JP4744972B2 - Curable polyorganosiloxane composition for building - Google Patents
Curable polyorganosiloxane composition for building Download PDFInfo
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- JP4744972B2 JP4744972B2 JP2005222478A JP2005222478A JP4744972B2 JP 4744972 B2 JP4744972 B2 JP 4744972B2 JP 2005222478 A JP2005222478 A JP 2005222478A JP 2005222478 A JP2005222478 A JP 2005222478A JP 4744972 B2 JP4744972 B2 JP 4744972B2
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- 239000000203 mixture Substances 0.000 title claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 150000001282 organosilanes Chemical class 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000003566 sealing material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229920005601 base polymer Polymers 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- -1 polysiloxane Polymers 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical compound CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WXWYJCSIHQKADM-ZNAKCYKMSA-N (e)-n-[bis[[(e)-butan-2-ylideneamino]oxy]-ethenylsilyl]oxybutan-2-imine Chemical compound CC\C(C)=N\O[Si](O\N=C(/C)CC)(O\N=C(/C)CC)C=C WXWYJCSIHQKADM-ZNAKCYKMSA-N 0.000 description 1
- OGZPYBBKQGPQNU-DABLZPOSSA-N (e)-n-[bis[[(e)-butan-2-ylideneamino]oxy]-methylsilyl]oxybutan-2-imine Chemical compound CC\C(C)=N\O[Si](C)(O\N=C(/C)CC)O\N=C(/C)CC OGZPYBBKQGPQNU-DABLZPOSSA-N 0.000 description 1
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- HNUKTDKISXPDPA-UHFFFAOYSA-N 2-oxopropyl Chemical group [CH2]C(C)=O HNUKTDKISXPDPA-UHFFFAOYSA-N 0.000 description 1
- RBLNICCKPGGVJW-UHFFFAOYSA-N C(C)O[Si](O[Sn])(OCC)OCC Chemical compound C(C)O[Si](O[Sn])(OCC)OCC RBLNICCKPGGVJW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- VXPYSZQGFPMWQU-UHFFFAOYSA-L [acetyloxy(diphenyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.C=1C=CC=CC=1[Sn+2]C1=CC=CC=C1 VXPYSZQGFPMWQU-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UKRVECBFDMVBPU-UHFFFAOYSA-N ethyl 3-oxoheptanoate Chemical compound CCCCC(=O)CC(=O)OCC UKRVECBFDMVBPU-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- XZZXKVYTWCYOQX-UHFFFAOYSA-J octanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O XZZXKVYTWCYOQX-UHFFFAOYSA-J 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は建築用硬化性ポリオルガノシロキサン組成物に係り、さらに詳しくは、高層ビルの窓などに用いるシーリング材として好適な艶消し状表面の硬化物を形成する建築用硬化性ポリオルガノシロキサン組成物に関する。 The present invention relates to a curable polyorganosiloxane composition for construction, and more particularly, a curable polyorganosiloxane composition for construction that forms a cured product having a matte surface suitable as a sealing material used for windows of high-rise buildings and the like. About.
高層ビルの窓による太陽の反射光は、反対側のビル内の人や路上の歩行者、運転者等をまぶしく照らすため一種の環境問題となっており、建築物としての美観を損なうという問題も引き起している。 The reflected light of the sun from the windows of high-rise buildings is a kind of environmental problem because it illuminates people in the building on the other side, pedestrians on the street, drivers, etc., and it also impairs the beauty of the building It has caused.
このため最近では、高層ビルの窓には防眩を考慮した設計が施されるようになってきている。 Therefore, recently, the windows of high-rise buildings have been designed with anti-glare consideration.
