JP2022190755A - Method for producing room temperature curable organopolysiloxane composition - Google Patents
Method for producing room temperature curable organopolysiloxane composition Download PDFInfo
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- JP2022190755A JP2022190755A JP2021099162A JP2021099162A JP2022190755A JP 2022190755 A JP2022190755 A JP 2022190755A JP 2021099162 A JP2021099162 A JP 2021099162A JP 2021099162 A JP2021099162 A JP 2021099162A JP 2022190755 A JP2022190755 A JP 2022190755A
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- 239000000203 mixture Substances 0.000 title claims abstract description 95
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- -1 silane compound Chemical class 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910000077 silane Inorganic materials 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 239000000047 product Substances 0.000 abstract description 17
- 238000002845 discoloration Methods 0.000 abstract description 11
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- 229920002379 silicone rubber Polymers 0.000 abstract description 9
- 125000000962 organic group Chemical group 0.000 abstract description 4
- 239000007859 condensation product Substances 0.000 abstract 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 19
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 18
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 13
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- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
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- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 8
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- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
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- 238000006116 polymerization reaction Methods 0.000 description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
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- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 3
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
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- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
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- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical group CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
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- XKBQRJBETDMEFN-ILRZCOILSA-N (e)-n-[bis[[(e)-butan-2-ylideneamino]oxy]-phenylsilyl]oxybutan-2-imine Chemical compound CC\C(C)=N\O[Si](O\N=C(/C)CC)(O\N=C(/C)CC)C1=CC=CC=C1 XKBQRJBETDMEFN-ILRZCOILSA-N 0.000 description 1
- ZKALVNREMFLWAN-VOTSOKGWSA-N (ne)-n-(4-methylpentan-2-ylidene)hydroxylamine Chemical compound CC(C)C\C(C)=N\O ZKALVNREMFLWAN-VOTSOKGWSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 description 1
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 1
- GOJOGRCNYATXLQ-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)CCCOCC1CO1 GOJOGRCNYATXLQ-UHFFFAOYSA-N 0.000 description 1
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 1
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- FGPCETMNRYMFJR-UHFFFAOYSA-L [7,7-dimethyloctanoyloxy(dimethyl)stannyl] 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCC(C)(C)C FGPCETMNRYMFJR-UHFFFAOYSA-L 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NNVDGGDSRRQJMV-UHFFFAOYSA-L [dioctyl(2,2,5,5-tetramethylhexanoyloxy)stannyl] 2,2,5,5-tetramethylhexanoate Chemical compound CCCCCCCC[Sn](OC(=O)C(C)(C)CCC(C)(C)C)(OC(=O)C(C)(C)CCC(C)(C)C)CCCCCCCC NNVDGGDSRRQJMV-UHFFFAOYSA-L 0.000 description 1
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- 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ICCDZMWNLNRHGP-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-bis(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)CCCOCC1CO1 ICCDZMWNLNRHGP-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- ZWXYOPPJTRVTST-UHFFFAOYSA-N methyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)OC(C)=C ZWXYOPPJTRVTST-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- OKXJFBREZUPSGZ-UHFFFAOYSA-N n'-benzyl-n'-(3-trimethoxysilylpropyl)methanediamine Chemical compound CO[Si](OC)(OC)CCCN(CN)CC1=CC=CC=C1 OKXJFBREZUPSGZ-UHFFFAOYSA-N 0.000 description 1
- HZGIOLNCNORPKR-UHFFFAOYSA-N n,n'-bis(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCC[Si](OC)(OC)OC HZGIOLNCNORPKR-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- XGIZTLFJCDBRDD-UHFFFAOYSA-N phenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C1=CC=CC=C1 XGIZTLFJCDBRDD-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000008096 xylene 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
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、大気中の湿気（水分）により室温（２３℃±１５℃）において硬化してシリコーンゴム硬化物（シリコーンエラストマー弾性体）を与える室温硬化性オルガノポリシロキサン組成物の製造方法であって、特定のアミノ官能性基含有加水分解性オルガノシラン化合物を特定の工程において組成物中に配合することによって、良好な耐スランプ性、硬化性、接着性を有すると共に、ＵＶ照射に対する変色が殆どないシリコーンゴム硬化物を与えることができる室温硬化性オルガノポリシロキサン組成物の製造方法に関する。 The present invention is a method for producing a room temperature curable organopolysiloxane composition that cures at room temperature (23° C.±15° C.) with atmospheric humidity (moisture) to give a silicone rubber cured product (silicone elastomer elastic body). , By incorporating a specific amino functional group-containing hydrolyzable organosilane compound into the composition in a specific step, it has good slump resistance, curability, and adhesion, and has almost no discoloration due to UV irradiation. The present invention relates to a method for producing a room temperature curable organopolysiloxane composition capable of giving a silicone rubber cured product.
湿気により架橋・硬化する室温硬化性（ＲＴＶ）シリコーンゴム組成物は、その取り扱いが容易な上、耐候性や電気特性に優れているため、建材用のシーリング材、電気電子分野での接着剤などの様々な用途を有している。一般的な室温硬化性オルガノポリシロキサン組成物は、分子鎖末端にシラノール基（ケイ素原子に結合した水酸基）やアルコキシシリル基を有するジオルガノポリシロキサン（ベースポリマー）、硬化剤、アミノアルキル基含有アルコキシシラン及び硬化触媒を含み、難燃性や熱伝導性、引張り強度等を付与するため、必要に応じて各種フィラーが添加される。 Room temperature vulcanizable (RTV) silicone rubber compositions that crosslink and cure with moisture are easy to handle and have excellent weather resistance and electrical properties. has a variety of uses. A typical room-temperature-curable organopolysiloxane composition consists of a diorganopolysiloxane (base polymer) having silanol groups (hydroxyl groups bonded to silicon atoms) or alkoxysilyl groups at the molecular chain ends, a curing agent, an aminoalkyl group-containing alkoxy It contains silane and a curing catalyst, and various fillers are added as necessary to impart flame retardancy, thermal conductivity, tensile strength, and the like.
ところで、室温硬化性（ＲＴＶ）シリコーンゴムを工業用または建築、構造用などのシーリング材として用いる場合には、施工されたシーリング材が垂れ落ちないこと（耐スランプ性）が重要である。そのため、一般的にはシリコーンとの分散性に優れ、補強性を付与することができる煙霧質シリカ（ヒュームドシリカ）が使用される。一般的に、シリカは表面にシラノール基が存在することで経時による水分の付着が多いため、ジクロロジメチルシランやヘキサメチルジシラザンなどのシラン化合物で表面処理される。処理されたシリカは、表面が疎水化されるため水分の吸着が抑えられることに加えて、シリコーンとの分散性にも優れるため、建材用のシーリング材や電気電子分野の接着剤などの様々な用途で使用される室温硬化性（ＲＴＶ）シリコーンゴムに汎用的に添加されている。 By the way, when room temperature vulcanizable (RTV) silicone rubber is used as a sealing material for industrial, construction, and structural purposes, it is important that the applied sealing material does not sag (slump resistance). Therefore, fumed silica is generally used because it has excellent dispersibility with silicone and can impart reinforcing properties. In general, silica is surface-treated with a silane compound such as dichlorodimethylsilane, hexamethyldisilazane, or the like, because the presence of silanol groups on the surface of silica causes a large amount of moisture to adhere over time. The surface of treated silica is hydrophobized, which suppresses the adsorption of moisture. In addition, it has excellent dispersibility with silicone. It is commonly added to room temperature vulcanizable (RTV) silicone rubbers used in applications.
一般的な建築、構造用シーリング材として知られる脱オキシム型の室温硬化性オルガノポリシロキサン組成物は、硬化性、耐久性、各種被着体に対する接着性を有することで汎用的に用いられているが、得られる硬化物が長期間の紫外線に曝露される環境下においてＵＶ照射に対するゴム物性変化の点では耐候性に問題はないものの、変色が顕著であり意匠性が悪くなることが知られている。
また、建築、構造用シーリング材としては脱酢酸型の室温硬化性オルガノポリシロキサン組成物も汎用的に使用されており、硬化性、接着性に優れ、かつＵＶ照射に対する変色も僅かであることが知られているが、硬化中に発生する酢酸のため作業性が悪い。
A deoxime-type room-temperature-curable organopolysiloxane composition known as a general building and structural sealant is widely used due to its curability, durability, and adhesiveness to various adherends. However, it is known that in an environment where the resulting cured product is exposed to UV rays for a long period of time, there is no problem with weather resistance in terms of changes in rubber physical properties due to UV irradiation, but discoloration is remarkable and design deteriorates. there is
Deacetic acid-type room-temperature-curing organopolysiloxane compositions are also commonly used as building and structural sealants, and are known to exhibit excellent curability and adhesiveness, as well as little discoloration upon UV irradiation. Although known, workability is poor due to acetic acid generated during curing.
