JP2019073611A - Curable organopolysiloxane composition - Google Patents
Curable organopolysiloxane composition Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 67
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 125000000732 arylene group Chemical group 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 11
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 12
- 239000000565 sealant Substances 0.000 claims description 12
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 41
- -1 Polysiloxanes Polymers 0.000 description 37
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 8
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 8
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002683 reaction inhibitor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- GVCIEWAYDUQTTQ-UHFFFAOYSA-J 1,2,3,4,5,6-hexamethylbenzene;ruthenium(2+);tetrachloride Chemical compound Cl[Ru]Cl.Cl[Ru]Cl.CC1=C(C)C(C)=C(C)C(C)=C1C.CC1=C(C)C(C)=C(C)C(C)=C1C GVCIEWAYDUQTTQ-UHFFFAOYSA-J 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 210000004899 c-terminal region Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 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 1
- YUYGUQQDGRTJMA-UHFFFAOYSA-M cyclopentane;ruthenium(1+);triphenylphosphane;chloride Chemical compound [Ru]Cl.[CH]1[CH][CH][CH][CH]1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YUYGUQQDGRTJMA-UHFFFAOYSA-M 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明は、主鎖中にアリーレン基を有するオルガノポリシロキサンを主剤（ベースポリマー）として含有し、かつ、ルテニウム硬化触媒を含有する硬化性オルガノポリシロキサン組成物に関し、特には、高い耐熱性を有する硬化物を与える硬化性オルガノポリシロキサン組成物、及び該組成物の硬化物を有する物品等に関する。 The present invention relates to a curable organopolysiloxane composition containing an organopolysiloxane having an arylene group in its main chain as a main component (base polymer) and containing a ruthenium curing catalyst, and in particular, having high heat resistance. The present invention relates to a curable organopolysiloxane composition giving a cured product, an article having a cured product of the composition, and the like.
ケイ素−酸素結合の繰り返し単位をもつポリシロキサン、いわゆるシリコーン樹脂又はシリコーンゴムは、一般的に耐熱性、耐候性、耐寒性、耐油性、耐薬品性、柔軟性等の特徴を有し、電気電子材料、シーラント、車載用部品等に広く用いられている。通常、これらの用途に用いられるシリコーン樹脂又はシリコーンゴムは、高耐熱性が要求されており、高耐熱性のシリコーン樹脂又はシリコーンゴムを得るために、セリウム塩を用いた耐熱性付与等に代表されるように（特許文献１）、希土類元素、チタン、ジルコニウム、マンガン、鉄、コバルト、ニッケル等の金属の酸化物、ケイ酸塩、脂肪酸塩又は炭酸塩を添加したり、シリカ等のフィラーを添加したりする手法がある。 Polysiloxanes having silicon-oxygen repeating units, so-called silicone resins or silicone rubbers, generally have characteristics such as heat resistance, weather resistance, cold resistance, oil resistance, chemical resistance, flexibility, etc. It is widely used in materials, sealants, automotive parts and the like. Generally, silicone resins or silicone rubbers used in these applications are required to have high heat resistance, and are typified by heat resistance imparting using a cerium salt, etc., in order to obtain highly heat resistant silicone resins or silicone rubbers. (Patent Document 1), rare earth elements, oxides of metals such as titanium, zirconium, manganese, iron, cobalt, nickel, silicates, fatty acid salts or carbonates, or fillers such as silica There is a way to do it.
しかし、上記の手法においては希土類元素の入手の安定性が問題となったり、事前に金属塩をオルガノポリシロキサンと混合し、加熱処理した反応生成物の添加が必要なため、工程の短縮化が問題となる（特許文献１及び２）。 However, in the above-mentioned method, the stability of the acquisition of the rare earth element becomes a problem, or the metal salt is mixed with the organopolysiloxane in advance, and it is necessary to add the heat-treated reaction product. It becomes a problem (patent documents 1 and 2).
したがって、本発明は、上記問題点がなく、高耐熱性の硬化物を与える硬化性オルガノポリシロキサン組成物、及び該組成物の硬化物を用いた電気電子部品、オイルシール、シーラント等を提供することを目的とする。 Accordingly, the present invention provides a curable organopolysiloxane composition which does not have the above problems and gives a cured product having high heat resistance, and an electric / electronic component, an oil seal, a sealant and the like using the cured product of the composition. The purpose is
本発明者らは、上記目的を達成するために鋭意研究を行った結果、主鎖中にアリーレン基を導入し、末端にビニル基を有するアリーレン基を有するオルガノポリシロキサン、１分子中に３個以上のＳｉＨ基を有するオルガノハイドロジェンポリシロキサン及びルテニウム触媒を含有する硬化性オルガノポリシロキサン組成物が高耐熱性の硬化物を与えることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors introduced an arylene group in the main chain, and an organopolysiloxane having an arylene group having a vinyl group at an end, three in one molecule. The inventors have found that a curable organopolysiloxane composition containing an organohydrogenpolysiloxane having a SiH group and a ruthenium catalyst gives a cured product having high heat resistance, and completed the present invention.
従って、本発明は、下記の硬化性オルガノポリシロキサン組成物、及び該組成物の硬化物を用いた電気電子部品、オイルシール、シーラント等を提供するものである。 Accordingly, the present invention provides the following curable organopolysiloxane composition, and electric and electronic parts, oil seals, sealants and the like using the cured product of the composition.
［１］
（Ａ）下記一般式（１）で示されるオルガノポリシロキサン：１００質量部、
（式（１）中、Ｒ１は−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）であり、Ｒ２は同一又は異種の炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基及びそれらの基の水素原子の一部がハロゲン原子で置換された基から選ばれる基であり、Ａｒは炭素数６以上のアリーレン基であり、ａは１〜１，０００の整数であり、ｂは１〜５，０００の整数であり、ａ＋ｂは１０〜６，０００の整数である。なお、各繰り返し単位の配列はランダムでもよい。）
（Ｂ）１分子中に３個以上のＳｉＨ基を有するオルガノハイドロジェンポリシロキサン：（Ａ）成分１００質量部に対して１〜２０質量部、及び
（Ｃ）ルテニウム硬化触媒：触媒量、
を含有する硬化性オルガノポリシロキサン組成物。
［２］
（Ｂ）成分が下記一般式（２）
（式（２）中、Ｒ２は同一又は異種の炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基及びそれらの基の水素原子の一部がハロゲン原子で置換された基から選ばれる基を示す。式（２）中、Ａは水素原子又はメチル基であり、ｃ、ｄはそれぞれ０〜６０の整数であり、ｃ＋ｄは１〜１２０の整数である。１分子中に３個以上のＳｉＨ基を有する。）で示されるオルガノハイドロジェンポリシロキサンである［１］に記載の硬化性オルガノポリシロキサン組成物。
［３］
（Ｃ）成分が下記一般式（３）で示されるルテニウム化合物を含有するルテニウム硬化触媒である［１］又は［２］に記載の硬化性オルガノポリシロキサン組成物。
（式（３）中、Ｒ３は水素原子、ヘテロ原子及び／若しくは芳香族環を含有してもよい炭素数２〜５０の炭化水素配位子を示す。式（３）中、Ｘはハロゲン原子であり、ｅは１〜５の整数、ｆ及びｇは０〜２０の整数である。但し、ｆ＝ｇ＝０の場合を除く。）
［４］
（Ｃ）成分が下記一般式（４）で示されるルテニウム化合物を含有するルテニウム硬化触媒である［１］から［３］のいずれか１項に記載の硬化性オルガノポリシロキサン組成物。
（式（４）中、Ａｒは炭素数６〜５０のη６−アレーン配位子を示し、Ｘはハロゲン原子であり、ｉは１〜５の整数、ｊ及びｋは０〜２０の整数である。）
［５］
［１］から［４］のいずれか１項に記載の硬化性オルガノポリシロキサン組成物の硬化物層を有する電気電子部品。
［６］
［１］から［４］のいずれか１項に記載の硬化性オルガノポリシロキサン組成物の硬化物からなるオイルシール。
［７］
［１］から［４］のいずれか１項に記載の硬化性オルガノポリシロキサン組成物の硬化物からなるシーラント。
[1]
(A) Organopolysiloxane represented by the following general formula (1): 100 parts by mass,
(In formula (1), R 1 is —Si (CH 3 ) 2 (—CH = CH 2 ), R 2 is the same or different alkyl group having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms Ar is a arylene group having 6 or more carbon atoms, and a is an integer of 1 to 1,000. b is an integer of 1 to 5,000, and a + b is an integer of 10 to 6,000. The arrangement of each repeating unit may be random.)
