silicone composition of the present invention is liquid at 23°C. Preferably, the viscosity at 23° C. measured with a viscosity/viscoelasticity measuring device (HAKKEMARS40, manufactured by Thermo Fisher Scientific Co., Ltd.) is 1,000 mPa·s to 5,000,000 mPa·s. In addition, when containing component (F), the preferable range of viscosity at 23°C is 10,000 mPa·s to 10,000,000 mPa·s, preferably 10,000 mPa·s to 5,000,000 mPa·s. becomes.
本発明の付加硬化性シリコーン組成物の成形、硬化方法は特に制限されず、従来公知の方法に従えばよい。成形法としては例えば、射出成形、トランスファー成形、注入成形、及び圧縮成形等から目的にあった最適な手段を選択すればよい。硬化条件としては、該組成物は、たとえば８０～２３０℃、好ましくは１００～１８０℃で加熱することにより一次硬化させることができる。加熱時間は、３０秒～３時間程度、特に１分～１時間程度が好ましい。また、硬化条件については、必要に応じて二次加硫（ポストキュア）を行ってもよい。二次加硫は、例えば、１５０～２００℃で６０分～２４時間程度行う。一次加硫のみで硬化できる利点は、二次加硫に要した時間が不要になるので、生産性が大幅に向上する点にある。又、製造時の熱エネルギーを削減できるため、環境負荷が低減できる成形が可能となる。 The method for molding and curing the addition-curable silicone composition of the present invention is not particularly limited, and any conventionally known method may be used. The molding method may be selected from among injection molding, transfer molding, injection molding, compression molding, and the like, as appropriate for the purpose. As for the curing conditions, the composition can be primarily cured by heating, for example, at 80 to 230°C, preferably 100 to 180°C. The heating time is preferably about 30 seconds to 3 hours, particularly about 1 minute to 1 hour. Regarding the curing conditions, secondary vulcanization (post-curing) may be performed as necessary. Secondary vulcanization is performed, for example, at 150 to 200°C for about 60 minutes to 24 hours. The advantage of being able to cure with only primary vulcanization is that the time required for secondary vulcanization is no longer required, so productivity is greatly improved. In addition, since thermal energy during manufacturing can be reduced, molding with reduced environmental impact is possible.
シリコーンゴム硬化物の厚さは特に制限されないが、０．５～１０ｍｍ、特には１～６ｍｍであるのがよい。 The thickness of the cured silicone rubber product is not particularly limited, but it is preferably 0.5 to 10 mm, particularly 1 to 6 mm.
本発明のシリコーン組成物を硬化して得られるシリコーンゴム硬化物は、上記厚さにおいて特に優れた難燃性を有する。特には、厚さ０．５ｍｍ以上、好ましくは１ｍｍ以上を有するシリコーンゴム硬化物にてＵＬ９４規格に基づく難燃性試験においてＶ－１の難燃性を有することができる。なお、本発明において難燃性試験はＵＬ９４規格の垂直燃焼試験の方法に基づいて、以下の方法で行った。
［測定方法］
１．幅１３．０ｍｍ。長さ１２５ｍｍ、厚さは実用上の最小値の短冊状試験片を固定用クランプで垂直につるす。
２．試験片の下端に高さ２０ｍｍのガスバーナーの炎の中心を１０秒間当てる。
３．炎を取り去って燃焼時間を測定し、３０秒以内に燃焼が止まったら、さらに１０秒間接炎する。
４．試験片は５本用い、ｎ＝５での評価結果とする。
［評価基準］
１．固定用クランプの位置まで燃焼する試料がない。
２．接炎は２回行い、個々の試験片の１回目接炎後の残炎時間（Ｔ１）と２回目接炎後の残炎時間（Ｔ２）が３０秒以下であること。
３．２回目接炎後の残炎時間（Ｔ２）とアフターグロー時間（Ｔ３）が６０秒以下であること。
４．５本の試験片の合計残炎時間（Ｔ１＋Ｔ２）が２５０秒以下であること。
５．試験片の下方に置かれた脱脂綿を発火、燃焼する粒子を落下させる試験片がない。
上記５つの評価基準を全て満たしたものを難燃性Ｖ－１と判断した。
The silicone rubber cured product obtained by curing the silicone composition of the present invention has particularly excellent flame retardancy at the above thickness. In particular, a silicone rubber cured product having a thickness of 0.5 mm or more, preferably 1 mm or more can have flame retardancy of V-1 in the flame retardancy test based on the UL94 standard. In the present invention, the flame retardancy test was conducted in the following manner based on the vertical combustion test method of the UL94 standard.