一方、脱アルコール型の室温硬化性オルガノポリシロキサン組成物は、上記脱オキシム型や脱酢酸型の室温硬化性オルガノポリシロキサン組成物と比べると調製方法が容易ではない。ベースポリマーとして分子鎖両末端にシラノール基を有するオルガノポリシロキサンを使用した場合、シラノール基をアルコキシシリル化する（アルコキシシリル基で末端封鎖する）必要が有るが、その反応速度は上記脱オキシム型や脱酢酸型の室温硬化性オルガノポリシロキサン組成物と比べて遅いことが、脱アルコール型の室温硬化性オルガノポリシロキサン組成物の調製方法が容易ではない理由として挙げられる。また、ベースポリマーとして予め分子鎖両末端がアルコキシシリル化されたオルガノポリシロキサンを使用する方法も知られているが、両末端シラノール基のものと比べてコストが高くなるため、該方法は汎用性にかける。 On the other hand, the dealcoholization type room temperature curable organopolysiloxane composition is not easy to prepare compared to the deoxime type or deacetic acid type room temperature curable organopolysiloxane composition. When an organopolysiloxane having silanol groups at both ends of the molecular chain is used as the base polymer, it is necessary to alkoxysilylate the silanol groups (block the ends with alkoxysilyl groups), but the reaction rate is the above-mentioned deoxime type and The fact that it is slower than the deacetic acid room temperature curable organopolysiloxane composition is one of the reasons why the dealcoholization type room temperature curable organopolysiloxane composition is not easy to prepare. Also known is a method of using an organopolysiloxane in which both ends of the molecular chain are alkoxysilylated in advance as the base polymer. put it on
分子鎖両末端にシラノール基を有するオルガノポリシロキサンを末端封鎖する手法として、特開昭６３－８３１６６号公報及び特開昭６３－８３１６７号公報（特許文献１～２）には、末端にシラノール基を有するオルガノポリシロキサンに、アルコキシ基含有シランと特定のアミノ基含有シランを末端封鎖触媒として配合することで、組成物の製造工程中に末端封鎖し、錫触媒を用いることなく、室温硬化性オルガノポリシロキサン組成物が得られることが開示されている。 As a technique for end-blocking organopolysiloxane having silanol groups at both ends of the molecular chain, JP-A-63-83166 and JP-A-63-83167 (Patent Documents 1 and 2) disclose silanol groups at the ends. By adding an alkoxy group-containing silane and a specific amino group-containing silane as a terminal blocking catalyst to an organopolysiloxane having It is disclosed that a polysiloxane composition is obtained.
アミノ基含有シランを、末端にシラノール基を有するオルガノポリシロキサンと事前に混合する方法としては、特開２０００－１２９１３０号公報（特許文献３）に、微粉末シリカと共存条件下で混合することで、流動性、セルフレベリング性などに優れる室温硬化性オルガノポリシロキサン組成物を製造する方法が開示されている。 As a method of pre-mixing an amino group-containing silane with an organopolysiloxane having a silanol group at its end, JP-A-2000-129130 (Patent Document 3) describes mixing with fine powder silica under coexistence conditions. Disclosed is a method for producing a room temperature curable organopolysiloxane composition having excellent fluidity, self-leveling properties, and the like.
また特定のアミノ基含有シランと末端にシラノール基を有するオルガノポリシロキサンとを事前に混合することにより系中で末端封鎖する手法が、特許第５８８８１１２号公報（特許文献４）に開示されている。 Further, Japanese Patent No. 5888112 (Patent Document 4) discloses a technique of pre-mixing a specific amino group-containing silane with an organopolysiloxane having a terminal silanol group to block the ends in the system.
これら従来の方法は、室温硬化性オルガノポリシロキサン組成物の製造工程中においてベースポリマーの末端を封鎖できるため、コスト面等で非常に有用な手段であるが、反応により発生するアルコールが系中に残存することにより保存安定性が問題となる場合がある。また末端封鎖触媒として酸触媒を使用する場合は、塩基性の接着性付与剤が中和されるため、接着性が不良となる可能性がある。さらに、これら従来の技術により調製される室温硬化性オルガノポリシロキサン組成物は良好な硬化特性は示すものの、得られる硬化物の変色耐性や劣化については言及されていなかった。 These conventional methods can block the terminals of the base polymer during the manufacturing process of the room-temperature-curable organopolysiloxane composition, and are very useful in terms of cost. Storage stability may become a problem by remaining. Also, when an acid catalyst is used as the terminal blocking catalyst, the adhesion may be poor because the basic adhesion-imparting agent is neutralized. Furthermore, although room-temperature-curable organopolysiloxane compositions prepared by these conventional techniques exhibit good curing properties, no mention has been made of discoloration resistance and deterioration of the resulting cured products.
そこで本発明の目的は、良好な耐スランプ性、硬化性、接着性を有すると共に、ＵＶ照射に対する変色が殆どないシリコーンゴム硬化物を与えることができる室温硬化性オルガノポリシロキサン組成物の製造方法を提供することを目的とする。 SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing a room-temperature-curable organopolysiloxane composition capable of giving a silicone rubber cured product which has good slump resistance, curability, and adhesiveness and which hardly discolors due to UV irradiation. intended to provide
本発明者らは上記目的を達成するため鋭意検討を行った結果、分子鎖両末端にシラノール基を有するオルガノポリシロキサンをベースポリマーの出発原料とし、特定のアミノ官能性基含有加水分解性オルガノシラン化合物を末端封鎖触媒として使用すると共に、該特定のアミノ官能性基含有加水分解性オルガノシラン化合物（末端封鎖触媒）を特定の工程において組成物中に配合することによって、良好な耐スランプ性、硬化性、接着性を有すると共に、得られる硬化物のＵＶ照射に対する変色が殆どないシリコーンゴム硬化物を与えることができる室温硬化性オルガノポリシロキサン組成物を製造することができることを見出し、本発明を完成した。 The inventors of the present invention have made intensive studies to achieve the above object, and found that an organopolysiloxane having silanol groups at both ends of the molecular chain is used as a starting material for a base polymer, and a specific amino functional group-containing hydrolyzable organosilane is obtained. By using the compound as a terminal blocking catalyst and incorporating the specific amino functional group-containing hydrolyzable organosilane compound (terminal blocking catalyst) into the composition in a specific step, good slump resistance, curing The inventors have found that it is possible to produce a room-temperature-curable organopolysiloxane composition capable of producing a silicone rubber cured product that has excellent properties and adhesive properties and that causes little discoloration of the resulting cured product when exposed to UV irradiation, thereby completing the present invention. did.
即ち、本発明は下記の室温硬化性オルガノポリシロキサン組成物の製造方法を提供するものである。 That is, the present invention provides the following method for producing a room temperature curable organopolysiloxane composition.
［１］
（Ａ）下記一般式（１）
（Ｂ）下記一般式（２）
（Ｃ）無機充填剤 １～２００質量部、及び、
（Ｄ）１分子中に窒素原子を３個以上有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物 ０．５～３質量部、
を含有する室温硬化性オルガノポリシロキサン組成物の製造方法であって、
予め（Ａ）成分、（Ｂ）成分の一部又は全部（（Ｂ）成分全体の１０～１００質量％）、及び（Ｄ）成分の一部又は全部（（Ｄ）成分全体の５０～１００質量％）を混合して均一な混合物を調製した後、該混合物に（Ｃ）成分及び残余の（Ｂ）成分（（Ｂ）成分全体の０～９０質量％）及び残余の（Ｄ）成分（（Ｄ）成分全体の０～５０質量％）を添加、混合して組成物を調製する工程を有する、室温硬化性オルガノポリシロキサン組成物の製造方法。
［２］
（Ｄ）成分が、下記一般式（３）又は一般式（３）’で示されるアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物である［１］に記載の室温硬化性オルガノポリシロキサン組成物の製造方法。
[1]
(A) the following general formula (1)
(B) the following general formula (2)
(C) inorganic filler 1 to 200 parts by mass, and
(D) an amino functional group-containing hydrolyzable organosilane compound having 3 or more nitrogen atoms in one molecule and/or a partial hydrolytic condensate thereof 0.5 to 3 parts by mass,
A method for producing a room temperature curable organopolysiloxane composition containing
Component (A), part or all of component (B) (10 to 100% by mass of the total component (B)), and part or all of component (D) (50 to 100 mass of the total component (D) %) to prepare a uniform mixture, and then the mixture is added with the remaining component (C) and the remaining component (B) (0 to 90% by mass of the total component (B)) and the remaining component (D) (( D) A method for producing a room-temperature-curable organopolysiloxane composition, comprising the step of adding and mixing 0 to 50% by mass of component D) to prepare a composition.
[2]
(D) Component according to [1], wherein the amino functional group-containing hydrolyzable organosilane compound represented by the following general formula (3) or general formula (3)′ and/or a partial hydrolytic condensate thereof A method for producing a room temperature curable organopolysiloxane composition.
本発明の室温硬化性オルガノポリシロキサン組成物の製造方法は、ベースポリマーである（Ａ）成分中の分子鎖両末端のシラノール基が、末端封鎖触媒（縮合触媒）である（Ｄ）成分との共存による塩基性条件下において、架橋剤・硬化剤である（Ｂ）成分から誘導される加水分解性シリル基で効果的に末端封鎖されることによって、得られる室温硬化性オルガノポリシロキサン組成物の硬化物が、長期間の紫外線照射条件下に晒された場合であっても、各種基材に対して良好な接着性を発現すると同時に、なおかつ優れたＵＶ照射に対する変色耐性が得られる。
また、本発明の製造方法は、室温硬化性オルガノポリシロキサン組成物の製造工程中においてベースポリマーの末端を封鎖できるため、コスト面等で非常に有利である。また、塩基性の接着性付与剤を組成物中に配合する場合であっても、本発明は酸触媒を使用しないため、塩基性の接着性付与剤が中和され、接着性が不良となることはない。
したがって、本発明の製造方法で製造された室温硬化性オルガノポリシロキサン組成物は、建材用のシーリング材、電気・電子用の接着剤として有用である。
In the method for producing the room-temperature-curable organopolysiloxane composition of the present invention, the silanol groups at both ends of the molecular chain in component (A), which is the base polymer, are combined with component (D), which is a terminal blocking catalyst (condensation catalyst). A room-temperature-curable organopolysiloxane composition obtained by effectively end-blocking hydrolyzable silyl groups derived from component (B), which is a cross-linking agent and a curing agent, under basic conditions due to coexistence. Even when the cured product is exposed to UV irradiation for a long period of time, it exhibits good adhesiveness to various substrates and at the same time provides excellent discoloration resistance to UV irradiation.
In addition, the production method of the present invention is very advantageous in terms of cost, etc., since the terminal of the base polymer can be blocked during the production process of the room-temperature-curable organopolysiloxane composition. Further, even when a basic adhesion-imparting agent is blended into the composition, since the present invention does not use an acid catalyst, the basic adhesion-imparting agent is neutralized, resulting in poor adhesion. never.
Therefore, the room-temperature-curable organopolysiloxane composition produced by the production method of the present invention is useful as a sealing material for building materials and an adhesive for electrical and electronic applications.
以下、本発明について詳しく説明する。 The present invention will be described in detail below.