(B) Organohydrogenpolysiloxanes having three or more SiH groups in one molecule: 1 to 20 parts by mass with respect to 100 parts by mass of (A) component, and (C) Ruthenium curing catalyst: catalytic amount,
Curable organopolysiloxane composition containing
[2]
Component (B) has the following general formula (2)
(In the formula (2), R 2 is the same or different alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and a group in which part of hydrogen atoms of those groups is substituted with a halogen atom In the formula (2), A represents a hydrogen atom or a methyl group, c and d each represent an integer of 0 to 60, and c + d represents an integer of 1 to 120. 3 in 1 molecule The curable organopolysiloxane composition according to [1], which is an organohydrogenpolysiloxane represented by the formula (1) having at least one SiH group.
[3]
The curable organopolysiloxane composition according to [1] or [2], which is a ruthenium curing catalyst wherein the component (C) contains a ruthenium compound represented by the following general formula (3).
(In the formula (3), R 3 represents a hydrogen atom, a heteroatom and / or a hydrocarbon ligand having 2 to 50 carbon atoms which may contain an aromatic ring, and in the formula (3), X represents a halogen It is an atom, e is an integer of 1 to 5 and f and g are integers of 0 to 20, except when f = g = 0)
[4]
The curable organopolysiloxane composition according to any one of [1] to [3], which is a ruthenium curing catalyst containing as the component (C) a ruthenium compound represented by the following general formula (4).
(In the formula (4), Ar represents an η 6 -arene ligand having 6 to 50 carbon atoms, X is a halogen atom, i is an integer of 1 to 5, j and k are integers of 0 to 20 is there.)
[5]
An electric and electronic component having a cured product layer of the curable organopolysiloxane composition according to any one of [1] to [4].
[6]
An oil seal comprising a cured product of the curable organopolysiloxane composition according to any one of [1] to [4].
[7]
A sealant comprising a cured product of the curable organopolysiloxane composition according to any one of [1] to [4].
本発明の硬化性オルガノポリシロキサン組成物は、原料入手が容易であり、本発明の硬化性オルガノポリシロキサン組成物の硬化物は耐熱性が高く、電気電子部品、オイルシール、シーラント等に好適である。近年、電気電子部品の高性能化及び小型化により、その動作温度は高温化している。これに伴い、電気電子部品に使用される部材も高耐熱性が要求されてきている。この様な状況の中で、本発明の硬化性オルガノポリシロキサン組成物は、現在広く用いられている、白金触媒を利用した付加反応硬化型オルガノポリシロキサン組成物と比較して、さらなる高耐熱性を発現させることが可能となるため、高温環境下での使用が要求される種々の電子部材の性能向上に大きく貢献可能なことが期待される。 The curable organopolysiloxane composition of the present invention is easily obtainable as a raw material, and the cured product of the curable organopolysiloxane composition of the present invention has high heat resistance and is suitable for electrical and electronic parts, oil seals, sealants, etc. is there. In recent years, the operating temperature has become high due to high performance and miniaturization of electric and electronic components. Along with this, members used for electrical and electronic parts are also required to have high heat resistance. Under such circumstances, the curable organopolysiloxane composition of the present invention has a further higher heat resistance than the currently widely used addition reaction-curable organopolysiloxane composition utilizing a platinum catalyst. It is expected that it can greatly contribute to the performance improvement of various electronic members that are required to be used under high temperature environment.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
［（Ａ）成分］
（Ａ）成分は、本発明の硬化性オルガノポリシロキサン組成物の主剤（ベースポリマー）であり、主鎖中に、シルアリーレンシロキサン単位［−Ｓｉ（Ｒ２）２−Ａｒ−Ｓｉ（Ｒ２）２Ｏ−］としてアリーレン基を有すると共に、分子鎖両末端にビニル基（ビニルジメチルシロキシ基）を有する直鎖状のオルガノポリシロキサンであり、下記一般式（１）で示されるものである。
（式（１）中、Ｒ１は−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）であり、Ｒ２は同一又は異種の炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基及びそれらの基の水素原子の一部がハロゲン原子で置換された基から選ばれる基であり、Ａｒは炭素数６以上のアリーレン基であり、ａは１〜１，０００の整数であり、ｂは１〜５，０００の整数であり、ａ＋ｂは１０〜６，０００の整数である。なお、各繰り返し単位の配列はランダムでもよい。）
[(A) component]
The component (A) is a main component (base polymer) of the curable organopolysiloxane composition of the present invention, and the silarylene siloxane unit [-Si (R 2 ) 2 -Ar-Si (R 2 ) is contained in the main chain. A linear organopolysiloxane having an arylene group as 2 O-] and a vinyl group (vinyldimethylsiloxy group) at both molecular chain terminals, and is represented by the following general formula (1).
(In formula (1), R 1 is —Si (CH 3 ) 2 (—CH = CH 2 ), R 2 is the same or different alkyl group having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms Ar is a arylene group having 6 or more carbon atoms, and a is an integer of 1 to 1,000. b is an integer of 1 to 5,000, and a + b is an integer of 10 to 6,000. The arrangement of each repeating unit may be random.)
上記の炭素数１〜２０のアルキル基としてはメチル基、エチル基、プロピル基、シクロヘキシル基等が例示され、上記の炭素数６〜２０のアリール基としてはフェニル基等が例示され、上記のハロゲン置換基としては３，３，３−トリフルオロプロピル基等が例示される。Ａｒは炭素数６以上のアリーレン基であり、特に６〜２０のアリーレン基が好ましく、炭素数６以上のアリーレン基としては、ｏ，ｍ，ｐ−フェニレン基、ナフチレン基、ビフェニレン基等が例示される。 Examples of the above-mentioned alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl and cyclohexyl groups. Examples of the above-mentioned aryl group having 6 to 20 carbon atoms include phenyl group and the like, and the above-mentioned halogens Examples of substituents include 3,3,3-trifluoropropyl and the like. Ar is an arylene group having 6 or more carbon atoms, preferably an arylene group having 6 to 20 carbons, and as the arylene group having 6 or more carbon atoms, o, m, p-phenylene group, naphthylene group, biphenylene group, etc. are exemplified Ru.
一般式（１）において、分子中のシルアリーレンシロキサン単位［−Ｓｉ（Ｒ２）２−Ａｒ−Ｓｉ（Ｒ２）２Ｏ−］の繰り返し数（重合度）を示すａは１〜１，０００の整数、好ましくは５〜６００の整数、より好ましくは１０〜３００程度の整数であり、分子中のジシロキサン単位［−Ｓｉ（Ｒ２）２Ｏ−］の繰り返し数（重合度）を示すｂは１〜５，０００の整数、好ましくは５０〜１，２００の整数、より好ましくは８０〜１，０００程度の整数であり、ａ＋ｂは１０〜６，０００の整数であり、通常、１０〜５，３００の整数、好ましくは１００〜１，６００の整数、より好ましくは２００〜１，２００程度の整数である。また、ｂ≧ａであることが好ましく、ｂ≧ａのとき、１００×ａ／（ａ＋ｂ）＝４〜５０であることが好ましい。例えば、ａ＝１００、ｂ＝１，９００のとき、１００×ａ／（ａ＋ｂ）＝５となり、ａ＝１００、ｂ＝１００であれば、１００×ａ／（ａ＋ｂ）＝５０である。また、１００×ａ／（ａ＋ｂ）＝５０より大きい場合、式（１）で示されるオルガノポリシロキサンは室温（２５℃±１０℃）下で高粘度オイル又は固体となり、作業性が低下する場合がある。逆に１００×ａ／（ａ＋ｂ）＝４より小さい場合、式（１）で示されるオルガノポリシロキサン中のアリーレン基の割合が少ないため、十分な耐熱性を得ることが困難となる場合がある。 In the general formula (1), a representing the repeating number (degree of polymerization) of the silarylene siloxane unit [-Si (R 2 ) 2 -Ar-Si (R 2 ) 2 O-] in the molecule is 1 to 1,000. Is an integer of preferably 5 to 600, more preferably about 10 to 300, and b represents the number of repetitions of the disiloxane unit [-Si (R 2 ) 2 O-] in the molecule (degree of polymerization) Is an integer of 1 to 5,000, preferably an integer of 50 to 1,200, and more preferably an integer of about 80 to 1,000, and a + b is an integer of 10 to 6,000, usually 10 to 5 And an integer of about 300, preferably an integer of about 100 to about 1,600, and more preferably an integer of about 200 to about 1,200. Further, b a a is preferable, and when b 、 a, it is preferable that 100 x a / (a + b) = 4 to 50. For example, when a = 100 and b = 1,900, 100 × a / (a + b) = 5, and when a = 100 and b = 100, 100 × a / (a + b) = 50. When 100 x a / (a + b) = 50 or more, the organopolysiloxane represented by the formula (1) becomes a high viscosity oil or solid at room temperature (25 ° C ± 10 ° C), which may lower the workability. is there. Conversely, when the ratio is smaller than 100 × a / (a + b) = 4, it may be difficult to obtain sufficient heat resistance because the proportion of arylene groups in the organopolysiloxane represented by the formula (1) is small.