[Measuring method]
1. Width 13.0mm. A strip-shaped test piece with a length of 125 mm and a practical minimum thickness is hung vertically using a fixing clamp.
2. The center of the flame of a gas burner with a height of 20 mm is applied to the lower end of the test piece for 10 seconds.
3. Remove the flame and measure the combustion time, and if combustion stops within 30 seconds, heat the flame indirectly for another 10 seconds.
4. Five test pieces are used, and the evaluation results are based on n=5.
[Evaluation criteria]
1. No sample burns to the position of the fixing clamp.
2. Flame contact shall be carried out twice, and the afterflame time (T1) after the first flame contact and the afterflame time (T2) after the second flame contact of each test piece shall be 30 seconds or less.
3. The afterflame time (T2) and afterglow time (T3) after the second contact with the flame should be 60 seconds or less.
4. The total afterflame time (T1+T2) of the five test pieces must be 250 seconds or less.
5. There is no test piece that allows particles to ignite and burn the absorbent cotton placed below the test piece.
Those that met all of the above five evaluation criteria were judged to have flame retardancy V-1.
本発明の付加硬化性シリコーン組成物は優れた難燃性を有するシリコーンゴムを提供することができ、且つ、保存安定性に優れるため、難燃性が要求される電化製品、ケーブル端末部品、ポリマー碍子、自動車材料等に有用である。 The addition-curable silicone composition of the present invention can provide silicone rubber with excellent flame retardancy and has excellent storage stability, so it can be used in electrical appliances, cable terminal parts, and polymers that require flame retardancy. Useful for insulators, automobile materials, etc.
以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記の実施例に制限されるものではない。平均重合度は、トルエンを展開溶媒としてゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析によるポリスチレン換算の数平均重合度を意味する。 EXAMPLES Hereinafter, the present invention will be explained in more detail by showing examples and comparative examples, but the present invention is not limited to the following examples. The average degree of polymerization means the number average degree of polymerization in terms of polystyrene as determined by gel permeation chromatography (GPC) analysis using toluene as a developing solvent.
下記実施例及び比較例で使用した（Ａ）成分は下記平均組成式で表される直鎖状ジメチルポリシロキサンである。
ＲａＳｉＯ（４－ａ）／２ （２）
（ａ≒２）
Component (A) used in the following Examples and Comparative Examples is a linear dimethylpolysiloxane represented by the following average composition formula.
R a SiO (4-a)/2 (2)
(a≒2)
下記実施例及び比較例で使用した（Ｂ）成分は下記化合物である。
２５℃で固体の（ＣＨ３）３ＳｉＯ１／２単位、ＣＨ２＝ＣＨ（ＣＨ３）２ＳｉＯ１／２単位及びＳｉＯ４／２単位からなるオルガノポリシロキサンレジン （ｂ１）
［（ＣＨ３）３ＳｉＯ１／２単位とＣＨ２＝ＣＨ（ＣＨ３）２ＳｉＯ１／２単位の合計モル］／ＳｉＯ４／２単位のモル＝０．８５、ビニル基含有量＝０．０００８６モル／ｇ
The component (B) used in the following Examples and Comparative Examples is the following compound.
Organopolysiloxane resin (b1) consisting of (CH 3 ) 3 SiO 1/2 units, CH 2 =CH(CH 3 ) 2 SiO 1/2 units and SiO 4/2 units that are solid at 25°C.
[Total moles of (CH 3 ) 3 SiO 1/2 units and CH 2 =CH(CH 3 ) 2 SiO 1/2 units]/mol of SiO 4/2 units = 0.85, vinyl group content = 0. 00086 mol/g
下記実施例及び比較例で使用した（Ｃ）成分は下記化合物である。
架橋剤（ｃ１）： 下記式（３）の両末端にヒドロシリル基を有するメチルハイドロジェンポリシロキサン（ヒドロシリル基量０．００４２４モル／ｇ）
Crosslinking agent (c1): Methyl hydrogen polysiloxane having hydrosilyl groups at both ends of the following formula (3) (hydrosilyl group amount 0.00424 mol/g)
下記実施例及び比較例で使用した（Ｅ）成分は下記の通りである。
（Ｅ）： ＢＥＴ法による比表面積が２００ｍ２／ｇであるヒュームドシリカ（ｅ１）
（日本アエロジル（株）製、アエロジル２００）
ＢＥＴ法による比表面積が３００ｍ２／ｇであるヒュームドシリカ（ｅ２）
（日本アエロジル（株）製、アエロジル３００）
ＢＥＴ法による比表面積が２００ｍ２／ｇであるヒュームドシリカ（ｅ３）
（（株）トクヤマ製、レオロシール（登録商標）ＤＭ－２０Ｓ）
The component (E) used in the following Examples and Comparative Examples is as follows.