本発明の室温硬化性オルガノポリシロキサン組成物の製造方法は、予め下記（Ａ）成分、（Ｂ）成分の一部又は全部（通常、組成物に配合する（Ｂ）成分全体の１０～１００質量％、好ましくは１５～８０質量％、より好ましくは２０～６０質量％）及び（Ｄ）成分の一部又は全部（通常、組成物に配合する（Ｄ）成分全体の５０～１００質量％、好ましくは７５～１００質量％、より好ましくは８０～１００質量％）を混合して均一な混合物を調製する工程（第１工程）、及び、
第１工程の後、該混合物に（Ｃ）成分及び残余の成分として、（Ｂ）成分の残余分（通常、（Ｂ）成分全体の０～９０質量％、好ましくは２０～８５質量％、より好ましくは４０～８０質量％）、（Ｄ）成分の残余分（通常、（Ｄ）成分全体の０～５０質量％、好ましくは０～２５質量％、より好ましくは０～２０質量％）、並びに必要に応じてその他の任意成分を添加、混合する工程（第２工程）
を有する。
In the method for producing the room-temperature-curable organopolysiloxane composition of the present invention, a part or all of the following components (A) and (B) (generally, 10 to 100 masses of the entire component (B) to be blended in the composition) %, preferably 15 to 80% by mass, more preferably 20 to 60% by mass) and part or all of component (D) (generally, 50 to 100% by mass of the total component (D) blended in the composition, preferably is 75 to 100% by mass, more preferably 80 to 100% by mass) to prepare a uniform mixture (first step), and
After the first step, as the component (C) and the remaining component in the mixture, the residue of the component (B) (usually 0 to 90% by mass of the total component (B), preferably 20 to 85% by mass, more preferably 40 to 80% by mass), the remainder of component (D) (usually 0 to 50% by mass, preferably 0 to 25% by mass, more preferably 0 to 20% by mass of the total component (D)), and Step of adding and mixing other optional ingredients as necessary (second step)
have
上記の第１工程及び第２工程において、各成分は減圧下で混合されてもよい。 In the above first and second steps, each component may be mixed under reduced pressure.
［（Ａ）成分］
（Ａ）成分は、下記一般式（１）で示される分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖された直鎖状のジオルガノポリシロキサンであり、本発明の組成物の主剤（ベースポリマー）として作用するものである。
Component (A) is a linear diorganopolysiloxane having both ends of the molecular chain blocked with silanol groups (hydroxyl groups bonded to silicon atoms) represented by the following general formula (1), and is used in the composition of the present invention. It acts as the main agent (base polymer) of
式（１）中、Ｒ1は独立に炭素数１～１０の置換又は非置換の一価の炭化水素基であり、例えばメチル基、エチル基、プロピル基などのアルキル基；シクロヘキシル基などの環状アルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、トリル基などのアリール基；およびこれらの基の水素原子が部分的にハロゲン原子で置換された基、例えば３，３，３－トリフルオロプロピル基等が挙げられる。これらの中では、特にメチル基が好ましい。
Ｒ1は同一の基であっても異種の基であってもよく、またｍは１０以上の数、好ましくは１０～２，０００の数、より好ましくは５０～１，５００の数、更に好ましくは１００～１，０００の数であり、特に該ジオルガノポリシロキサンの２３℃における粘度が２５～５００，０００ｍＰａ・ｓ、好ましくは５０～１００，０００ｍＰａ・ｓ、より好ましくは１００～５０，０００ｍＰａ・ｓとなる数である。なお、本発明において、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）等による２３℃での測定値であり、ジオルガノポリシロキサン中の主鎖を構成する繰り返し単位（（Ｒ1）2ＳｉＯ2/2）の繰り返し数ｍの値（又は重合度）は、例えば、トルエン等を展開溶媒とした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）等として求めた値である。
（Ａ）成分は１種単独でも又は２種以上を併用してもよい。
In formula (1), R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group or a propyl group; a cyclic group such as a cyclohexyl group; alkyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group and tolyl group; A fluoropropyl group and the like can be mentioned. Among these, a methyl group is particularly preferred.
R 1 may be the same group or different groups, and m is a number of 10 or more, preferably a number of 10 to 2,000, more preferably a number of 50 to 1,500, more preferably a number of is a number of 100 to 1,000, and in particular the diorganopolysiloxane has a viscosity of 25 to 500,000 mPa·s, preferably 50 to 100,000 mPa·s, more preferably 100 to 50,000 mPa·s s is the number. In the present invention, viscosity is a value measured at 23° C. by a rotational viscometer (e.g., BL type, BH type, BS type, cone plate type, rheometer) or the like, and constitutes the main chain in diorganopolysiloxane. The value (or the degree of polymerization) of the repeating number m of the repeating unit ((R 1 ) 2 SiO 2/2 ) is, for example, the number average degree of polymerization in terms of polystyrene in gel permeation chromatography analysis using toluene or the like as a developing solvent ( or number average molecular weight).
Component (A) may be used alone or in combination of two or more.
［（Ｂ）成分］
（Ｂ）成分は、下記一般式（２）で示される加水分解性（オルガノ）シラン化合物及び／又はその部分加水分解縮合物であり、本発明の組成物の架橋剤・硬化剤として作用するものであると共に、（Ｂ）成分の一部は、上記（Ａ）成分の分子鎖両末端シラノール基封鎖ジオルガノポリシロキサンの末端シラノール基を、加水分解性シリル基で封鎖するためのシリル化剤としても作用するものである。
本発明において、「部分加水分解縮合物」とは、加水分解性（オルガノ）シラン化合物を部分的に加水分解・縮合して生成する分子中に残存加水分解性基を３個以上有する（オルガノ）シロキサンオリゴマーを意味する。
Component (B) is a hydrolyzable (organo)silane compound represented by the following general formula (2) and/or a partial hydrolytic condensate thereof, and acts as a cross-linking agent/curing agent for the composition of the present invention. and part of the component (B) is used as a silylating agent for blocking the terminal silanol groups of the silanol group-blocked diorganopolysiloxane having both molecular chain ends of the component (A) with hydrolyzable silyl groups. also works.
In the present invention, the term "partially hydrolyzed condensate" means a molecule formed by partially hydrolyzing and condensing a hydrolyzable (organo)silane compound and having three or more residual hydrolyzable groups in the molecule (organo). means a siloxane oligomer.
式（２）中、Ｒ2は、炭素数１～１０の非置換一価炭化水素基であり、例えばメチル基、エチル基、プロピル基などのアルキル基；シクロヘキシル基などのシクロアルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、トリル基などのアリール基；及びこれらの基の水素原子が部分的にハロゲン原子で置換された基、例えば３，３，３－トリフルオロプロピル基等が挙げられる。これらの中では、メチル基、エチル基、ビニル基が好ましく、メチル基、ビニル基が特に好ましい。ａは３又は４である。Ｒ2は、同一であってもよく、異なっていてもよい。 In formula (2), R 2 is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, such as alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclohexyl group; vinyl group; , an alkenyl group such as an allyl group; an aryl group such as a phenyl group and a tolyl group; and groups in which hydrogen atoms of these groups are partially substituted with halogen atoms, such as a 3,3,3-trifluoropropyl group mentioned. Among these, a methyl group, an ethyl group and a vinyl group are preferred, and a methyl group and a vinyl group are particularly preferred. a is 3 or 4; R 2 may be the same or different.
式（２）中のＯＲ3は加水分解性基であり、該加水分解性基は、炭素数１～４のアルコキシ基、炭素数２～４のケトオキシム基、炭素数２～４のアルケニルオキシ基、炭素数２又は３のアシロキシ基及び炭素数２～４のジアルキルアミノキシ基からなる群から選択される基であることが好ましい。該加水分解性基（ＯＲ3）としては、例えばメトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１～４、特に炭素数１又は２のアルコキシ基、エチルメチルケトオキシム基等の炭素数２～４のケトオキシム基、イソプロペノキシ基等の炭素数２～４のアルケニルオキシ基、アセトキシ基等の炭素数２又は３のアシロキシ基、ジメチルアミノキシ基等の炭素数２～４のジアルキルアミノキシ基等が挙げられ、ケトオキシム基、アルコキシ基、アルケニルオキシ基が好ましく、アルコキシ基、イソプロペノキシ基が特に好ましい。ＯＲ3は、同一であってもよく、異なっていてもよい。 OR 3 in formula (2) is a hydrolyzable group, and the hydrolyzable group is an alkoxy group having 1 to 4 carbon atoms, a ketoxime group having 2 to 4 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms. , an acyloxy group having 2 or 3 carbon atoms and a dialkylaminooxy group having 2 to 4 carbon atoms. Examples of the hydrolyzable group (OR 3 ) include carbon atoms such as methoxy, ethoxy, propoxy, and butoxy groups having 1 to 4 carbon atoms, particularly alkoxy groups having 1 or 2 carbon atoms and ethylmethylketoxime groups. ketoxime groups of 2 to 4 carbon atoms, alkenyloxy groups of 2 to 4 carbon atoms such as isopropenoxy groups, acyloxy groups of 2 or 3 carbon atoms such as acetoxy groups, dialkylaminooxy groups of 2 to 4 carbon atoms such as dimethylaminoxy groups A ketoxime group, an alkoxy group and an alkenyloxy group are preferred, and an alkoxy group and an isopropenoxy group are particularly preferred. OR 3 may be the same or different.