一般式（１）で示される化合物において、シルアリーレンシロキサン単位［−Ｓｉ（Ｒ２）２−Ａｒ−Ｓｉ（Ｒ２）２Ｏ−］とジオルガノシロキサン単位［−Ｓｉ（Ｒ２）２Ｏ−］との配列はランダムでもよい。 In the compound represented by the general formula (1), a silarylene siloxane unit [-Si (R 2 ) 2 -Ar-Si (R 2 ) 2 O-] and a diorganosiloxane unit [-Si (R 2 ) 2 O- The arrangement of] may be random.
一般式（１）で示される化合物としては、フェニレン基、ナフチレン基及び／又はビフェニレン基を有するオルガノポリシロキサン等が挙げられる。これらは、１種単独で使用してもよいし、２種以上の組み合わせで使用してもよい。 As a compound shown by General formula (1), the organopolysiloxane etc. which have a phenylene group, a naphthylene group, and / or a biphenylene group are mentioned. These may be used alone or in combination of two or more.
本発明において、繰り返し単位の繰り返し数（重合度）は、例えば、テトラヒドロフラン等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。より具体的には、上記一般式（１）で示される化合物等のポリスチレン換算での数平均分子量は、ゲルパーミエーションクロマトグラフィ分析において、東ソー株式会社製のカラム：ＴＳＫｇｅｌ Ｓｕｐｅｒ Ｈ２５００（１本）及びＴＳＫｇｅｌ Ｓｕｐｅｒ ＨＭ−Ｎ（１本）、溶媒：テトラヒドロフラン、流量：０．６ｍＬ／ｍｉｎ、検出器：ＲＩ（４０℃）、カラム温度：４０℃、注入量：５０μＬ、サンプル濃度：０．３質量％の条件にて測定した値である（以下同じ）。 In the present invention, the repeating number (degree of polymerization) of the repeating unit can be determined, for example, as a polystyrene-equivalent number average degree of polymerization (or number average molecular weight) in gel permeation chromatography (GPC) analysis using tetrahydrofuran or the like as a developing solvent. . More specifically, the number average molecular weight of the compound represented by the above general formula (1) and the like in terms of polystyrene is determined by gel permeation chromatography analysis using a column manufactured by Tosoh Corp .: TSKgel Super H2500 (one) and TSKgel Super HM-N (one), solvent: tetrahydrofuran, flow rate: 0.6 mL / min, detector: RI (40 ° C), column temperature: 40 ° C, injection amount: 50 μL, sample concentration: 0.3% by mass It is the value measured under the conditions (the same applies below).
（Ａ）成分は、本発明の組成物中、好ましくは１７〜９９質量％、より好ましくは５０〜９８質量％含有する。 The component (A) is contained in the composition of the present invention preferably at 17 to 99% by mass, more preferably 50 to 98% by mass.
［（Ｂ）成分］
（Ｂ）成分は、本発明の硬化性オルガノポリシロキサン組成物の架橋剤であり、上記（Ａ）成分と付加反応し、アリーレン基を有するオルガノポリシロキサン硬化物を形成する構成要素である。該（Ｂ）成分は、１分子中に３個以上のＳｉＨ基を有するオルガノハイドロジェンポリシロキサンであり、下記一般式（２）で示される、分子鎖（両）末端及び／又は分子鎖途中（非末端）のケイ素原子に結合した水素原子（ＳｉＨ基）を１分子中に３個以上有す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が好ましい。
（式（２）中、Ｒ２は同一又は異種の炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基及びそれらの基の水素原子の一部がハロゲン原子で置換された基から選ばれる基を示す。式（２）中、Ａは水素原子又はメチル基であり、ｃ，、ｄはそれぞれ０〜６０の整数であり、ｃ＋ｄは１〜１２０の整数である。）
[(B) component]
The component (B) is a crosslinking agent for the curable organopolysiloxane composition of the present invention, and is a component which is addition-reacted with the component (A) to form a cured organopolysiloxane having an arylene group. The component (B) is an organohydrogenpolysiloxane having three or more SiH groups in one molecule, and has a molecular chain (both) terminal and / or a molecular chain midway represented by the following general formula (2) It is preferable that it is a linear organohydrogenpolysiloxane having three or more hydrogen atoms (SiH groups) bonded to a non-terminal silicon atom in one molecule.
(In the formula (2), R 2 is the same or different alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and a group in which part of hydrogen atoms of those groups is substituted with a halogen atom In the formula (2), A represents a hydrogen atom or a methyl group, c and d each represent an integer of 0 to 60, and c + d represents an integer of 1 to 120.
一般式（２）で示される化合物としては、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖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、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖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・ジフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖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・メチルフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖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、分子鎖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、分子鎖両末端トリメチルシロキシ基封鎖ジフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン・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。これらは、１種単独で使用してもよいし、２種以上の組み合わせで使用してもよい。 Examples of the compound represented by the general formula (2) include methylhydrogenpolysiloxane blocked by molecular chain both ends dimethylhydrogensiloxy group, dimethylhydrogensiloxy group blocked dimethylhydrogensiloxy group blocked dimethylhydrogensiloxy group, molecular Chain-terminated dimethylhydrogensiloxy group-capped diphenylsiloxane-methylhydrogensiloxane copolymer, molecular chain-terminated dimethylhydrogensiloxy group-capped methylphenylsiloxane-methylhydrogensiloxane copolymer, molecular chain-terminated dimethylhydrogensiloxy Blocked Dimethylsiloxane · Diphenylsiloxane · Methyl Hydrogen Siloxane Copolymer, Molecular Chain Both Ends Dimethyl Hydrogen Siloxy Group-Capped Dimethyl Siloxane · Methylphenyl Loxane / methyl hydrogen siloxane copolymer, methyl chain polysiloxane terminated with methylsiloxy group at both ends of molecular chain, trimethylsiloxy group capped with methylsiloxy group at both ends of chain, trimethylsiloxy group terminated with molecular chain both ends Blocked diphenyl siloxane / methyl hydrogen siloxane copolymer, Molecular chain both terminal trimethylsiloxy group blocked methyl phenyl siloxane / methyl hydrogen siloxane copolymer, Molecular chain both terminal trimethylsiloxy group blocked dimethyl siloxane / diphenyl siloxane / methyl hydrogen siloxane Copolymers, trimethylsiloxy group-blocked dimethyl siloxane, methyl phenyl siloxane, methyl hydrogen siloxane copolymer etc. It is. These may be used alone or in combination of two or more.
（Ｂ）成分のオルガノハイドロジェンポリシロキサン中のＳｉＨ基量は、５．０〜２，０００ ｍｍｏｌ／１００ｇであることが好ましく、１０〜１，５００ ｍｍｏｌ／１００ｇであることがより好ましい。
（Ｂ）成分のオルガノハイドロジェンポリシロキサンの粘度は特に限定されないが、作業性および分散性の観点から、２５℃における粘度が０．５〜１，０００ ｍＰａ・ｓであることが好ましく、１〜５００ ｍＰａ・ｓであることがより好ましい。なお、本発明における粘度は、回転粘度計（例えば、ＢＬ型、ＢＨ型、ＢＳ型、コーンプレート型、レオメータ等）により測定した値である。
The amount of SiH groups in the organohydrogenpolysiloxane of component (B) is preferably 5.0 to 2,000 mmol / 100 g, more preferably 10 to 1,500 mmol / 100 g.