(E): Fumed silica (e1) with a specific surface area of 200 m 2 /g by BET method
(Manufactured by Nippon Aerosil Co., Ltd., Aerosil 200)
Fumed silica (e2) with a specific surface area of 300 m 2 /g by BET method
(Manufactured by Nippon Aerosil Co., Ltd., Aerosil 300)
Fumed silica (e3) with a specific surface area of 200 m 2 /g by BET method
(Manufactured by Tokuyama Co., Ltd., Reolo Seal (registered trademark) DM-20S)
［実施例１］
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が５１０で２３℃粘度が
１０Ｐａ・ｓである直鎖状ジメチルポリシロキサン（ａ１）４０質量部、上記オルガノポリシロキサンレジン（ｂ１）５．０質量部、両末端がジメチルビニルシロキシ基で封鎖された平均重合度が４５０である直鎖状ジメチルポリシロキサン（ａ２）５．０質量部、上記ヒュームドシリカ（ｅ１）２７質量部、ヘキサメチルジシラザン５．０質量部、ビス（Ｎ，Ｎ－トリメチルシリルアミノ）メチルビニルシラン０．１質量部、及び水２．５質量部を室温で１２０分混合した。その後、上記直鎖状ジメチルポリシロキサン（ａ１）をさらに１０質量部を添加し、２５℃で６０分混合後、１５０℃に昇温して１５０分撹拌を続けた。次いで、該混合物を冷却し、上記直鎖状ジメチルポリシロキサン（ａ１）をさらに４０質量部、分子鎖両末端がトリメチルシロキシ基で封鎖され、Ｍ２Ｄ２００ＤＶｉ
１０で示され、ビニル価６．５×１０－４モル／ｇを有する、平均重合度２００の直鎖状ジメチルポリシロキサン（ａ３）５質量部、平均重合度が４２である分子鎖両末端にトリメチルシロキシ基を有する無官能性直鎖状ジメチルポリシロキサン５質量部を添加し、３０分混合後、シリコーンベースを得た。
[Example 1]
40 parts by mass of linear dimethylpolysiloxane (a1), which has both ends blocked with dimethylvinylsiloxy groups and has an average degree of polymerization of 510 and a viscosity at 23°C of 10 Pa·s, 5.0 parts of the above organopolysiloxane resin (b1) Parts by mass, 5.0 parts by mass of linear dimethylpolysiloxane (a2) with an average degree of polymerization of 450, both ends of which are blocked with dimethylvinylsiloxy groups, 27 parts by mass of the fumed silica (e1), hexamethyldi 5.0 parts by mass of silazane, 0.1 parts by mass of bis(N,N-trimethylsilylamino)methylvinylsilane, and 2.5 parts by mass of water were mixed at room temperature for 120 minutes. Thereafter, another 10 parts by mass of the linear dimethylpolysiloxane (a1) was added, and after mixing at 25°C for 60 minutes, the temperature was raised to 150°C and stirring was continued for 150 minutes. Next, the mixture was cooled, and 40 parts by mass of the linear dimethylpolysiloxane (a1) was added, both ends of the molecular chain were blocked with trimethylsiloxy groups, M 2 D 200 D Vi 10 , and the vinyl value was 6. 5 x 10 -4 mol/g, 5 parts by mass of linear dimethylpolysiloxane (a3) with an average degree of polymerization of 200, non-functional with trimethylsiloxy groups at both ends of the molecular chain and an average degree of polymerization of 42. 5 parts by mass of linear dimethylpolysiloxane were added and mixed for 30 minutes to obtain a silicone base.