（Ｂ）成分の具体例としては、テトラメトキシシラン、テトラエトキシシラン、メチルトリス（ジメチルケトオキシム）シラン、メチルトリス（メチルエチルケトオキシム）シラン、エチルトリス（メチルエチルケトオキシム）シラン、メチルトリス（メチルイソブチルケトオキシム）シラン、ビニルトリス（メチルエチルケトオキシム）シラン、フェニルトリス（メチルエチルケトオキシム）シラン等のケトオキシムシラン；メチルトリメトキシシラン、ビニルトリメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、テトラメトキシシラン、テトラエトキシシラン等のアルコキシシラン；メチルトリイソプロペノキシシラン、エチルトリイソプロペノキシシラン、ビニルトリイソプロペノキシシラン、フェニルトリイソプロペノキシシラン等のイソプロペノキシ基含有シラン；メチルトリアセトキシシラン、エチルトリアセトキシシラン、ビニルトリアセトキシシラン等のアセトキシシラン、並びにこれらシランの部分加水分解縮合物が挙げられる。（Ｂ）成分は１種を単独で使用しても２種以上を併用してもよい。 Specific examples of component (B) include tetramethoxysilane, tetraethoxysilane, methyltris(dimethylketoxime)silane, methyltris(methylethylketoxime)silane, ethyltris(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, and vinyltris. ketoxime silanes such as (methylethylketoxime)silane, phenyltris(methylethylketoxime)silane ; alkoxysilanes such as methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane; isopropenoxy group-containing silanes such as methyltriisopropenoxysilane, ethyltriisopropenoxysilane, vinyltriisopropenoxysilane , and phenyltriisopropenoxysilane; methyltriacetoxysilane , ethyltriacetoxysilane, vinyltriacetoxysilane, etc. and partial hydrolytic condensates of these silanes. (B) component may be used individually by 1 type, or may use 2 or more types together.
（Ｂ）成分の配合量は、（Ａ）成分１００質量部に対して０．１～３０質量部、好ましくは０．５～２０質量部、より好ましくは１～１５質量部の範囲である。０．１質量部未満では、十分な架橋性が得られず、目的とするゴム弾性を有するシリコーンゴム硬化物を得ることができない場合がある。また３０質量部を超えると、得られるシリコーンゴム硬化物は機械特性が低下したり、組成物の硬化速度も遅くなる場合がある。 Component (B) is added in an amount of 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass per 100 parts by mass of component (A). If the amount is less than 0.1 parts by mass, sufficient crosslinkability may not be obtained, and a cured silicone rubber having the desired rubber elasticity may not be obtained. On the other hand, if the amount exceeds 30 parts by mass, the resulting cured silicone rubber may have poor mechanical properties and the curing speed of the composition may be slow.
［（Ｃ）成分］
（Ｃ）成分は、室温硬化性オルガノポリシロキサン組成物を硬化して得られるシリコーンゴム硬化物の機械的強度等の物性を向上させるための無機充填剤であり、例えば、粉砕シリカ、煙霧質シリカ（ヒュームドシリカ）、湿式シリカ、結晶性シリカ、水酸化アルミニウム、アルミナ、ベーマイト、水酸化マグネシウム、酸化マグネシウム、水酸化カルシウム、炭酸カルシウム、炭酸亜鉛、塩基性炭酸亜鉛、酸化亜鉛、酸化チタン、カーボンブラック、ガラスビーズ、ガラスバルーンなどが挙げられ、単独で使用してもよく、また２種類以上を組み合わせてもよい。これらの無機充填剤は、表面処理されていなくても、公知の処理剤で表面処理されていてもよい。公知の処理剤としては例えば、特開２０００－２５６５５８号公報に記載の加水分解性基含有ポリシロキサンが好ましいが、これに限定されるものではない。これらの中では、粉砕シリカ、煙霧質シリカ、湿式シリカ、結晶性シリカ等のシリカ系充填剤が好ましく、煙霧質シリカ、湿式シリカが特に好ましい。
[(C) component]
Component (C) is an inorganic filler for improving physical properties such as mechanical strength of the silicone rubber cured product obtained by curing the room temperature curable organopolysiloxane composition. Examples include pulverized silica and fumed silica. (fumed silica), wet silica, crystalline silica, aluminum hydroxide, alumina, boehmite, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium carbonate, zinc carbonate, basic zinc carbonate, zinc oxide, titanium oxide, carbon Black, glass beads, glass balloons, etc. may be mentioned, and may be used alone or in combination of two or more. These inorganic fillers may be surface-treated with a known treating agent even if they are not surface-treated. As a known treating agent, for example, hydrolyzable group-containing polysiloxane described in JP-A-2000-256558 is preferable, but the present invention is not limited to this. Among these, silica-based fillers such as pulverized silica, fumed silica, wet silica and crystalline silica are preferred, and fumed silica and wet silica are particularly preferred.
（Ｃ）成分で使用するシリカの比表面積（ＢＥＴ法）は、通常、５０～３００ｍ2／ｇが好ましく、５０～２５０ｍ2／ｇがより好ましく、５０～２００ｍ2／ｇが特に好ましい。比表面積が５０ｍ2／ｇ未満の場合、良好なチキソトロピー性を有する組成物が得られず、目的とするゴム強度やゴム弾性を有する硬化物が得難い場合がある。また３００ｍ2／ｇを超えると、オルガノポリシロキサンに対して添加できる量が限られ、汎用性に富む室温硬化性オルガノポリシロキサン組成物を調製するのが困難となる場合がある。 The specific surface area (BET method) of silica used as component (C) is generally preferably 50 to 300 m 2 /g, more preferably 50 to 250 m 2 /g, particularly preferably 50 to 200 m 2 /g. If the specific surface area is less than 50 m 2 /g, it may not be possible to obtain a composition having good thixotropy, and it may be difficult to obtain a cured product having the desired rubber strength and rubber elasticity. On the other hand, if it exceeds 300 m 2 /g, the amount that can be added to the organopolysiloxane is limited, and it may become difficult to prepare a versatile room-temperature-curable organopolysiloxane composition.
（Ｃ）成分の配合量は、（Ａ）成分１００質量部に対して１～２００質量部、好ましくは１～１００質量部、特に好ましくは１～５０質量部である。１質量部未満では、良好なチキソトロピー性を有する組成物が得られず、目的とするゴム強度やゴム弾性を有する硬化物が得難い場合がある。また２００質量部を超えると、前記（Ａ）成分との混練が困難となり、良好な室温硬化性オルガノポリシロキサン組成物を調製するのが難しい場合がある。 Component (C) is blended in an amount of 1 to 200 parts by mass, preferably 1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass per 100 parts by mass of component (A). If it is less than 1 part by mass, a composition having good thixotropy cannot be obtained, and it may be difficult to obtain a cured product having the desired rubber strength and rubber elasticity. If it exceeds 200 parts by mass, it may become difficult to knead with the component (A), making it difficult to prepare a good room-temperature-curable organopolysiloxane composition.
［（Ｄ）成分］
（Ｄ）成分は、室温硬化性オルガノポリシロキサン組成物において、上記（Ａ）成分の分子鎖両末端シラノール基封鎖ジオルガノポリシロキサンの末端シラノール基を（Ｂ）成分から誘導される加水分解性シリル基で封鎖する（（Ａ）成分の分子鎖両末端を加水分解性シロキシ化する）ために作用するための末端封鎖触媒（縮合触媒）として働く重要な化合物であり、具体的には、１分子中に窒素原子を３個以上、好ましくは３～６個、より好ましくは３～５個有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物であり、特には、下記一般式（３）又は一般式（３）’で示される、触媒機能を発現する１価又は２価の塩基性部位（Ｙ）を有するアミノ基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物である。
Component (D) is a room-temperature-curable organopolysiloxane composition in which hydrolyzable silyl groups derived from component (B) are used as the terminal silanol groups of component (A), a diorganopolysiloxane having both molecular chain ends blocked with silanol groups. It is an important compound that acts as a terminal-blocking catalyst (condensation catalyst) for blocking with a group (hydrolyzably siloxylating both ends of the molecular chain of component (A)). An amino functional group-containing hydrolyzable organosilane compound and/or a partial hydrolysis condensate thereof having 3 or more, preferably 3 to 6, more preferably 3 to 5 nitrogen atoms therein, particularly An amino group-containing hydrolyzable organosilane compound and/or a portion thereof having a monovalent or divalent basic site (Y) exhibiting a catalytic function, represented by the following general formula (3) or general formula (3)' It is a hydrolytic condensate.
式（３）及び（３）’中、Ｙは、その構造中に窒素原子を２個以上含有する炭素数１～１５の１価又は２価炭化水素基を示し、Ｚは、ヘテロ原子を含んでもよい炭素数１～１０の非置換又は置換の２価炭化水素基を示す。Ｒは、炭素数１～６の加水分解性基及び炭素数１～６の１価炭化水素基から選ばれる１種又は２種以上の１価の基であり、ケイ素原子に結合する３個のＲのうち、少なくとも２個のＲは加水分解性基である。 In formulas (3) and (3)′, Y represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms containing 2 or more nitrogen atoms in its structure, and Z contains a heteroatom. It represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted. R is one or more monovalent groups selected from a hydrolyzable group having 1 to 6 carbon atoms and a monovalent hydrocarbon group having 1 to 6 carbon atoms, and three groups bonded to a silicon atom Of R, at least two R are hydrolyzable groups.
一般式（３）又は一般式（３）’において、触媒機能を発現する１価又は２価の塩基性部位（Ｙ）は、その構造中に窒素原子を２個以上、好ましくは２～５個、より好ましくは２～４個有する炭素数１～１５の１価又は２価炭化水素基を示し、塩基性部位（Ｙ）のうち、１価の基としては、例えば、下記式（４）で示される１，５，７－トリアザビシクロ［４.４.０］デカ－５－エンから誘導される基など、２価の基としては、例えば、下記式（５）で示されるＮ－置換又は非置換のグアニジル基等が挙げられる。なお、下記式（４）及び（５）において、波線部は、式（３）又は式（３）’の窒素原子との結合部位を示す。
式（５）中のＲ4～Ｒ7はそれぞれ、水素原子又は炭素数１～１０の直鎖状、分岐状もしくは環状のアルキル基、アルケニル基、アリール基を示し、例えば、メチル基、エチル基、プロピル基等のアルキル基；シクロヘキシル基等の環状アルキル基；ビニル基、アリル基等のアルケニル基；フェニル基、トリル基等のアリール基などが挙げられる。これらの中では、メチル基、エチル基、フェニル基が好ましく、特にメチル基が好ましい。また、Ｒ4～Ｒ7は同じであっても、異なっていてもよい。 R 4 to R 7 in formula (5) each represent a hydrogen atom or a linear, branched or cyclic alkyl group, alkenyl group or aryl group having 1 to 10 carbon atoms, such as a methyl group or an ethyl group. , a propyl group; a cyclic alkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group and an allyl group; and an aryl group such as a phenyl group and a tolyl group. Among these, a methyl group, an ethyl group and a phenyl group are preferred, and a methyl group is particularly preferred. Also, R 4 to R 7 may be the same or different.