The viscosity of the organohydrogenpolysiloxane of component (B) is not particularly limited, but in view of workability and dispersibility, the viscosity at 25 ° C. is preferably 0.5 to 1,000 mPa · s, and 1 to 1 More preferably, it is 500 mPa · s. The viscosity in the present invention is a value measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.).
本発明の組成物における（Ｂ）成分の配合量は、（Ａ）成分１００質量部に対して、１〜２０質量部であり、１〜１０質量部であることが好ましく、２〜５質量部であることがより好ましい。該（Ｂ）成分の配合量が１質量部未満であると硬化不良を引き起こし、目的の硬化物を得ることが不可能であったり、該（Ｂ）成分の配合量が２０質量部よりも多いと、期待される耐熱性硬化物を得ることが困難となったり、得られる硬化物が硬くなったりするおそれがある。また、同様の理由により、（Ｂ）成分は、（Ａ）成分中のビニル基に対する（Ｂ）成分中のＳｉＨ基のモル比が、０．８〜３モル／モル、好ましくは１．０〜２．５モル／モルとなる量で配合することもできる。 The compounding amount of the component (B) in the composition of the present invention is 1 to 20 parts by mass, preferably 1 to 10 parts by mass, and 2 to 5 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable that If the compounding amount of the component (B) is less than 1 part by mass, curing failure is caused, and it is impossible to obtain a target cured product, or the compounding amount of the component (B) is more than 20 parts by mass Thus, it may be difficult to obtain the expected heat resistant cured product, or the obtained cured product may become hard. In addition, for the same reason, the component (B) has a molar ratio of SiH group in the component (B) to vinyl group in the component (A) of 0.8 to 3 mol / mol, preferably 1.0 to It can also be blended in an amount of 2.5 mol / mol.
［（Ｃ）成分］
（Ｃ）成分は、（Ａ）成分中のビニル基と（Ｂ）成分中のヒドロシリル基との付加反応を促進し、硬化物を得るためのルテニウム硬化触媒であり、例えば、下記一般式（３）で示されるルテニウム化合物が挙げられる。
The component (C) is a ruthenium curing catalyst for accelerating the addition reaction of the vinyl group in the component (A) and the hydrosilyl group in the component (B) to obtain a cured product, and, for example, The ruthenium compound shown by) is mentioned.
式（３）中、Ｒ３は水素原子または、ヘテロ原子及び／若しくは芳香族環を有してもよい炭素数２〜５０の炭化水素配位子であり、該配位子としては、ベンゼン、シメン、シクロペンタジエン等のアレーン配位子；ブタジエン、シクロオクタジエン、アセチレン等のオレフィン配位子；アルキン配位子；アセチルアセトン、カルボニルに代表される様な酸素原子を配位中心として有する配位子；リン、窒素、硫黄等の配位性原子を有する配位子が挙げられる。
式（３）中、Ｘはハロゲン原子であり、好ましくは塩素原子である。ｅは１〜５の整数、ｆ及びｇは０〜２０の整数である。但し、ｆ＝ｇ＝０の場合を除く。
In the formula (3), R 3 is a hydrogen atom or a hydrocarbon ligand of 2 to 50 carbon atoms which may have a hetero atom and / or an aromatic ring, and examples of the ligand include benzene, Arene ligands such as cymene and cyclopentadiene; olefin ligands such as butadiene, cyclooctadiene and acetylene; alkyne ligands; ligands having an oxygen atom such as acetylacetone and carbonyl as a coordination center And ligands having coordinating atoms such as phosphorus, nitrogen and sulfur.
In formula (3), X is a halogen atom, preferably a chlorine atom. e is an integer of 1 to 5, and f and g are integers of 0 to 20. However, the case of f = g = 0 is excluded.
また上記ルテニウム化合物の中でも、入手の簡便性及び期待される耐熱性を発現させる観点から、下記一般式（４）で示されるルテニウム硬化触媒が好適である。
（式（４）中、Ａｒは炭素数６〜５０のη６−アレーン配位子を示し、Ｘはハロゲン原子であり、ｉは１〜５の整数、ｊ及びｋは０〜２０の整数である。）
Further, among the ruthenium compounds described above, a ruthenium curing catalyst represented by the following general formula (4) is preferable from the viewpoint of obtaining the convenience of obtaining and the expected heat resistance.
(In the formula (4), Ar represents an η 6 -arene ligand having 6 to 50 carbon atoms, X is a halogen atom, i is an integer of 1 to 5, j and k are integers of 0 to 20 is there.)
ルテニウム化合物の具体例としては、ルテニウム二核錯体である下記式（５）で表されるジ−μ−クロロ−ビス［クロロ（ｐ−シメン）ルテニウム（ＩＩ）］に代表されるハロゲン架橋アレーンルテニウム二核錯体及びその類縁体等が好ましい。
上記ルテニウム化合物を触媒として使用する際の状態は問わないが、他の成分との相溶性の観点から、トルエン等の有機溶媒に溶解させた溶液、もしくは該溶液を分散剤（例えば、オルガノポリシロキサン等）に分散させ、該有機溶媒を揮発させたものを該ルテニウム化合物含有硬化触媒として使用することが好ましい。分散剤として用いられるオルガノポリシロキサンとしては、下記式（６）で表される分子鎖中（分子鎖途中あるいは分子鎖非末端のジオルガノシロキサン単位中）にフェニル基を有するオルガノポリシロキサン等が挙げられる。
（式（６）中、Ｒ１は−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）であり、Ｒ２は同一又は異種の炭素数１〜２０のアルキル基及びその基の水素原子の一部がハロゲン原子で置換された基から選ばれる基であり、Ｒ４は炭素数６〜２０のアリール基及びそれらの基の水素原子の一部がハロゲン原子で置換された基から選ばれる基であり、ｌは１〜５，０００の整数、好ましくは５〜１，０００の整数、より好ましくは１０〜５００の整数であり、ｍは１〜１，０００の整数、好ましくは２〜２００の整数、より好ましくは３〜５０の整数であり、ｌ＋ｍは１０〜６，０００の整数、好ましくは２０〜１，２００の整数、より好ましくは３０〜６００の整数である。なお、各繰り返し単位の配列はランダムでもよい。）
The state when using the above-mentioned ruthenium compound as a catalyst is not limited, but from the viewpoint of compatibility with other components, a solution dissolved in an organic solvent such as toluene or a dispersant (for example, organopolysiloxane And the like, and the organic solvent volatilized is preferably used as the ruthenium compound-containing curing catalyst. Examples of the organopolysiloxane used as the dispersant include an organopolysiloxane having a phenyl group in the molecular chain represented by the following formula (6) (in the middle of the molecular chain or in the diorganosiloxane unit at the end of the molecular chain). Be
(In formula (6), R 1 is —Si (CH 3 ) 2 (—CH = CH 2 ), R 2 is the same or different alkyl group having 1 to 20 carbon atoms and one hydrogen atom of the group R 4 is a group selected from an aryl group having 6 to 20 carbon atoms and a group in which a part of the hydrogen atoms of these groups are substituted by a halogen atom; And l is an integer of 1 to 5,000, preferably an integer of 5 to 1,000, more preferably an integer of 10 to 500, m is an integer of 1 to 1,000, preferably an integer of 2 to 200 More preferably, it is an integer of 3 to 50, and l + m is an integer of 10 to 6,000, preferably an integer of 20 to 1,200, more preferably an integer of 30 to 600. The arrangement of each repeating unit May be random.)
式（６）で表される分子鎖中にフェニル基を有するオルガノポリシロキサンの具体例として、例えば、下記式（７）で示される様な分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体や該共重合体中のジフェニルシロキサン単位をメチルフェニルシロキサン単位で置換した分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体などが挙げられる。
（式（７）中、Ｍｅはメチル基を示し、Ｐｈはフェニル基を示す。）
As a specific example of the organopolysiloxane having a phenyl group in the molecular chain represented by the formula (6), for example, a molecular chain both terminal vinyldimethylsiloxy group-blocked dimethylsiloxane / diphenyl siloxane as shown by the following formula (7) The copolymer and the molecular chain both terminal vinyl dimethyl siloxy group block dimethylsiloxane * methylphenyl siloxane copolymer etc. which substituted the diphenyl siloxane unit in this copolymer by the methylphenyl siloxane unit etc. are mentioned.