このシリコーンベース１４０質量部に、分子鎖両末端がジメチルビニルシロキシ基で封鎖された平均重合度が７５０である直鎖状ジメチルポリシロキサン（ａ４）５質量部、上記架橋剤（ｃ１）を５．７０質量部［配合成分中の架橋剤のヒドロシリル基／配合成分中のアルケニル基＝１．６（モル／モル）］、反応制御剤として１，３，５，７－テトラビニルテトラメチルシクロテトラシロキサンを０．２質量部、エチニルシクロヘキサノール０．０８質量部、白金触媒（Ｐｔ濃度１質量％）０．３０質量部、１，２，３－ベンゾトリアゾールのエタノール１０質量％溶液０．２質量部を添加し、１５分攪拌混合し、液状シリコーン組成物を得た。 To 140 parts by mass of this silicone base, 5 parts by mass of linear dimethylpolysiloxane (a4) having an average degree of polymerization of 750, in which both ends of the molecular chain are blocked with dimethylvinylsiloxy groups, and 5.0 parts by mass of the above-mentioned crosslinking agent (c1) were added. 70 parts by mass [hydrosilyl group of crosslinking agent in compounding component/alkenyl group in compounding component = 1.6 (mol/mol)], 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane as a reaction control agent 0.2 parts by mass, 0.08 parts by mass of ethynylcyclohexanol, 0.30 parts by mass of platinum catalyst (Pt concentration 1% by mass), 0.2 parts by mass of a 10% by mass solution of 1,2,3-benzotriazole in ethanol. was added and stirred and mixed for 15 minutes to obtain a liquid silicone composition.
〔粘度測定〕
上記シリコーン組成物の粘度を、サーモフィッシャーサイエンティフィック株式会社製のＨＡＡＫＥ ＭＡＲＳ４０にて、２３℃におけるせん断速度２．０ｓ－１で測定した。その結果を表１に示す。
[Viscosity measurement]
The viscosity of the silicone composition was measured using HAAKE MARS40 manufactured by Thermo Fisher Scientific Co., Ltd. at a shear rate of 2.0 s −1 at 23° C. The results are shown in Table 1.
〔硬化物の物性測定〕
上記シリコーン組成物の硬化物の物性測定を行った。
該組成物を１５０℃／１０分のプレスキュアーを行い、得られた硬化物についてＪＩＳ Ｋ６２４９：２００３に基づき、硬さ、引張強さ、切断時伸び、及び引裂強さ（アングル型）を測定した結果を表１に示した。
[Measurement of physical properties of cured product]
The physical properties of the cured product of the silicone composition were measured.
The composition was press cured at 150°C for 10 minutes, and the hardness, tensile strength, elongation at break, and tear strength (angle type) of the obtained cured product were measured based on JIS K6249:2003. The results are shown in Table 1.
〔難燃性測定〕
上記シリコーン組成物を１５０℃／１０分のプレスキュアーを行い、厚さ１ｍｍの硬化シートを作製し、下記に示す方法により難燃性を測定した。
難燃性測定はＵＬ９４規格に基づく垂直燃焼試験に規定する方法に従った。詳細は上述した通りである。
[Flame retardancy measurement]
The above silicone composition was press-cured at 150° C. for 10 minutes to prepare a cured sheet with a thickness of 1 mm, and its flame retardance was measured by the method shown below.
Flame retardancy was measured in accordance with the method prescribed for the vertical combustion test based on the UL94 standard. The details are as described above.