また、上記式（３）又は（３）’において、Ｒは、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｔｅｒｔ－ブトキシ基等のアルコキシ基、ビニロキシ基、アリロキシ基、プロペノキシ基、イソプロペノキシ基等のアルケニルオキシ基、ジメチルケトオキシム基、ジエチルケトオキシム基、メチルエチルケトオキシム基等のケトオキシム基、アセトキシ基等のアシルオキシ基などの炭素数１～６、好ましくは炭素数１～４の加水分解性基（即ち、ケイ素原子に結合してＳｉ－Ｏ－Ｃ結合を形成し得る基）、及び、メチル基、エチル基等のアルキル基、ビニル基等のアルケニル基、フェニル基等のアリール基などの炭素数１～６、好ましくは炭素数１～４の１価炭化水素基から選ばれる１種又は２種以上の１価の基であり、ケイ素原子に結合する３個のＲのうち、少なくとも２個、好ましくは３個のＲは加水分解性基である。 Further, in the above formula (3) or (3)', R is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, an alkoxy group such as a tert-butoxy group, a vinyloxy group, and an allyloxy group. , a propenoxy group, an alkenyloxy group such as an isopropenoxy group, a ketoxime group such as a dimethylketoxime group, a diethylketoxime group, a methylethylketoxime group, an acyloxy group such as an acetoxy group having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms. 4 hydrolyzable group (that is, a group capable of forming a Si—O—C bond by bonding to a silicon atom), and an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group, a phenyl group, etc. One or more monovalent groups selected from monovalent hydrocarbon groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as an aryl group, and 3 R bonded to a silicon atom Among them, at least two, preferably three R's are hydrolyzable groups.
また、上記式（３）又は（３）’において、加水分解性シリル基（－ＳｉＲ3）としては、例えば、トリメトキシシリル基、メチルジメトキシシリル基、ビニルジメトキシシリル基、フェニルジメトキシシリル基、トリエトキシシリル基等のアルコキシシリル基；トリイソプロペノキシシリル基、メチルジイソプロペノキシシリル基、エチルジイソプロペノキシシリル基、ビニルジイソプロペノキシシリル基、フェニルジイソプロペノキシシリル基等のイソプロペノキシシリル基；トリス（ジメチルケトオキシム）シリル基、トリス（ジエチルケトオキシム）シリル基、トリス（エチルメチルケトオキシム）シリル基等のケトオキシムシリル基などが挙げられる。 In the above formula (3) or (3)′, the hydrolyzable silyl group (—SiR 3 ) includes, for example, a trimethoxysilyl group, a methyldimethoxysilyl group, a vinyldimethoxysilyl group, a phenyldimethoxysilyl group, a trimethoxysilyl group, a Alkoxysilyl groups such as ethoxysilyl groups; isopropenoxysilyl groups such as triisopropenoxysilyl groups, methyldiisopropenoxysilyl groups, ethyldiisopropenoxysilyl groups, vinyldiisopropenoxysilyl groups and phenyldiisopropenoxysilyl groups; penoxysilyl group; ketoxime silyl groups such as tris(dimethylketoxime)silyl group, tris(diethylketoxime)silyl group and tris(ethylmethylketoxime)silyl group;
上記式（３）又は（３）’において、Ｚは、酸素原子、窒素原子等のヘテロ原子を含んでもよい、炭素数１～１０、特には炭素数３～６の、直鎖状、分岐状もしくは環状のアルキレン基、アルケニレン基、アリーレン基等又はこれらが組み合わされた基などの非置換又は置換の２価炭化水素基を示す。Ｚとしては、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ヘキサメチレン基、オクタメチレン基、デカメチレン基、２－メチルプロピレン基等のアルキレン基；フェニレン基等のアリーレン基、これらアルキレン基とアリーレン基が結合した基、ケトン、エステル、アミド等が介在した上記アルキレン基などが挙げられるが、好ましくはメチレン基、エチレン基、トリメチレン基、プロピレン基、アミド結合を介したプロピレン基等であり、特に好ましくはトリメチレン基である。 In the above formula (3) or (3)′, Z is a linear or branched chain having 1 to 10 carbon atoms, particularly 3 to 6 carbon atoms, which may contain a heteroatom such as an oxygen atom or a nitrogen atom. Alternatively, it represents an unsubstituted or substituted divalent hydrocarbon group such as a cyclic alkylene group, alkenylene group, arylene group, or a combination thereof. Z is, for example, a methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, alkylene group such as 2-methylpropylene group; arylene group such as phenylene group; Examples include groups in which these alkylene groups and arylene groups are bonded, and the above alkylene groups interposed by ketones, esters, amides, etc., preferably methylene group, ethylene group, trimethylene group, propylene group, or propylene group via an amide bond. etc., and a trimethylene group is particularly preferred.
一般式（３）又は一般式（３）’で示されるアミノ基含有加水分解性オルガノシランの具体例としては、下記一般式（６）～（１１）に示されるもの等を挙げることができる。なお、Ｍｅ、Ｅｔ、Ｐｈはそれぞれ、メチル基、エチル基、フェニル基を示す。
上記一般式（６）～（１１）のうち、式（６）、式（７）又は式（８）で示される、特には、式（８）で示される、Ｎ－メチル置換のグアニジル基含有トリメトキシシラン（例えば、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン）等の、Ｎ－メチル置換グアニジル基含有トリアルコキシシランが好ましい。 Among the above general formulas (6) to (11), the N-methyl-substituted guanidyl group-containing represented by formula (6), formula (7) or formula (8), particularly represented by formula (8) Preferred are trialkoxysilanes containing N-methyl-substituted guanidyl groups, such as trimethoxysilane (eg, γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane).
（Ｄ）成分の配合量は、（Ａ）成分１００質量部に対して、０．５～３質量部であり、０．５～２質量部が好ましく、０．５～１．５質量部がより好ましい。０．５質量部未満では、目的とする末端封鎖触媒としての機能を果たさない場合がある。３質量部を超えると、末端封鎖には有利に働くが、コスト的に不利となるため好ましくない。 The blending amount of component (D) is 0.5 to 3 parts by mass, preferably 0.5 to 2 parts by mass, and 0.5 to 1.5 parts by mass based on 100 parts by mass of component (A). more preferred. If it is less than 0.5 parts by mass, it may fail to function as the intended end-blocking catalyst. If the amount exceeds 3 parts by mass, it works advantageously for terminal blocking, but it is disadvantageous in terms of cost, which is not preferable.
［その他の成分］
本発明の室温硬化性オルガノポリシロキサン組成物の製造方法は、上述の（Ａ）成分～（Ｄ）成分に加えて、必要に応じて任意成分を組成物に配合する工程を有していてもよい。該工程は、上記第１工程後であってもよいし、上記第２工程中であってもよいし、上記第２工程後であってもよい。
該組成物の硬化物の各種被着体への接着性をさらに向上させるために、必要に応じて配合できる任意成分として、シランカップリング剤（１分子中に、窒素、硫黄及び酸素から選ばれるヘテロ原子を含有する官能性基（但し、グアニジル基を除く）を有する１価炭化水素基を有するアルコキシシラン等の加水分解性シラン化合物、又はいわゆるカーボンファンクショナルシラン化合物）を接着性付与剤として組成物に配合してもよい。シランカップリング剤としては、加水分解性基として、アルコキシシリル基又はアルケノキシシリル基を有するシラン化合物が挙げられ、ビニルトリス（β－メトキシエトキシ）シラン、γ－メタクリロキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、Ｎ－β－（アミノエチル）γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、３－（Ｎ－アミノメチルベンジルアミノ）プロピルトリメトキシシラン、Ｎ，Ｎ’－ビス［３－（トリメトキシシリル）プロピル］エチレンジアミン、Ｎ，Ｎ－ビス［３－（トリメトキシシリル）プロピル］アミン、γ－メルカプトプロピルトリメトキシシラン、γ－グリシドキシプロピルトリイソプロペノキシシラン、γ－グリシドキシプロピルメチルジイソプロペノキシシラン、（メタ）アクリルシランとアミノシランの反応物、エポキシシランとアミノシランの反応物等、アミノシランとハロゲン化アルキル基含有シランとの反応物などが例示される。特にはアミノ基を１分子内に少なくとも１つ有するシランカップリング剤の使用が好ましい。
[Other ingredients]
The method for producing the room-temperature-curable organopolysiloxane composition of the present invention may have a step of blending optional components into the composition as necessary in addition to the components (A) to (D) described above. good. The step may be after the first step, during the second step, or after the second step.
In order to further improve the adhesion of the cured product of the composition to various adherends, a silane coupling agent (in one molecule, selected from nitrogen, sulfur and oxygen A hydrolyzable silane compound such as an alkoxysilane having a monovalent hydrocarbon group having a heteroatom-containing functional group (excluding a guanidyl group), or a so-called carbon functional silane compound) is used as an adhesion imparting agent. You can mix it with the product. Silane coupling agents include silane compounds having an alkoxysilyl group or an alkenoxysilyl group as a hydrolyzable group, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-(N-aminomethylbenzylamino)propyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N-bis[3-( Trimethoxysilyl)propyl]amine, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, reaction of (meth)acrylsilane and aminosilane reaction products of epoxysilane and aminosilane; and reaction products of aminosilane and halogenated alkyl group-containing silanes. In particular, it is preferable to use a silane coupling agent having at least one amino group in one molecule.