(In the formula (7), Me represents a methyl group and Ph represents a phenyl group.)
本発明の組成物における（Ｃ）成分の配合量は、いわゆる触媒量でよく、好ましくは、（Ａ）成分に対して、ルテニウム原子の質量換算で０．１〜１，０００ｐｐｍ、より好ましくは５〜１００ｐｐｍである。これらの範囲から逸脱した配合を行うと、本発明の組成物の硬化物を得るための硬化時間の著しい増大や、該硬化物の高耐熱性が十分に発現されない可能性がある。 The compounding amount of the component (C) in the composition of the present invention may be a so-called catalytic amount, preferably 0.1 to 1,000 ppm, more preferably 5 with respect to the component (A) in terms of mass of ruthenium atom. ~ 100 ppm. If the formulation deviates from these ranges, the curing time for obtaining a cured product of the composition of the present invention may be significantly increased, and the high heat resistance of the cured product may not be sufficiently exhibited.
［耐熱性］
本発明の組成物を硬化して得られる硬化物の耐熱性に関して、２３０℃空気雰囲気下において初期の硬度と２３０℃にて６００時間経過後の硬度との差が、ＪＩＳ Ｋ７３１２に規定されるアスカー（Ｔｙｐｅ Ｃ）にて１５以下であることを特徴としており、この硬度差よりも大きい変化を呈する硬化物であると、高温下に曝された際の該硬化物の硬度変化が大きすぎるため、電気電子部品、オイルシール（自動車用オイルシール）、シーラント（建築用シーラント）等への用途に適さない。また、本発明の組成物を硬化して得られる硬化物に関して、２３０℃における６００時間経過後の質量変化が、初期値（０時間）の９０％以上の質量を維持することを特徴としている。質量変化が９０％未満の硬化物の場合、該硬化物から揮発する成分が多くなり、電気電子部品用途に用いた際の接点障害の要因となり得る。以上の点から上記条件を満たす本発明の組成物は、電気電子部品、オイルシール（自動車用オイルシール）、シーラント（建築用シーラント）等への用途に適している。
[Heat-resistant]
With regard to the heat resistance of a cured product obtained by curing the composition of the present invention, the difference between the initial hardness and the hardness after an elapse of 600 hours at 230 ° C. in an air atmosphere at 230 ° C. is asker defined in JIS K7312. (15) or less in (Type C), and if the cured product exhibits a change larger than this hardness difference, the hardness change of the cured product when exposed to high temperature is too large, Not suitable for use in electrical and electronic parts, oil seals (oil seals for automobiles), sealants (architectural sealants), etc. In addition, with respect to a cured product obtained by curing the composition of the present invention, it is characterized in that a mass change after lapse of 600 hours at 230 ° C. maintains a mass of 90% or more of the initial value (0 hour). In the case of a cured product having a mass change of less than 90%, the component volatilized from the cured product increases, which may cause contact failure when used in electrical and electronic component applications. From the above points, the composition of the present invention satisfying the above conditions is suitable for use in electric and electronic parts, oil seals (oil seals for automobiles), sealants (sealing sealants), and the like.
［その他の成分］
本発明の硬化性オルガノポリシロキサン組成物には、上記（Ａ）〜（Ｃ）成分以外にも、本発明の効果を損なわない範囲で任意成分を配合することができる。この任意成分としては、例えば、反応抑制剤、無機質充填剤、ケイ素原子結合水素原子及びケイ素原子結合アルケニル基を有しない無官能性オルガノポリシロキサン（いわゆる無官能性ジメチルシリコーンオイル等）、耐熱性付与剤、難燃性付与剤、チクソ性付与剤、顔料、染料等が挙げられる。
[Other ingredients]
Other than the components (A) to (C), optional components can be added to the curable organopolysiloxane composition of the present invention as long as the effects of the present invention are not impaired. Examples of such optional components include reaction inhibitors, inorganic fillers, nonfunctional organopolysiloxanes having no silicon-bonded hydrogen atoms and silicon-bonded alkenyl groups (so-called nonfunctional dimethylsilicone oil etc.), heat resistance Agents, flame retardants, thixotropes, pigments, dyes and the like.
反応抑制剤は、上記の付加反応等を抑制するための成分であって、具体的には、例えば、アセチレン系、アミン系、カルボン酸エステル系、亜リン酸エステル系等の反応抑制剤が挙げられる。 The reaction inhibitor is a component for suppressing the above-mentioned addition reaction etc. Specifically, for example, reaction inhibitors such as acetylene type, amine type, carboxylic acid ester type, phosphite type and the like are mentioned. Be
無機質充填剤としては、例えば、ヒュームドシリカ、結晶性シリカ、沈降性シリカ、中空フィラー、シルセスキオキサン、ヒュームド二酸化チタン、酸化マグネシウム、酸化亜鉛、酸化鉄、水酸化アルミニウム、炭酸マグネシウム、炭酸カルシウム、炭酸亜鉛、層状マイカ、カーボンブラック、ケイ藻土、ガラス繊維等の無機質充填剤；該無機質充填剤の表面を、オルガノアルコキシシラン化合物、オルガノクロロシラン化合物、オルガノシラザン化合物、低分子量シロキサン化合物等の有機ケイ素化合物で疎水化処理をした無機質充填剤等が挙げられる。また、シリコーンゴムパウダー、シリコーンレジンパウダー等を配合してもよい。 As the inorganic filler, for example, fumed silica, crystalline silica, precipitated silica, hollow filler, silsesquioxane, fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, aluminum carbonate, magnesium carbonate, calcium carbonate Inorganic fillers such as zinc carbonate, layered mica, carbon black, kieselguhr, glass fibers, etc .; organic inorganic compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, low molecular weight siloxane compounds, etc. The mineral filler etc. which hydrophobized with the silicon compound are mentioned. Also, silicone rubber powder, silicone resin powder, etc. may be blended.
本発明の硬化性オルガノポリシロキサン組成物及び該組成物の硬化物の製造方法
本発明の硬化性オルガノポリシロキサン組成物は、上記（Ａ）〜（Ｃ）成分、及び必要により、その他の成分の所定量を乾燥雰囲気中において均一に混合することにより得ることができる。
また、得られた硬化性オルガノポリシロキサン組成物は、１５０℃±１０℃で約１２〜４００時間、好ましくは２４〜１７０時間、より好ましくは３６〜１２０時間程度加熱することにより硬化するが、その成形方法、硬化条件などは、組成物の種類に応じた公知の方法、条件を採用することができる。
The curable organopolysiloxane composition of the present invention and the method for producing a cured product of the composition The curable organopolysiloxane composition of the present invention comprises the components (A) to (C) and, if necessary, other components. It can be obtained by uniformly mixing a predetermined amount in a dry atmosphere.
The curable organopolysiloxane composition obtained is cured by heating at 150 ° C. ± 10 ° C. for about 12 to 400 hours, preferably 24 to 170 hours, and more preferably 36 to 120 hours. As the molding method, curing conditions and the like, known methods and conditions depending on the type of composition can be adopted.
本発明の硬化性オルガノポリシロキサン組成物は、その硬化物が高い耐熱性を有することから、高温環境下で使用される電気電子部品、オイルシール、シーラント等として好適に使用でき、具体的には、本発明の硬化性オルガノポリシロキサン組成物の硬化物層を有する電気電子部品、該組成物の硬化物からなる自動車用オイルシール、該組成物の硬化物からなる建築用シーラント等を例示することができる。 The curable organopolysiloxane composition of the present invention can be suitably used as an electrical and electronic component, an oil seal, a sealant, etc. used in a high temperature environment, because the cured product has high heat resistance. An electric and electronic part having a cured product layer of the curable organopolysiloxane composition of the present invention, an oil seal for an automobile comprising the cured product of the composition, an architectural sealant comprising the cured product of the composition, etc. Can.
［実施例］
以下に、本発明を実施例及び比較例により具体的に説明するが、本発明は下記の実施例に制限されるものではない。
[Example]
EXAMPLES The present invention will be specifically described below by examples and comparative examples, but the present invention is not limited to the following examples.