［実施例２］
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が７５０で２３℃粘度が
３０Ｐａ．ｓである直鎖状ジメチルポリシロキサン（ａ５）６０質量部、上記ヒュームドシリカ（ｅ２）４０質量部、ヘキサメチルジシラザン８．０質量部、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン０．２質量部、及び水２．０質量部を室温で１２０分混合した。その後、１５０℃に昇温して１５０分撹拌を続け、冷却し、上記直鎖状ジメチルポリシロキサン（ａ５）をさらに３０質量部添加し、３０分混合後シリコーンベースを得た。
このシリコーンベース１４０質量部に、上記直鎖状ジメチルポリシロキサン（ａ５）をさらに１３．７５質量部、上記オルガノポリシロキサンレジン（ｂ１） ５質量部、分子鎖両末端がジメチルビニルシロキシ基で封鎖された平均重合度が１８０である直鎖状ジメチルポリシロキサン（ａ７）０．６質量部、白色着色剤として、酸化チタン（昭和電工（株）製、スーパータイタニアＦ－４Ａ）２．５質量部、及び酸化チタン（石原産業（株）製、タイペークＣＲ－６０）１．２５質量部、黒色着色剤としてカーボン（電気化学（株）製、デンカブラック粒状）０．１０質量部、上記架橋剤（ｃ１）を３．２５質量部［配合成分中の架橋剤のヒドロシリル基／配合成分中のアルケニル基＝１．６（モル／モル）］、反応制御剤として１，３，５，７－テトラビニルテトラメチルシクロテトラシロキサンを０．２質量部、及びエチニルシクロヘキサノール０．０８質量部、白金触媒（Ｐｔ濃度１質量％）０．３０質量部、及び１，２，３－ベンゾトリアゾールのエタノール１０％溶液０．２質量部を添加し、１５分攪拌混合し、液状シリコーン組成物を得た。
得られたシリコーン組成物について、実施例１と同じ方法で、粘度測定、硬化物の物性測定及び難燃性測定を行った。結果を表１に示す。
[Example 2]
Both ends are blocked with dimethylvinylsiloxy groups, the average degree of polymerization is 750, and the viscosity at 23°C is 30 Pa. 60 parts by mass of linear dimethylpolysiloxane (a5), 40 parts by mass of the above fumed silica (e2), 8.0 parts by mass of hexamethyldisilazane, 1,3-divinyl-1,1,3,3 -0.2 parts by mass of tetramethyldisilazane and 2.0 parts by mass of water were mixed at room temperature for 120 minutes. Thereafter, the temperature was raised to 150° C., stirring was continued for 150 minutes, and the mixture was cooled. 30 parts by mass of the above-mentioned linear dimethylpolysiloxane (a5) was further added, and after mixing for 30 minutes, a silicone base was obtained.
To 140 parts by mass of this silicone base, an additional 13.75 parts by mass of the above-mentioned linear dimethylpolysiloxane (a5), 5 parts by mass of the above-mentioned organopolysiloxane resin (b1), and both ends of the molecular chain are blocked with dimethylvinylsiloxy groups. 0.6 parts by mass of linear dimethylpolysiloxane (a7) having an average degree of polymerization of 180, 2.5 parts by mass of titanium oxide (manufactured by Showa Denko K.K., Super Titania F-4A) as a white colorant, and 1.25 parts by mass of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Taipeiku CR-60), 0.10 parts by mass of carbon (manufactured by Denki Kagaku Co., Ltd., Denka Black Granular) as a black coloring agent, and the above crosslinking agent (c1 ), 3.25 parts by mass [hydrosilyl group of crosslinking agent in compounded component/alkenyl group in compounded component = 1.6 (mol/mol)], and 1,3,5,7-tetravinyltetra as a reaction control agent. 0.2 parts by mass of methylcyclotetrasiloxane, 0.08 parts by mass of ethynylcyclohexanol, 0.30 parts by mass of platinum catalyst (Pt concentration 1% by mass), and 10% ethanol solution of 1,2,3-benzotriazole. 0.2 part by mass was added and mixed with stirring for 15 minutes to obtain a liquid silicone composition.
The obtained silicone composition was subjected to viscosity measurement, physical property measurement of the cured product, and flame retardancy measurement in the same manner as in Example 1. The results are shown in Table 1.