シランカップリング剤を配合する場合、その配合量は、（Ａ）成分１００質量部当たり、通常、０．１～２０質量部、好ましくは０．１～１０質量部、特に好ましくは０．１～５質量部である。０．１質量部未満では十分な接着性が得られない場合があり、２０質量部を超えると良好な機械特性が得られなかったり、また価格的に不利となる場合がある。 When a silane coupling agent is blended, the blending amount is usually 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, particularly preferably 0.1 to 10 parts by mass, per 100 parts by mass of component (A). 5 parts by mass. If the amount is less than 0.1 part by mass, sufficient adhesion may not be obtained, and if the amount exceeds 20 parts by mass, good mechanical properties may not be obtained and the cost may be disadvantageous.
また、本発明の室温硬化性オルガノポリシロキサン組成物の製造方法は、必要に応じて配合できる任意成分として、上記（Ｄ）成分以外の硬化触媒（縮合触媒）を組成物に配合する工程を有していてもよい。この（Ｄ）成分以外の硬化触媒は、金属系縮合触媒や非金属系縮合触媒を好適に使用することができ、１種を単独で使用しても２種以上の混合物として使用してもよい。（Ｄ）成分以外の硬化触媒（縮合触媒）としては、例えば、錫、チタン、ジルコニウム、鉄、アンチモン、ビスマス、マンガン等の金属の有機カルボン酸塩及びアルコキサイド；有機チタン酸エステル；有機チタンキレート化合物が例示され、より具体的には、ジブチル錫ジラウレート、ジブチル錫ジオクトエート、ジオクチル錫ジラウレート、ジブチル錫マレートエステル、ジメチル錫ジネオデカノエート、ジブチル錫ジメトキサイド、ジオクチル錫ジネオデカノエート、スタナスオクトエート等の錫化合物；テトラブチルチタネート、ジイソプロポキシビス（アセチルアセトネート）チタン、ジイソプロポキシビス（エチルアセトアセテート）等のチタン化合物などの金属系縮合触媒；ジブチルアミン、ラウリルアミン等のアミン化合物及びその塩；ヘキサメチルジシラザン等のオルガノシラザン化合物などの非金属系縮合触媒等が例示される。本発明の製造方法で製造される室温硬化性オルガノポリシロキサン組成物は、速硬化性や深部硬化性などの硬化特性が優れることから、有機錫化合物を添加することが好ましく、中でも、ジアルキル錫ジアルコキサイド、ジアルキル錫ジカルボン酸塩であることが特に好ましい。 In addition, the method for producing a room-temperature-curable organopolysiloxane composition of the present invention has a step of adding a curing catalyst (condensation catalyst) other than the component (D) to the composition as an optional component that can be blended as needed. You may have As the curing catalyst other than the component (D), a metallic condensation catalyst or a non-metallic condensation catalyst can be suitably used, and one kind may be used alone or two or more kinds may be used as a mixture. . Curing catalysts (condensation catalysts) other than component (D) include, for example, organic carboxylates and alkoxides of metals such as tin, titanium, zirconium, iron, antimony, bismuth, and manganese; organic titanate esters; organic titanium chelate compounds. More specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dibutyltin maleate ester, dimethyltin dineodecanoate, dibutyltin dimethoxide, dioctyltin dineodecanoate, stannus Tin compounds such as octoate; metal-based condensation catalysts such as titanium compounds such as tetrabutyl titanate, diisopropoxybis(acetylacetonate) titanium, diisopropoxybis(ethylacetoacetate); amines such as dibutylamine and laurylamine compounds and salts thereof; and non-metallic condensation catalysts such as organosilazane compounds such as hexamethyldisilazane. Since the room-temperature-curable organopolysiloxane composition produced by the production method of the present invention exhibits excellent curing properties such as rapid curing and deep-curing properties, it is preferable to add an organic tin compound. Coxides and dialkyltin dicarboxylates are particularly preferred.
（Ｄ）成分以外の硬化触媒（縮合触媒）を配合する場合、その添加量は、（Ａ）成分１００質量部に対して、０．００１～２０質量部、好ましくは０．０１～５質量部、特に好ましくは０．０３～３質量部である。０．００１質量部未満では、充分な架橋性（硬化性）が得られない場合があり、２０質量部を超えると、価格的に不利になる場合や硬化速度が低下するなどの不都合が生じる場合がある。 When a curing catalyst (condensation catalyst) other than component (D) is added, the amount added is 0.001 to 20 parts by mass, preferably 0.01 to 5 parts by mass, per 100 parts by mass of component (A). , and particularly preferably 0.03 to 3 parts by mass. If it is less than 0.001 parts by mass, sufficient crosslinkability (curability) may not be obtained. There is
また、本発明の室温硬化性オルガノポリシロキサン組成物の製造方法は上記成分以外に、各種の添加剤を任意成分として配合する工程を有していてもよい。該工程は、上記第１工程後であってもよいし、上記第２工程中であってもよいし、上記第２工程後であってもよい。
添加剤としては、公知の添加剤を本発明の目的を損なわない範囲で添加してもよい。例えば、ウェッターやチキソトロピー向上剤としてのポリエーテル化合物、可塑剤としての非反応性ジメチルシリコーンオイル（分子鎖両末端トリアルキルシリル基封鎖ジメチルポリシロキサン）、イソパラフィン、架橋密度向上剤としてのトリメチルシロキシ単位〔（ＣＨ3）3ＳｉＯ1/2単位〕とＳｉＯ2単位とからなる三次元網状構造のオルガノポリシロキサンレジン等が挙げられる。
In addition, the method for producing the room-temperature-curable organopolysiloxane composition of the present invention may have a step of blending various additives as optional components in addition to the above components. The step may be after the first step, during the second step, or after the second step.
As additives, known additives may be added as long as they do not impair the object of the present invention. For example, polyether compounds as wetters and thixotropy improvers, non-reactive dimethylsilicone oils (dimethylpolysiloxane blocked with trialkylsilyl groups at both molecular chain ends) as plasticizers, isoparaffins, and trimethylsiloxy units [as crosslink density improvers]. (CH 3 ) 3 SiO 1/2 units] and SiO 2 units, and organopolysiloxane resins having a three-dimensional network structure.
更に、必要に応じて、顔料、染料、蛍光増白剤等の着色剤；防かび剤；抗菌剤；非反応性フェニルシリコーンオイル（分子鎖両末端トリアルキルシリル基封鎖メチルフェニルポリシロキサン）、フルオロシリコーンオイル（分子鎖両末端トリアルキルシリル基封鎖メチル（３，３，３－トリフルオロプロピル）ポリシロキサン）等のブリードオイル；シリコーンと非相溶性である有機液体等の表面改質剤；及びトルエン、キシレン、溶剤揮発油、シクロヘキサン、メチルシクロヘキサン、低沸点イソパラフィン等の溶剤も添加してよい。 Furthermore, if necessary, coloring agents such as pigments, dyes, and fluorescent brighteners; antifungal agents; antibacterial agents; Bleed oil such as silicone oil (methyl (3,3,3-trifluoropropyl) polysiloxane blocked with trialkylsilyl groups at both molecular chain ends); surface modifier such as organic liquid incompatible with silicone; and toluene , xylene, solvent volatile oils, cyclohexane, methylcyclohexane, low boiling isoparaffins and the like may also be added.
本発明の製造方法により製造された本発明の室温硬化性オルガノポリシロキサン組成物は、湿分を避けた雰囲気下で保存することができ、これを室温（２３℃±１５℃）で、空気雰囲気下に放置すると、空気中の水分により通常５分～１週間で硬化する。 The room-temperature-curable organopolysiloxane composition of the present invention produced by the production method of the present invention can be stored in a moisture-free atmosphere and stored at room temperature (23° C.±15° C.) in an air atmosphere. When left standing, it usually cures in 5 minutes to 1 week due to moisture in the air.
以下、本発明を具体的に説明する実施例及び比較例を示すが、本発明は下記の実施例に制限されるものではない。なお、実施例において、粘度は２３℃における回転粘度計による測定値であり、重合度は、トルエンを展開溶媒とした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を示す。なお、Ｍｅはメチル基を示す。 EXAMPLES Examples and comparative examples for specifically explaining the present invention are shown below, but the present invention is not limited to the following examples. In the examples, the viscosity is a value measured by a rotational viscometer at 23° C., and the degree of polymerization is the number-average degree of polymerization in terms of polystyrene in gel permeation chromatography analysis using toluene as a developing solvent. In addition, Me shows a methyl group.
実施例１
分子鎖両末端がシラノール基で封鎖され２３℃における粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン（一般式（１）において、Ｒ1＝メチル基、ｍ＝約９７０に相当するもの）６０質量部、メチルトリメトキシシラン３．０質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン１．０質量部を減圧下にて６０分混合して均一な混合物を調製した。次いで、該混合物に比表面積が１３０ｍ2／ｇの煙霧質シリカ９．０質量部を減圧下にて３０分混合した後、分子鎖両末端がトリメチルシリル基で封鎖され２３℃における粘度が１００ｍＰａ・ｓのジメチルポリシロキサン２５質量部を減圧下にて１５分混合した。最後に、メチルトリメトキシシラン３．０質量部、γ－アミノプロピルトリエトキシシラン１．０質量部、ヘキサメチルジシラザン０．５質量部、ジオクチル錫ジラウレート０．２質量部を減圧下にて１５分混合して組成物１を得た。
Example 1
60 parts by mass of dimethylpolysiloxane (corresponding to R 1 = methyl group and m = about 970 in general formula (1)) having a viscosity of 50,000 mPa·s at 23°C and having both ends of the molecular chain blocked with silanol groups , 3.0 parts by weight of methyltrimethoxysilane, and 1.0 parts by weight of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane were mixed under reduced pressure for 60 minutes to prepare a uniform mixture. Next, 9.0 parts by mass of fumed silica having a specific surface area of 130 m 2 /g was mixed with the mixture under reduced pressure for 30 minutes, and both ends of the molecular chain were blocked with trimethylsilyl groups so that the viscosity at 23° C. was 100 mPa·s. was mixed under reduced pressure for 15 minutes. Finally, 3.0 parts by mass of methyltrimethoxysilane, 1.0 parts by mass of γ-aminopropyltriethoxysilane, 0.5 parts by mass of hexamethyldisilazane, and 0.2 parts by mass of dioctyltin dilaurate were added to 15 parts by mass under reduced pressure. A composition 1 was obtained by mixing for minutes.