室温は２５℃を示し、部は質量部を示し、（Ａ）成分の各重合度（ａ、ｂ）は、ゲルパーミエーションクロマトグラフィ分析において、東ソー株式会社製のカラム：ＴＳＫｇｅｌ Ｓｕｐｅｒ Ｈ２５００（１本）及びＴＳＫｇｅｌ Ｓｕｐｅｒ ＨＭ−Ｎ（１本）、溶媒：テトラヒドロフラン、流量：０．６ｍＬ／ｍｉｎ、検出器：ＲＩ（４０℃）、カラム温度：４０℃、注入量：５０μＬ、サンプル濃度：０．３質量％の条件にて測定した数平均重合度を示す。粘度は２５℃における回転粘度計による測定値である。 The room temperature indicates 25 ° C., part indicates parts by mass, and the degree of polymerization (a, b) of the component (A) is a column manufactured by Tosoh Corporation: TSK gel Super H2500 (one) in gel permeation chromatography analysis And TSKgel Super HM-N (one), solvent: tetrahydrofuran, flow rate: 0.6 mL / min, detector: RI (40 ° C.), column temperature: 40 ° C., injection amount: 50 μL, sample concentration: 0.3 mass It shows the number average degree of polymerization measured under the condition of%. The viscosity is a value measured by a rotational viscometer at 25 ° C.
［実施例１］
（Ａ）成分である、下記式（１）で表されるフェニレン基を有するオルガノポリシロキサン（Ｒ１＝−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）、Ｒ２＝メチル基、Ａ＝ｐ−フェニレン基、ａ＝１１、ｂ＝２５０）１００部に対して、（Ｃ）成分である、下記式（５）で表されるジ−μ−クロロ−ビス［クロロ（ｐ−シメン）ルテニウム（ＩＩ）］を、下記式（７）で表される分子鎖中にフェニル基を有するオルガノポリシロキサンに分散した溶液５．９部（（Ａ）成分に対してルテニウム原子換算で１６ｐｐｍ）及び（Ｂ）成分である、下記式（２）で表され、２５℃での粘度が１００ ｍＰａ・ｓの分子鎖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（Ａ＝メチル基、Ｒ２＝メチル基、ｃ＝１６、ｄ＝２８、ＳｉＨ量；５．５ ｍｍｏｌ／１００ｇ）２．４部を添加し、室温下で均一になるまでよく混合し、遠心脱泡することで硬化性組成物１とし、該組成物１を１５０℃、１００時間加熱処理することで硬化物１を作製した。
Example 1
An organopolysiloxane having a phenylene group represented by the following formula (1) which is a component (A) (R 1 = -Si (CH 3 ) 2 (-CH = CH 2 ), R 2 = methyl group, A = Di-μ-chloro-bis [chloro (p-cymene) ruthenium represented by the following formula (5), which is the component (C), relative to 100 parts of a p-phenylene group, a = 11, b = 250) A solution obtained by dispersing (II)] in an organopolysiloxane having a phenyl group in a molecular chain represented by the following formula (7) (16 ppm in terms of ruthenium atom with respect to the component (A)) and Component (B) represented by the following formula (2) and having a viscosity at 25 ° C. of 100 mPa · s and having a molecular chain both terminal trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer (A = methyl group, R 2 = methyl , C = 16, d = 28, SiH content; 5.5 mmol / 100 g), and thoroughly mixed until uniform at room temperature, and defoamed by centrifugation to obtain a curable composition 1 The cured product 1 was produced by heat-treating the composition 1 at 150 ° C. for 100 hours.
（式（７）中、Ｍｅはメチル基、Ｐｈはフェニル基を示す。）
(In the formula (7), Me represents a methyl group and Ph represents a phenyl group.)
［実施例２］
（Ａ）成分である、上記式（１）で表されるフェニレン基を有するオルガノポリシロキサン（Ｒ１＝−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）、Ｒ２＝メチル基、Ａ＝ｐ−フェニレン基、ａ＝１１、ｂ＝２５０）１００部に対して、（Ｃ）成分である、上記式（５）で表されるジ−μ−クロロ−ビス［クロロ（ｐ−シメン）ルテニウム（ＩＩ）］を、上記式（７）で表される分子鎖中にフェニル基を有するオルガノポリシロキサンに分散した溶液３０．３部（（Ａ）成分に対してルテニウム原子換算で８５ｐｐｍ）及び（Ｂ）成分である、上記式（２）で表され、２５℃での粘度が１００ ｍＰａ・ｓの分子鎖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（Ａ＝メチル基、Ｒ２＝メチル基、ｃ＝１６、ｄ＝２８、ＳｉＨ量；５．５ ｍｍｏｌ／１００ｇ）２．９部を添加し、室温下で均一になるまでよく混合し、遠心脱泡することで硬化性組成物２とし、該組成物２を１５０℃、１００時間加熱処理することで硬化物２を作製した。
Example 2
An organopolysiloxane having a phenylene group represented by the above formula (1) which is a component (A) (R 1 = -Si (CH 3 ) 2 (-CH = CH 2 ), R 2 = methyl group, A = Di-μ-chloro-bis [chloro (p-cymene) ruthenium represented by the above formula (5) which is the component (C) with respect to 100 parts of a p-phenylene group, a = 11, b = 250) 30.3 parts of a solution in which (II)] is dispersed in an organopolysiloxane having a phenyl group in the molecular chain represented by the above formula (7) (85 ppm in terms of ruthenium atom with respect to the component (A)) Component (B) represented by the above formula (2) and having a viscosity at 25 ° C. of 100 mPa · s and having a molecular chain both terminal trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer (A = methyl group, R 2 = methylate Group, c = 16, d = 28, SiH content; 5.5 mmol / 100 g), 2.9 parts are added, mixed well until uniform at room temperature, and defoamed by centrifugal separation. Then, the composition 2 was heat-treated at 150 ° C. for 100 hours to prepare a cured product 2.
［実施例３］
（Ａ）成分である、上記式（１）で表されるフェニレン基を有するオルガノポリシロキサン（Ｒ１＝−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）、Ｒ２＝メチル基、Ａ＝ｐ−フェニレン基、ａ＝１１、ｂ＝２５０）１００部に対して、（Ｃ）成分である、上記式（８）で表されるシクロペンタジエニルビス（トリフェニルホスフィン）ルテニウム（ＩＩ）クロリドを、上記式（７）で表される分子鎖中にフェニル基を有するオルガノポリシロキサンに分散した溶液１０．４部（（Ａ）成分に対してルテニウム原子換算で３０ｐｐｍ）及び（Ｂ）成分である上記式（２）で表され、２５℃での粘度が１００ ｍＰａ・ｓの分子鎖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（Ａ＝メチル基、Ｒ２＝メチル基、ｃ＝１６、ｄ＝２８、ＳｉＨ量；５．５ ｍｍｏｌ／１００ｇ）２．９部を添加し、室温下で均一になるまでよく混合し、遠心脱泡することで硬化性組成物３とし、該組成物３を１５０℃、８５時間加熱処理することで硬化物３を作製した。
[Example 3]
An organopolysiloxane having a phenylene group represented by the above formula (1) which is a component (A) (R 1 = -Si (CH 3 ) 2 (-CH = CH 2 ), R 2 = methyl group, A = Cyclopentadienyl bis (triphenylphosphine) ruthenium (II) chloride represented by the above formula (8) which is the component (C) with respect to 100 parts of p-phenylene group, a = 11, b = 250) And 10.4 parts of a solution dispersed in an organopolysiloxane having a phenyl group in the molecular chain represented by the above formula (7) (30 ppm in terms of ruthenium atom relative to the component (A)) and the component (B) It is represented by a certain said Formula (2), and the viscosity in 25 degreeC is 100 mPa * s and the molecular chain both terminal trimethylsiloxy group blocked dimethyl siloxane * methyl hydrogen siloxane copolymer (A = methyl group) R 2 = a methyl group, c = 16, d = 28 , SiH content; 5.5 mmol / 100g) was added 2.9 parts of curing by well mixed until uniform at room temperature, centrifuged defoaming It was set as the sex composition 3, and the hardened | cured material 3 was produced by heat-processing this composition 3 at 150 degreeC for 85 hours.