［実施例３］
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が２１５で２３℃粘度が
１Ｐａ．ｓである直鎖状ジメチルポリシロキサン（ａ８）４０質量部、上記オルガノポリシロキサンレジン（ｂ１）５．０質量部、両末端がジメチルビニルシロキシ基で封鎖された平均重合度が４５０である直鎖状ジメチルポリシロキサン（ａ９）５．０質量部、上記ヒュームドシリカ（ｅ３）２７質量部、ヘキサメチルジシラザン２．０質量部、ビス（Ｎ，Ｎ－トリメチルシリルアミノ）メチルビニルシラン０．１質量部、及び水２．５質量部を室温で１２０分混合した。その後、上記直鎖状ジメチルポリシロキサン（ａ８）をさらに１０質量部添加し、２５℃で６０分混合後、１５０℃に昇温して１５０分撹拌を続けた。次いで、冷却し、上記直鎖状ジメチルポリシロキサン（ａ８）をさらに４０質量部、分子鎖両末端がトリメチルシロキシ基で封鎖され側鎖に５．０ｍｏｌ％のビニル基を有する平均重合度２００の直鎖状ジメチルポリシロキサン（ａ１０）５質量部、平均重合度が４２である分子鎖両末端にトリメチルシロキシ基を有する無官能性直鎖状ジメチルポリシロキサン５質量部を添加し、３０分混合後シリコーンベースを得た。
このシリコーンベース１４０質量部に、上記直鎖状ジメチルポリシロキサン（ａ８）をさらに５質量部、平均重合度が８６である分子鎖両末端にトリメチルシロキシ基を有する無官能性直鎖状ジメチルポリシロキサン５質量部、上記架橋剤（ｃ２）を９．８０質量部［配合成分中の架橋剤のヒドロシリル基／配合成分中のアルケニル基＝１．５（モル／モル）］、分子鎖両末端がジメチルビニルシロキシ基で封鎖された平均重合度が１，０８０である直鎖状ジメチルポリシロキサン（ａ１１）２．５質量部、分子鎖両末端がジメチルビニルシロキシ基で封鎖された平均重合度が１８０である直鎖状ジメチルポリシロキサン（ａ１２）１．７質量部、白色着色剤として、酸化チタン（石原産業（株）製、タイペークＣＲ－６０）２．５質量部、黒色着色剤として、カーボン（電気化学（株）製、デンカブラック粒状）０．３０質量部、反応制御剤として１，３，５，７－テトラビニルテトラメチルシクロテトラシロキサンを０．２質量部、及びエチニルシクロヘキサノール０．０８質量部、白金触媒（Ｐｔ濃度１質量％）１．００質量部、１，２，３－ベンゾトリアゾールのエタノール１０質量％溶液０．２質量部を添加し、１５分攪拌混合し、液状シリコーン組成物を得た。
得られたシリコーン組成物について、実施例１と同じ方法で、粘度測定、硬化物の物性測定及び難燃性測定を行った。結果を表１に示す。
[Example 3]
Both ends are blocked with dimethylvinylsiloxy groups, the average degree of polymerization is 215, and the viscosity at 23°C is 1 Pa. 40 parts by mass of linear dimethylpolysiloxane (a8) which is s, 5.0 parts by mass of the above organopolysiloxane resin (b1), a linear chain having an average degree of polymerization of 450 and having both ends blocked with dimethylvinylsiloxy groups. 5.0 parts by mass of dimethylpolysiloxane (a9), 27 parts by mass of the fumed silica (e3), 2.0 parts by mass of hexamethyldisilazane, 0.1 part by mass of bis(N,N-trimethylsilylamino)methylvinylsilane. , and 2.5 parts by mass of water were mixed at room temperature for 120 minutes. Thereafter, 10 parts by mass of the linear dimethylpolysiloxane (a8) was further added, and after mixing at 25°C for 60 minutes, the temperature was raised to 150°C and stirring was continued for 150 minutes. Next, after cooling, 40 parts by mass of the linear dimethylpolysiloxane (a8) was added to the linear dimethylpolysiloxane (a8), which had an average degree of polymerization of 200 and had both ends of the molecular chain blocked with trimethylsiloxy groups and 5.0 mol% of vinyl groups in the side chains. 5 parts by mass of linear dimethylpolysiloxane (a10) and 5 parts by mass of non-functional linear dimethylpolysiloxane having trimethylsiloxy groups at both ends of the molecular chain with an average degree of polymerization of 42 were added, and after mixing for 30 minutes, silicone was formed. Got the base.
To 140 parts by mass of this silicone base, 5 parts by mass of the above-mentioned linear dimethylpolysiloxane (a8) was added, a non-functional linear dimethylpolysiloxane having trimethylsiloxy groups at both ends of the molecular chain and having an average degree of polymerization of 86. 5 parts by mass, 9.80 parts by mass of the above crosslinking agent (c2) [hydrosilyl group of crosslinking agent in compounded component/alkenyl group in compounded component = 1.5 (mol/mol)], both ends of the molecular chain are dimethyl 2.5 parts by mass of linear dimethylpolysiloxane (a11) which is capped with vinylsiloxy groups and has an average degree of polymerization of 1,080; both ends of the molecular chain are capped with dimethylvinylsiloxy groups and has an average degree of polymerization of 180. 1.7 parts by mass of a certain linear dimethylpolysiloxane (a12), 2.5 parts by mass of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Taipeiku CR-60) as a white colorant, and carbon (electronic) as a black colorant. Kagaku Co., Ltd., Denka Black granules) 0.30 parts by mass, 0.2 parts by mass of 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane as a reaction control agent, and 0.08 parts by mass of ethynylcyclohexanol. 1.00 parts by mass of a platinum catalyst (Pt concentration 1% by mass) and 0.2 parts by mass of a 10% by mass solution of 1,2,3-benzotriazole in ethanol were added and mixed with stirring for 15 minutes to form a liquid silicone composition. I got it.