実施例２
分子鎖両末端がシラノール基で封鎖され２３℃における粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン（一般式（１）において、Ｒ1＝メチル基、ｍ＝約９７０に相当するもの）６０質量部、メチルトリメトキシシラン３．０質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン１．０質量部を減圧下にて６０分混合して均一な混合物を調製した。次いで、該混合物に比表面積が１３０ｍ2／ｇの煙霧質シリカ９．０質量部を減圧下にて３０分混合した後、分子鎖両末端がトリメチルシリル基で封鎖され２３℃における粘度が１００ｍＰａ・ｓのジメチルポリシロキサン２５質量部を減圧下にて１５分混合した。最後に、メチルトリメトキシシラン３．０質量部、Ｎ－β－（アミノエチル）γ－アミノプロピルトリメトキシシラン１．０質量部、ヘキサメチルジシラザン０．５質量部、ジオクチル錫ジラウレート０．２質量部を減圧下にて１５分混合して組成物２を得た。
Example 2
60 parts by mass of dimethylpolysiloxane (corresponding to R 1 = methyl group and m = about 970 in general formula (1)) having a viscosity of 50,000 mPa·s at 23°C and having both ends of the molecular chain blocked with silanol groups , 3.0 parts by weight of methyltrimethoxysilane, and 1.0 parts by weight of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane were mixed under reduced pressure for 60 minutes to prepare a homogeneous mixture. Next, 9.0 parts by mass of fumed silica having a specific surface area of 130 m 2 /g was mixed with the mixture under reduced pressure for 30 minutes, and both ends of the molecular chain were blocked with trimethylsilyl groups so that the viscosity at 23° C. was 100 mPa·s. was mixed under reduced pressure for 15 minutes. Finally, 3.0 parts by weight of methyltrimethoxysilane, 1.0 parts by weight of N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, 0.5 parts by weight of hexamethyldisilazane, and 0.2 parts by weight of dioctyltin dilaurate. A composition 2 was obtained by mixing parts by mass for 15 minutes under reduced pressure.
実施例３
分子鎖両末端がシラノール基で封鎖され２３℃における粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン（一般式（１）において、Ｒ1＝メチル基、ｍ＝約９７０に相当するもの）６０質量部、メチルトリメトキシシラン３．０質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン１．０質量部を減圧下にて６０分混合して均一な混合物を調製した。次いで、該混合物に比表面積が１３０ｍ2／ｇの煙霧質シリカ９．０質量部を減圧下にて３０分混合した後、分子鎖両末端がトリメチルシリル基で封鎖され２３℃における粘度が１００ｍＰａ・ｓのジメチルポリシロキサン２５質量部を減圧下にて１５分混合した。最後に、ビニルトリメトキシシラン３．０質量部、γ－アミノプロピルトリエトキシシラン１．０質量部、ヘキサメチルジシラザン０．５質量部、ジオクチル錫ジラウレート０．２質量部を減圧下にて１５分混合して組成物３を得た。
Example 3
60 parts by mass of dimethylpolysiloxane (corresponding to R 1 = methyl group and m = about 970 in general formula (1)) having a viscosity of 50,000 mPa·s at 23°C and having both ends of the molecular chain blocked with silanol groups , 3.0 parts by weight of methyltrimethoxysilane, and 1.0 parts by weight of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane were mixed under reduced pressure for 60 minutes to prepare a homogeneous mixture. Next, 9.0 parts by mass of fumed silica having a specific surface area of 130 m 2 /g was mixed with the mixture under reduced pressure for 30 minutes, and both ends of the molecular chain were blocked with trimethylsilyl groups so that the viscosity at 23° C. was 100 mPa·s. was mixed under reduced pressure for 15 minutes. Finally, 3.0 parts by mass of vinyltrimethoxysilane, 1.0 parts by mass of γ-aminopropyltriethoxysilane, 0.5 parts by mass of hexamethyldisilazane, and 0.2 parts by mass of dioctyltin dilaurate were added to 15 parts by mass under reduced pressure. A composition 3 was obtained by mixing for minutes.
実施例４
分子鎖両末端がシラノール基で封鎖され２３℃における粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン（一般式（１）において、Ｒ1＝メチル基、ｍ＝約９７０に相当するもの）６０質量部、メチルトリメトキシシラン３．０質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン１．０質量部を減圧下にて６０分混合して均一な混合物を調製した。次いで、該混合物に比表面積が１３０ｍ2／ｇの煙霧質シリカ９．０質量部を減圧下にて３０分混合した後、分子鎖両末端がトリメチルシリル基で封鎖され２３℃における粘度が１００ｍＰａ・ｓのジメチルポリシロキサン２５質量部を減圧下にて１５分混合した。最後に、２３℃における粘度が５ｍＰａ・ｓであるメチルトリメトキシシランのオリゴマー（信越化学工業（株）製 ＫＣ－８９Ｅ）を２．０質量部、γ－アミノプロピルトリエトキシシラン１．０質量部、ヘキサメチルジシラザン０．５質量部、ジオクチル錫ジラウレート０．２質量部を減圧下にて１５分混合して組成物４を得た。
Example 4
60 parts by mass of dimethylpolysiloxane (corresponding to R 1 = methyl group and m = about 970 in general formula (1)) having a viscosity of 50,000 mPa·s at 23°C and having both ends of the molecular chain blocked with silanol groups , 3.0 parts by weight of methyltrimethoxysilane, and 1.0 parts by weight of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane were mixed under reduced pressure for 60 minutes to prepare a uniform mixture. Next, 9.0 parts by mass of fumed silica having a specific surface area of 130 m 2 /g was mixed with the mixture under reduced pressure for 30 minutes, and both ends of the molecular chain were blocked with trimethylsilyl groups so that the viscosity at 23° C. was 100 mPa·s. was mixed under reduced pressure for 15 minutes. Finally, 2.0 parts by mass of an oligomer of methyltrimethoxysilane (KC-89E manufactured by Shin-Etsu Chemical Co., Ltd.) having a viscosity of 5 mPa s at 23° C., and 1.0 parts by mass of γ-aminopropyltriethoxysilane. , 0.5 parts by mass of hexamethyldisilazane, and 0.2 parts by mass of dioctyltin dilaurate were mixed under reduced pressure for 15 minutes to obtain composition 4.
比較例１
分子鎖両末端がシラノール基で封鎖され２３℃における粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン（一般式（１）において、Ｒ1＝メチル基、ｍ＝約９７０に相当するもの）６０質量部、メチルトリメトキシシラン３．０質量部、下記式（１２）で示される１分子中にアミノ基を２個有するアミノ官能性基含有加水分解性オルガノシラン化合物１．０質量部を減圧下にて６０分混合して均一な混合物を調製した。次いで、該混合物に比表面積が１３０ｍ2／ｇの煙霧質シリカ９．０質量部を減圧下にて３０分混合した後、分子鎖両末端がトリメチルシリル基で封鎖され２３℃における粘度が１００ｍＰａ・ｓのジメチルポリシロキサン２５質量部を減圧下にて１５分混合した。最後に、メチルトリメトキシシラン３．０質量部、γ－アミノプロピルトリエトキシシラン１．０質量部、ヘキサメチルジシラザン０．５質量部、ジオクチル錫ジラウレート０．２質量部を減圧下にて１５分混合して組成物５を得た。
Ｍｅはメチル基を示す。
Comparative example 1
60 parts by mass of dimethylpolysiloxane (corresponding to R 1 = methyl group and m = about 970 in general formula (1)) having a viscosity of 50,000 mPa·s at 23°C and having both ends of the molecular chain blocked with silanol groups , 3.0 parts by mass of methyltrimethoxysilane, and 1.0 parts by mass of a hydrolyzable organosilane compound containing two amino groups in one molecule represented by the following formula (12) under reduced pressure. Mixed for 60 minutes to prepare a homogeneous mixture. Next, 9.0 parts by mass of fumed silica having a specific surface area of 130 m 2 /g was mixed with the mixture under reduced pressure for 30 minutes, and both ends of the molecular chain were blocked with trimethylsilyl groups so that the viscosity at 23° C. was 100 mPa·s. was mixed under reduced pressure for 15 minutes. Finally, 3.0 parts by mass of methyltrimethoxysilane, 1.0 parts by mass of γ-aminopropyltriethoxysilane, 0.5 parts by mass of hexamethyldisilazane, and 0.2 parts by mass of dioctyltin dilaurate were added to 15 parts by mass under reduced pressure. A composition 5 was obtained by mixing for minutes.
Me represents a methyl group.
比較例２
分子鎖両末端がシラノール基で封鎖され２３℃における粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン（一般式（１）において、Ｒ1＝メチル基、ｍ＝約９７０に相当するもの）６０質量部、メチルトリメトキシシラン３．０質量部、γ－アミノプロピルトリエトキシシラン１．０質量部を減圧下にて６０分混合して均一な混合物を調製した。次いで、該混合物に比表面積が１３０ｍ2／ｇの煙霧質シリカ９．０質量部を減圧下にて３０分混合した後、分子鎖両末端がトリメチルシリル基で封鎖され２３℃における粘度が１００ｍＰａ・ｓのジメチルポリシロキサン２５質量部を減圧下にて１５分混合した。最後に、メチルトリメトキシシラン３．０質量部、γ－アミノプロピルトリエトキシシラン１．０質量部、ヘキサメチルジシラザン０．５質量部、ジオクチル錫ジラウレート０．２質量部を減圧下にて１５分混合して組成物６を得た。
Comparative example 2
60 parts by mass of dimethylpolysiloxane (corresponding to R 1 = methyl group and m = about 970 in general formula (1)) having a viscosity of 50,000 mPa·s at 23°C and having both ends of the molecular chain blocked with silanol groups , 3.0 parts by mass of methyltrimethoxysilane, and 1.0 parts by mass of γ-aminopropyltriethoxysilane were mixed under reduced pressure for 60 minutes to prepare a uniform mixture. Next, 9.0 parts by mass of fumed silica having a specific surface area of 130 m 2 /g was mixed with the mixture under reduced pressure for 30 minutes, and both ends of the molecular chain were blocked with trimethylsilyl groups so that the viscosity at 23° C. was 100 mPa·s. was mixed under reduced pressure for 15 minutes. Finally, 3.0 parts by mass of methyltrimethoxysilane, 1.0 parts by mass of γ-aminopropyltriethoxysilane, 0.5 parts by mass of hexamethyldisilazane, and 0.2 parts by mass of dioctyltin dilaurate were added to 15 parts by mass under reduced pressure. A composition 6 was obtained by mixing for minutes.