［実施例４］
（Ａ）成分である、上記式（１）で表されるフェニレン基を有するオルガノポリシロキサン（Ｒ１＝−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）、Ｒ２＝メチル基、Ａ＝ｐ−フェニレン基、ａ＝１１、ｂ＝２５０）１００部に対して、（Ｃ）成分である、上記式（９）で表される（ヘキサメチルベンゼン）ルテニウム（ＩＩ）ジクロリドダイマーを、上記式（７）で表される分子鎖中にフェニル基を有するオルガノポリシロキサンに分散した溶液２８．０部（（Ａ）成分に対してルテニウム原子換算で８０ｐｐｍ）及び（Ｂ）成分である、上記式（２）で表され、２５℃での粘度が１００ ｍＰａ・ｓの分子鎖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（Ａ＝メチル基、Ｒ２＝メチル基、ｃ＝１６、ｄ＝２８、ＳｉＨ量；５．５ ｍｍｏｌ／１００ｇ）２．９部を添加し、室温下で均一になるまでよく混合し、遠心脱泡することで硬化性組成物４とし、該組成物４を１５０℃、８５時間加熱処理することで硬化物４を作製した。
Example 4
An organopolysiloxane having a phenylene group represented by the above formula (1) which is a component (A) (R 1 = -Si (CH 3 ) 2 (-CH = CH 2 ), R 2 = methyl group, A = The (hexamethylbenzene) ruthenium (II) dichloride dimer represented by the above formula (9) which is the component (C) with respect to 100 parts of the p-phenylene group, a = 11, b = 250, 28.0 parts of a solution dispersed in an organopolysiloxane having a phenyl group in the molecular chain represented by (7) (80 ppm in terms of ruthenium atom with respect to the component (A)) and the component (B), The molecular chain both terminal trimethylsiloxy group blocked dimethyl siloxane / methyl hydrogen siloxane copolymer represented by (2) and having a viscosity of 100 mPa · s at 25 ° C. (A = methyl group, R 2 = methyl) Group, c = 16, d = 28, SiH content; 5.5 mmol / 100 g), 2.9 parts are added, mixed well until uniform at room temperature, and defoamed by centrifugal separation 4 Then, the composition 4 was heat treated at 150 ° C. for 85 hours to produce a cured product 4.
［比較例１］
（Ａ）成分である、上記式（１）で表されるフェニレン基を有するオルガノポリシロキサン（Ｒ１＝−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）、Ｒ２＝メチル基、Ａ＝ｐ−フェニレン基、ａ＝１１、ｂ＝２５０）１００部に対して、硬化触媒として白金原子を０．５質量％含有する塩化白金酸ビニルシロキサン錯体のトルエン溶液を０．１部及び（Ｂ）成分である、上記式（２）で表され、２５℃での粘度が１００ ｍＰａ・ｓの分子鎖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（Ａ＝メチル基、Ｒ２＝メチル基、ｃ＝１６、ｄ＝２８、ＳｉＨ量；５．５ ｍｍｏｌ／１００ｇ）２．２部を添加し、室温下で均一になるまでよく混合し、遠心脱泡することで硬化性組成物５とし、該組成物５を１５０℃、０．５時間加熱処理することで硬化物５を作製した。
Comparative Example 1
An organopolysiloxane having a phenylene group represented by the above formula (1) which is a component (A) (R 1 = -Si (CH 3 ) 2 (-CH = CH 2 ), R 2 = methyl group, A = 0.1 parts of a toluene solution of a chloroplatinic acid vinyl siloxane complex containing 0.5 mass% of a platinum atom as a curing catalyst relative to 100 parts of a p-phenylene group (a = 11, b = 250) and (B) Component, which is represented by the above formula (2) and has a viscosity of 100 mPa · s at 25 ° C. and a molecular chain both terminal trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer (A = methyl group, R 2 = A methyl group, c = 16, d = 28, SiH content; 5.5 mmol / 100g) 2.2 parts are added, mixed well until it becomes uniform at room temperature, and hardenable composition by centrifugal degassing And 5 Narubutsu 5 0.99 ° C., to produce a cured product 5 by heat treatment for 0.5 hours.
［比較例２］
上記式（１）で表されるフェニレン基を有しないオルガノポリシロキサン（Ｒ１＝−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）、Ｒ２＝メチル基、Ａ＝ｐ−フェニレン基、ａ＝０、ｂ＝２００）１００部に対して、（Ｃ）成分である、上記式（５）で表されるジ−μ−クロロ−ビス［クロロ（ｐ−シメン）ルテニウム（ＩＩ）］を、上記式（７）で表される分子鎖中にフェニル基を有するオルガノポリシロキサンに分散した溶液５．７部（（Ａ）成分に対してルテニウム原子換算で１６ｐｐｍ）及び（Ｂ）成分である、上記式（２）で表され、２５℃での粘度が１００ ｍＰａ・ｓの分子鎖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（Ａ＝メチル基、Ｒ２＝メチル基、ｃ＝１６、ｄ＝２８、ＳｉＨ量；５．５ ｍｍｏｌ／１００ｇ）２．３部を添加し、室温下で均一になるまでよく混合し、遠心脱泡することで硬化性組成物６とし、該組成物６を１５０℃、１００時間加熱処理することで硬化物６を作製した。
Comparative Example 2
Organopolysiloxane (R 1 = -Si (CH 3 ) 2 (-CH = CH 2 ), R 2 = methyl, A = p-phenylene, a) having no phenylene group represented by the above formula (1) Di-μ-chloro-bis [chloro (p-cymene) ruthenium (II)] represented by the above formula (5), which is the component (C), relative to 100 parts of = 0, b = 200), 5.7 parts of a solution dispersed in an organopolysiloxane having a phenyl group in the molecular chain represented by the above formula (7) (16 ppm in terms of ruthenium atom with respect to the component (A)) and the component (B) represented by the above formula (2), both molecular chain terminals trimethyl with a viscosity of 100 mPa · s siloxy group dimethylsiloxane-methylhydrogensiloxane copolymer at 25 ° C. (a = methyl, R 2 = methyl, c = 16, d = 8. Add 2.3 parts of SiH; 5.5 mmol / 100 g), mix well until uniform at room temperature, and degas by centrifugal degassing to make a curable composition 6; C. for 100 hours to produce a cured product 6.
［比較例３］
（Ａ）成分である、上記式（１）で表されるフェニレン基を有するオルガノポリシロキサン（（Ｒ１＝−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）、Ｒ２＝メチル基、Ａ＝ｐ−フェニレン基、ａ＝１１、ｂ＝２５０）１００部に対して、（Ｂ）成分である、上記式（２）で表され、２５℃での粘度が１００ ｍＰａ・ｓの分子鎖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（Ａ＝メチル基、Ｒ２＝メチル基、ｃ＝１６、ｄ＝２８、ＳｉＨ量；５．５ ｍｍｏｌ／１００ｇ）２．９部を添加し、室温下で均一になるまでよく混合し、遠心脱泡することで組成物７とし、該組成物７を１５０℃、１００時間加熱処理したが、該組成物７は硬化せず、該組成物７の硬化物を得ることはできなかった。
Comparative Example 3
Organopolysiloxane ((R 1 = -Si (CH 3 ) 2 (-CH = CH 2 ), R 2 = methyl group, A having a phenylene group represented by the above formula (1)) which is the component (A) = 100 parts of p-phenylene group, a = 11, b = 250), both molecular chains represented by the above formula (2) which is the component (B) and having a viscosity of 100 mPa · s at 25 ° C Terminal trimethylsiloxy group-blocked dimethylsiloxane / methyl hydrogen siloxane copolymer (A = methyl group, R 2 = methyl group, c = 16, d = 28, SiH content: 5.5 mmol / 100 g) 2.9 parts It was added, mixed well until uniform at room temperature, and centrifugally defoamed to give a composition 7, which was heat-treated at 150 ° C. for 100 hours, but the composition 7 did not cure, and the composition 7 was not cured. Can I obtain a cured product of Composition 7? It was.
上記硬化物１〜６について、２３０℃空気雰囲気下における経時のゴム硬度変化をＪＩＳ Ｋ７３１２に規定されるアスカー（Ｔｙｐｅ Ｃ）を用いて測定した。測定した硬度の、初期値（０時間）と６００時間経過後の測定値との変動差を求めた。また残存質量率（％）を精密天秤（ＭＥＴＴＬＥＲ ＴＯＬＥＤＯ社製 ＸＳ２０４）で随時計量することで求めた。これら２つの値の変化から耐熱性の評価を行った。結果を表１、２に示す。 With respect to the cured products 1 to 6, the change in rubber hardness with time in an air atmosphere at 230 ° C. was measured using Asker (Type C) defined in JIS K7312. The difference in the measured hardness between the initial value (0 hour) and the measured value after 600 hours was determined. The residual mass ratio (%) was determined by measuring at any time with a precision balance (XS 204 manufactured by METTLER TOLEDO). The heat resistance was evaluated from the change of these two values. The results are shown in Tables 1 and 2.