The obtained silicone composition was subjected to viscosity measurement, physical property measurement of the cured product, and flame retardancy measurement in the same manner as in Example 1. The results are shown in Table 1.
［比較例１］
実施例１において、上記架橋剤（ｃ１）を６．５０質量部［配合成分中の架橋剤のヒドロシリル基／配合成分中のアルケニル基＝１．８（モル／モル）］とした以外は、実施例１を繰り返して液状シリコーン組成物を得た。
得られたシリコーン組成物について、実施例１と同じ方法で、粘度測定、硬化物物性測定及び難燃性測定を行った。結果を表１に記載した。
[Comparative example 1]
In Example 1, the crosslinking agent (c1) was 6.50 parts by mass [hydrosilyl group of crosslinking agent in compounded component/alkenyl group in compounded component = 1.8 (mol/mol)]. Example 1 was repeated to obtain a liquid silicone composition.
The obtained silicone composition was subjected to viscosity measurement, cured product physical property measurement, and flame retardancy measurement in the same manner as in Example 1. The results are shown in Table 1.
［比較例２］
実施例１において、上記架橋剤（ｃ１）を５．００質量部［配合成分中の架橋剤のヒドロシリル基／配合成分中のアルケニル基＝１．４（モル／モル）］とした以外は、実施例１を繰り返して液状シリコーン組成物を得た。
得られたシリコーン組成物について、実施例１と同じ方法で、粘度測定、硬化物物性測定及び難燃性測定を行った。結果を表１に記載した。
[Comparative example 2]
In Example 1, the above crosslinking agent (c1) was changed to 5.00 parts by mass [hydrosilyl group of crosslinking agent in compounded component/alkenyl group in compounded component = 1.4 (mol/mol)]. Example 1 was repeated to obtain a liquid silicone composition.
The obtained silicone composition was subjected to viscosity measurement, cured product physical property measurement, and flame retardancy measurement in the same manner as in Example 1. The results are shown in Table 1.
［比較例３］
実施例１において、架橋剤（ｃ１）を上記比較用架橋剤（ｃ３）３．２７質量部［配合成分中の架橋剤のヒドロシリル基／配合成分中のアルケニル基＝１．６（モル／モル）］にした以外は、実施例１を繰り返して液状シリコーン組成物を得た。
得られたシリコーン組成物について、実施例１と同じ方法で、粘度測定、硬化物物性測定及び難燃性測定を行った。結果を表１に記載した。
[Comparative example 3]
In Example 1, the crosslinking agent (c1) was replaced with 3.27 parts by mass of the comparative crosslinking agent (c3) [hydrosilyl group of crosslinking agent in compounded component/alkenyl group in compounded component = 1.6 (mol/mol)] A liquid silicone composition was obtained by repeating Example 1 except that the following was changed.
The obtained silicone composition was subjected to viscosity measurement, cured product physical property measurement, and flame retardancy measurement in the same manner as in Example 1. The results are shown in Table 1.
［比較例４］
実施例１において、架橋剤（ｃ１）を上記比較用架橋剤（ｃ４）１０．６０質量部［配合成分中の架橋剤のヒドロシリル基／配合成分中のアルケニル基＝１．６（モル／モル）］以外は、実施例１を繰り返して液状シリコーン組成物を得た。
得られたシリコーン組成物について、実施例１と同じ方法で、粘度測定、硬化物物性測定及び難燃性測定を行った。結果を表１に記載した。
[Comparative example 4]
In Example 1, the crosslinking agent (c1) was replaced with 10.60 parts by mass of the comparative crosslinking agent (c4) [hydrosilyl group of crosslinking agent in the compounded component/alkenyl group in the compounded component = 1.6 (mol/mol)] Except for the following steps, Example 1 was repeated to obtain a liquid silicone composition.