比較例３
分子鎖両末端がシラノール基で封鎖され２３℃における粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン（一般式（１）において、Ｒ1＝メチル基、ｍ＝約９７０に相当するもの）６０質量部、分子鎖両末端がトリメチルシリル基で封鎖され２３℃における粘度が１００ｍＰａ・ｓのジメチルポリシロキサン２５質量部、メチルトリメトキシシラン６．０質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン１．０質量部、比表面積が１３０ｍ2／ｇの煙霧質シリカ９．０質量部、γ－アミノプロピルトリエトキシシラン１．０質量部、ヘキサメチルジシラザン０．５質量部、ジオクチル錫ジラウレート０．２質量部を一括して同時に（同一工程中に）配合し、減圧下にて１５分混合して組成物７を得た。
Comparative example 3
60 parts by mass of dimethylpolysiloxane (corresponding to R 1 = methyl group and m = about 970 in general formula (1)) having a viscosity of 50,000 mPa·s at 23°C and having both ends of the molecular chain blocked with silanol groups , 25 parts by mass of dimethylpolysiloxane having a viscosity of 100 mPa s at 23 ° C., 6.0 parts by mass of methyltrimethoxysilane, γ-(N,N'-dimethylguanidyl) 1.0 parts by weight of propyltrimethoxysilane, 9.0 parts by weight of fumed silica having a specific surface area of 130 m 2 /g, 1.0 parts by weight of γ-aminopropyltriethoxysilane, 0.5 parts by weight of hexamethyldisilazane, 0.2 part by mass of dioctyltin dilaurate was simultaneously blended (during the same process) and mixed under reduced pressure for 15 minutes to obtain composition 7.
上記で調製した各組成物１～７について、それぞれ以下の特性を確認した。 The following properties were confirmed for each of Compositions 1 to 7 prepared above.
・タックフリータイム
調製した組成物１から７のそれぞれを、ＪＩＳ Ｋ ６２４９に記載の方法に従い、２３℃／５０％ＲＨ環境下にて指触によるタックフリータイム（分）を評価した。得られた結果を表１に示す。
- Tack-free time Each of the prepared compositions 1 to 7 was evaluated for tack-free time (minutes) by touch under a 23°C/50% RH environment according to the method described in JIS K 6249. Table 1 shows the results obtained.
・吐出性
組成物１から７のそれぞれを密閉可能容器（ポリカーボネート製３３０ｍｌカートリッジ）に入れた後、先端にφ４．５ｍｍの吐出口を開けたノズルを取り付け、０．２ＭＰａの吐出圧にて５秒間各組成物を押し出す。５秒後、押し出された重さ（ｇ）を測定し、吐出性を評価した。得られた結果を表１に示す。
・Ejectability After putting each of compositions 1 to 7 into a sealable container (polycarbonate 330 ml cartridge), a nozzle with a φ4.5 mm ejection port was attached to the tip, and the ejection pressure was 0.2 MPa for 5 seconds. Extrude each composition. After 5 seconds, the extruded weight (g) was measured to evaluate the jettability. Table 1 shows the results obtained.
・耐スランプ性
調製した組成物１から７のそれぞれを、ＪＩＳ Ａ １４３９（建築用シーリング材の試験方法）に記載のスランプ試験の方法に従い、耐スランプ性の確認を行った。
• Slump resistance Each of the prepared compositions 1 to 7 was checked for slump resistance according to the slump test method described in JIS A 1439 (testing method for building sealants).
・硬化性
調製した組成物１から７のそれぞれを、２３℃／５０％ＲＨ環境下にて厚さが３ｍｍになるように７日放置し硬化させ、ＪＩＳ Ｋ ６２４９に従い硬さ、伸び、引張り強度を測定した。
Curability Each of the prepared compositions 1 to 7 was left to cure for 7 days in a 23 ° C. / 50% RH environment so that the thickness became 3 mm, and the hardness, elongation, and tensile strength were measured according to JIS K 6249. was measured.
・接着性
調製した組成物１から７のそれぞれを、エタノールで表面を洗浄した表１に示す各種基材からなる被着体に、厚さが３ｍｍになるように塗布し、２３℃／５０％ＲＨ環境下にて７日硬化させた。７日後、被着体からゴム（組成物の硬化物）を剥がし、接着性を確認し、下記の基準で評価した。
○：被着体とゴム界面に１ｃｍ程度の切込みを入れ、手でせん断方向に引張った際に、ゴムが被着体から剥離しない。
×：被着体とゴム界面に１ｃｍ程度の切込みを入れ、手でせん断方向に引張った際に、ゴムが被着体から剥離する。
Adhesion Each of the prepared compositions 1 to 7 was applied to an adherend made of various substrates shown in Table 1 whose surface was washed with ethanol so that the thickness was 3 mm, and the temperature was 23 ° C./50%. It was cured for 7 days under RH environment. After 7 days, the rubber (cured product of the composition) was peeled off from the adherend, and the adhesion was confirmed and evaluated according to the following criteria.
◯: The rubber does not separate from the adherend when an incision of about 1 cm is made at the interface between the adherend and the rubber and the adherend is pulled in the shear direction by hand.
x: When an incision of about 1 cm was made at the interface between the adherend and the rubber and the adherend was pulled in the shear direction by hand, the rubber was peeled off from the adherend.
・ＵＶ照射に対する変色耐性
調製した組成物１から７のそれぞれを、２３℃／５０％ＲＨ環境下にて厚さが３ｍｍになるように７日放置し硬化させ、ＫＯＮＩＣＡ ＭＩＮＯＬＴＡ社製 色彩色差計ＣＲ－４００にて色差を測定した。測定後、硬化物に２５４ｎｍのＵＶを１日照射し、再度色差を測定した。ＵＶ照射前後の色差をΔＥで算出した。
以下の基準により、ＵＶ照射に対する変色耐性を評価した。得られた結果を表１に示す。
○：ΔＥが３．０未満である。
×：ΔＥが３．０以上である。
Discoloration resistance to UV irradiation Each of the prepared compositions 1 to 7 was allowed to stand for 7 days in a 23 ° C. / 50% RH environment so that the thickness was 3 mm, and was measured with a color difference meter CR manufactured by KONICA MINOLTA. Color difference was measured at -400. After the measurement, the cured product was irradiated with UV light of 254 nm for one day, and the color difference was measured again. The color difference before and after UV irradiation was calculated as ΔE.
Discoloration resistance to UV irradiation was evaluated according to the following criteria. Table 1 shows the results obtained.
○: ΔE is less than 3.0.
x: ΔE is 3.0 or more.
分子鎖両末端がシラノール基のポリジメチルシロキサンをγ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン存在下、メチルトリメトキシシランで末端封鎖することで、耐スランプ性、硬化性、接着性が良好でかつ、ＵＶ照射に対する変色が少ない室温硬化性オルガノポリシロキサンとなることを確認した（組成物１～４）。
γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシランの代わりに、特定のアミノシランを配合するとＵＶ照射に対する変色が大きいか、あるいは耐スランプ性、硬化性、接着性に乏しい室温硬化性オルガノポリシロキサンとなった（組成物５、６）。
実施例１と同じ成分を同じ量で全て同一工程中に同時に配合し混合した組成物では、混合中にゲル化してしまい、目的とする硬化物が得られなかった（組成物７）。
Slump resistance, curability, It was confirmed that room-temperature-curable organopolysiloxanes exhibiting good adhesion and little discoloration upon UV irradiation were obtained (compositions 1 to 4).
If a specific aminosilane is blended instead of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane, the room temperature curability results in large discoloration due to UV irradiation, or poor slump resistance, curability, and adhesion. Organopolysiloxane was obtained (compositions 5 and 6).
A composition in which the same components as in Example 1 were mixed in the same amount at the same time was gelled during mixing, and the desired cured product could not be obtained (composition 7).
Claims (2)
（Ｂ）下記一般式（２）
（Ｃ）無機充填剤 １～２００質量部、及び、
（Ｄ）１分子中に窒素原子を３個以上有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物 ０．５～３質量部、
を含有する室温硬化性オルガノポリシロキサン組成物の製造方法であって、
予め（Ａ）成分、（Ｂ）成分の一部又は全部（（Ｂ）成分全体の１０～１００質量％）、及び（Ｄ）成分の一部又は全部（（Ｄ）成分全体の５０～１００質量％）を混合して均一な混合物を調製した後、該混合物に（Ｃ）成分及び残余の（Ｂ）成分（（Ｂ）成分全体の０～９０質量％）及び残余の（Ｄ）成分（（Ｄ）成分全体の０～５０質量％）を添加、混合して組成物を調製する工程を有する、室温硬化性オルガノポリシロキサン組成物の製造方法。 (A) the following general formula (1)
(B) the following general formula (2)
(C) inorganic filler 1 to 200 parts by mass, and
(D) an amino functional group-containing hydrolyzable organosilane compound having 3 or more nitrogen atoms in one molecule and/or a partial hydrolytic condensate thereof 0.5 to 3 parts by mass,
A method for producing a room temperature curable organopolysiloxane composition containing
Component (A), part or all of component (B) (10 to 100% by mass of the total component (B)), and part or all of component (D) (50 to 100 mass of the total component (D) %) to prepare a uniform mixture, and then the mixture is added with the remaining component (C) and the remaining component (B) (0 to 90% by mass of the total component (B)) and the remaining component (D) (( D) A method for producing a room-temperature-curable organopolysiloxane composition, comprising the step of adding and mixing 0 to 50% by mass of component D) to prepare a composition.
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