実施例１〜４の組成物１〜４から得られた硬化物１〜４は、本発明の要件を満たすものであり、６００時間経過後の硬度変化は、変動差８〜９であり、良好な耐熱性を有していることが明らかとなった。また６００時間経過後の残存質量率（％）に関しても全ての時間において９５％以上を有していた。
一方、比較例１の組成物５から得られた硬化物５の６００時間経過時における硬度変化は、変動差１６となった。これは、本発明に必須である（Ｃ）成分の代わりの白金触媒が、硬化物中に含まれるために、耐熱性が低下したと考えられる。
また、比較例２の組成物６から得られた硬化物６の６００時間経過時における硬度変化は、変動差４７となった。これは、本発明に必須である（Ａ）成分が含まれていないため、アリーレン基を主鎖に有するオルガノポリシロキサン由来の耐熱性が発現されなかったと考えられる。以上、比較例１、２の硬度変化は、実施例１〜４の硬度変化と比較して大幅に増加しており、硬化物５、６は、硬化物１〜４と比較して、耐熱性が劣っていた。
また比較例１、２の残存質量率（％）に関しても６００時間経過後に９０％以下となっており、実施例１〜４の残存質量率（％）と比較して低かった。以上の結果から、（Ａ）成分及び（Ｃ）成分は本発明の組成物に必須であることが明らかとなった。
更に、比較例３の組成物は、本発明の組成物に必須である（Ｃ）成分が含まれていないため、（Ａ）成分と（Ｂ）成分との付加反応が進行せず、架橋構造が形成されないため、硬化物を得ることができなった。このことから（Ｃ）成分は本発明の組成物に必須である。
以上のことから、本発明の硬化性オルガノポリシロキサン組成物から得られる硬化物が高耐熱性の発現に有効である。
The cured products 1 to 4 obtained from the compositions 1 to 4 of Examples 1 to 4 satisfy the requirements of the present invention, and the hardness change after 600 hours is 8 to 9, with a variation difference It became clear that it had good heat resistance. The residual mass ratio (%) after 600 hours also had 95% or more in all the time.
On the other hand, the hardness change of the cured product 5 obtained from the composition 5 of Comparative Example 1 after 600 hours had a variation difference of 16. It is considered that this is because the platinum catalyst instead of the component (C), which is essential to the present invention, is contained in the cured product, so the heat resistance is lowered.
The change in hardness of the cured product 6 obtained from the composition 6 of Comparative Example 2 after 600 hours was a variation difference 47. This is considered to be because the heat resistance derived from the organopolysiloxane having an arylene group in the main chain was not expressed because the component (A) which is essential to the present invention is not contained. As mentioned above, the hardness change of the comparative examples 1 and 2 is increasing significantly compared with the hardness change of Examples 1-4, and the hardened | cured material 5 and 6 is heat resistance compared with the hardened | cured material 1 to 4 Was inferior.
The residual mass ratio (%) of Comparative Examples 1 and 2 was 90% or less after 600 hours, and was lower than the residual mass ratio (%) of Examples 1 to 4. From the above results, it has become clear that the components (A) and (C) are essential to the composition of the present invention.
Furthermore, since the composition of Comparative Example 3 does not contain the component (C), which is an essential component of the composition of the present invention, the addition reaction between the components (A) and (B) does not proceed, and a crosslinked structure is obtained. As a result, no cured product could be obtained. From this, the component (C) is essential to the composition of the present invention.
From the above, the cured product obtained from the curable organopolysiloxane composition of the present invention is effective for the development of high heat resistance.
本発明の硬化性オルガノポリシロキサン組成物を硬化することにより得られる硬化物は、高い耐熱性を有することから、高温環境下で使用されるシーリング剤、接着剤及びコーティング剤等として有用である。 The cured product obtained by curing the curable organopolysiloxane composition of the present invention has high heat resistance, and is useful as a sealing agent, an adhesive, a coating agent and the like used in a high temperature environment.
Claims (7)
（式（１）中、Ｒ１は−Ｓｉ（ＣＨ３）２（−ＣＨ＝ＣＨ２）であり、Ｒ２は同一又は異種の炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基及びそれらの基の水素原子の一部がハロゲン原子で置換された基から選ばれる基であり、Ａｒは炭素数６以上のアリーレン基であり、ａは１〜１，０００の整数であり、ｂは１〜５，０００の整数であり、ａ＋ｂは１０〜６，０００の整数である。なお、各繰り返し単位の配列はランダムでもよい。）
（Ｂ）１分子中に３個以上のＳｉＨ基を有するオルガノハイドロジェンポリシロキサン：（Ａ）成分１００質量部に対して１〜２０質量部、及び
（Ｃ）ルテニウム硬化触媒：触媒量、
を含有する硬化性オルガノポリシロキサン組成物。 (A) Organopolysiloxane represented by the following general formula (1): 100 parts by mass,
(In formula (1), R 1 is —Si (CH 3 ) 2 (—CH = CH 2 ), R 2 is the same or different alkyl group having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms Ar is a arylene group having 6 or more carbon atoms, and a is an integer of 1 to 1,000. b is an integer of 1 to 5,000, and a + b is an integer of 10 to 6,000. The arrangement of each repeating unit may be random.)
(B) Organohydrogenpolysiloxanes having three or more SiH groups in one molecule: 1 to 20 parts by mass with respect to 100 parts by mass of (A) component, and (C) Ruthenium curing catalyst: catalytic amount,
Curable organopolysiloxane composition containing
（式（２）中、Ｒ２は同一又は異種の炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基及びそれらの基の水素原子の一部がハロゲン原子で置換された基から選ばれる基を示す。式（２）中、Ａは水素原子又はメチル基であり、ｃ、ｄはそれぞれ０〜６０の整数であり、ｃ＋ｄは１〜１２０の整数である。ただし、１分子中に３個以上のＳｉＨ基を有する。）で示されるオルガノハイドロジェンポリシロキサンである請求項１に記載の硬化性オルガノポリシロキサン組成物。 Component (B) has the following general formula (2)
(In the formula (2), R 2 is the same or different alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and a group in which part of hydrogen atoms of those groups is substituted with a halogen atom In the formula (2), A represents a hydrogen atom or a methyl group, c and d each represent an integer of 0 to 60, and c + d represents an integer of 1 to 120. However, in one molecule The curable organopolysiloxane composition according to claim 1, which is an organohydrogenpolysiloxane represented by (3) having three or more SiH groups.
（式（３）中、Ｒ３は水素原子または、ヘテロ原子及び／若しくは芳香族環を含有してもよい炭素数２〜５０の炭化水素配位子を示す。式（３）中、Ｘはハロゲン原子であり、ｅは１〜５の整数、ｆ及びｇは０〜２０の整数である。但し、ｆ＝ｇ＝０の場合を除く。） The curable organopolysiloxane composition according to claim 1 or 2, wherein the component (C) is a ruthenium curing catalyst containing a ruthenium compound represented by the following general formula (3).
(In the formula (3), R 3 represents a hydrogen atom or a hydrocarbon ligand having 2 to 50 carbon atoms which may contain a hetero atom and / or an aromatic ring. In the formula (3), X represents A halogen atom, e is an integer of 1 to 5 and f and g are integers of 0 to 20, except in the case of f = g = 0)
（式（４）中、Ａｒは炭素数６〜５０のη６−アレーン配位子を示し、Ｘはハロゲン原子であり、ｉは１〜５の整数、ｊ及びｋは０〜２０の整数である。） The curable organopolysiloxane composition according to any one of claims 1 to 3, wherein the component (C) is a ruthenium curing catalyst containing a ruthenium compound represented by the following general formula (4).
(In the formula (4), Ar represents an η 6 -arene ligand having 6 to 50 carbon atoms, X is a halogen atom, i is an integer of 1 to 5, j and k are integers of 0 to 20 is there.)
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