The obtained silicone composition was subjected to viscosity measurement, cured product physical property measurement, and flame retardancy measurement in the same manner as in Example 1. The results are shown in Table 1.
［比較例５］
実施例２において、架橋剤（ｃ１）を上記比較用架橋剤（ｃ４）５．９０質量部［配合成分中の架橋剤のヒドロシリル基／配合成分中のアルケニル基＝１．６（モル／モル）］以外は、実施例２を繰り返して液状シリコーン組成物を得た。
得られたシリコーン組成物について、実施例１と同じ方法で、粘度測定、硬化物物性測定及び難燃性測定を行った。結果を表１に記載した。
[Comparative example 5]
In Example 2, the crosslinking agent (c1) was replaced with 5.90 parts by mass of the comparative crosslinking agent (c4) [hydrosilyl group of crosslinking agent in compounded component/alkenyl group in compounded component = 1.6 (mol/mol)] Except for the following steps, Example 2 was repeated to obtain a liquid silicone composition.
The obtained silicone composition was subjected to viscosity measurement, cured product physical property measurement, and flame retardancy measurement in the same manner as in Example 1. The results are shown in Table 1.
Claims (7)
（Ｂ）Ｒ１ ３ＳｉＯ１／２単位（式中、Ｒ１は互いに独立に１価炭化水素基である）とＳｉＯ４／２単位を含有し、ＳｉＯ４／２単位に対するＲ１ ３ＳｉＯ１／２単位のモル比［Ｒ１ ３ＳｉＯ１／２／ＳｉＯ４／２］が０．５～１．５であり、アルケニル基含有量が１×１０－４～５×１０－３ｍｏｌ／ｇである三次元網状構造のオルガノポリシロキサンレジン：３～５０質量部
（Ｃ）下記式（１）で示される直鎖状のオルガノハイドロジェンポリシロキサン
：前記（Ａ）成分及び（Ｂ）成分中のケイ素原子結合アルケニル基の総数に対して（Ｃ）成分中のケイ素原子結合水素原子の個数の比が１．５～１．７となる量
（Ｄ）付加反応触媒：触媒量
（Ｅ）ＢＥＴ法による比表面積１００ｍ２／ｇ以上のヒュームドシリカ：１０～５０質量部、及び
（Ｆ）トリアゾール化合物：０．００１～０．５質量部
を含有する、付加硬化型シリコーン組成物。 (A) 100 parts by mass of organopolysiloxane that is liquid at 23°C and has two or more alkenyl groups in one molecule that bond to silicon atoms;
(B) Contains R 1 3 SiO 1/2 units (in the formula, R 1 is a monovalent hydrocarbon group independently of each other) and SiO 4/2 units, and R 1 3 SiO 1 to SiO 4/2 units /2 unit molar ratio [R 1 3 SiO 1/2 /SiO 4/2 ] is 0.5 to 1.5, and the alkenyl group content is 1×10 −4 to 5×10 −3 mol/g. Organopolysiloxane resin with a three-dimensional network structure: 3 to 50 parts by mass (C) Linear organohydrogenpolysiloxane represented by the following formula (1)
: An amount such that the ratio of the number of silicon-bonded hydrogen atoms in component (C) to the total number of silicon-bonded alkenyl groups in components (A) and (B) is 1.5 to 1.7. D) Addition reaction catalyst: catalyst amount
(E) An addition-curing silicone composition containing 10 to 50 parts by mass of fumed silica having a specific surface area of 100 m 2 /g or more by BET method, and (F) 0.001 to 0.5 parts by mass of a triazole compound. .
7. The method for producing a flame-retardant silicone rubber composition according to claim 6, comprising the step of curing the addition-curing silicone composition to obtain a silicone rubber molded product after molding, the curing method comprising: primary vulcanization. The above-mentioned manufacturing method is characterized in that:
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| CN117004234A (en) * | 2023-10-07 | 2023-11-07 | 广州市瑞合新材料科技有限公司 | Flame-retardant wire and cable silicone rubber and preparation method thereof |
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| CN117004234A (en) * | 2023-10-07 | 2023-11-07 | 广州市瑞合新材料科技有限公司 | Flame-retardant wire and cable silicone rubber and preparation method thereof |
| CN117004234B (en) * | 2023-10-07 | 2023-12-19 | 广州市瑞合新材料科技有限公司 | Flame-retardant wire and cable silicone rubber and preparation method thereof |
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