ところで建築物の外装、特に窓枠部には、防水や防食のため硬化性ポリオルガノシロキサン樹脂がパテやシーリング材として要所要所に用いられているが、従来のポリシロキサン樹脂の硬化物は光沢がきわめて良好で、表面が汚損されるまでの間、太陽光を反射して付近の人を眩しくさせ、またビルの建築物としての美観も損ねるという問題があった。 By the way, curable polyorganosiloxane resin is used as a putty or sealing material for building exteriors, especially window frame parts for waterproofing and anticorrosion, but the cured products of conventional polysiloxane resins are glossy. However, until the surface was damaged, there was a problem that sunlight was reflected and dazzled nearby people, and the aesthetics of the building as a building were also lost.
この問題を解決し、艶消し状表面の硬化物を形成する建築用硬化性ポリオルガノシロキサン組成物を得る従来の方法として、特定粒径の充填剤の併用配合(特許文献1)、特定の低分子有機化合物の配合(特許文献2)が提案されている。
が、その効果が十分でないと共に、コスト面、配合された添加物の組成物強度への影響等の点で満足すべきものではなかった。
However, the effect is not sufficient, and it is not satisfactory in terms of cost, influence of the blended additive on the composition strength, and the like.
上記特許文献1、2の手法によれば、ある程度の艶消し効果は得られるものの、その効果が十分でないと共に、コスト面、配合された添加物の組成物強度への影響等の点で満足すべきものではなかった。 According to the methods of Patent Documents 1 and 2 described above, a certain amount of matting effect can be obtained, but the effect is not sufficient, and it should be satisfactory in terms of cost and the effect of the added additive on the composition strength. It was not kimono.
本発明は、かかる従来の問題を解消すべくなされたもので、特別な添加物を用いることなく、艶消し状表面の硬化物を形成する建築用硬化性ポリオルガノシロキサン組成物を提供することを目的とする。 The present invention has been made to solve such conventional problems, and provides a curable polyorganosiloxane composition for building that forms a cured product of a matte surface without using a special additive. Objective.
本発明は、上記目的を達成すべく検討した結果、室温硬化性ポリオルガノシロキサン組成物の基本成分を配合する際に、ポリオルガノシロキサンと架橋剤とを予め混合し、この後に未処理の微粉末シリカ等の他の成分と共にポリオルガノシロキサンの残りの一部を添加することによって、特別な添加剤を使用することなく艶消し状表面の硬化物を形成する建築用硬化性ポリオルガノシロキサン組成物が得られることを見出し、本発明を完成するに至った。 The present invention has been studied to achieve the above object, and as a result, when the basic components of the room temperature curable polyorganosiloxane composition are blended, the polyorganosiloxane and the crosslinking agent are mixed in advance, and thereafter, an untreated fine powder. An architectural curable polyorganosiloxane composition that forms a cured matte surface without the use of special additives by adding the remainder of the polyorganosiloxane with other ingredients such as silica. As a result, the present invention was completed.
即ち本発明は、
基本的に(A)一般式:
That is, the present invention
Basically (A) General formula:
(式中、Rは置換または非置換の1価の炭化水素基を示し、nは正の整数である)で実質的に表され、25℃における粘度が100〜500000cPであるポリオルガノシロキサン100重量部、
(B)一般式:
(Wherein R represents a substituted or unsubstituted monovalent hydrocarbon group, and n is a positive integer), 100 weight of polyorganosiloxane having a viscosity at 25 ° C. of 100 to 500,000 cP Part,
(B) General formula:
(式中、R1は置換または非置換の1価の炭化水素基を、R2は同一または相異なる1価の炭化水素基を示し、mは0、1または2である)で表されるオルガノシランおよび/またはその部分加水分解縮合物1〜10重量部、
(C)比表面積100〜300m2/gの未処理の微粉末シリカ5〜20重量部、および
(D)硬化用触媒0.01〜5重量部を構成成分とし、
前記(A)成分のポリオルガノシロキサン100重量部のうち95.0〜99.5重量部と(B)成分のオルガノシランおよび/またはその部分加水分解物のみを予め所定の比率で湿気を断った状態で混合し、この混合物に(C)成分の微粉末シリカと(D)成分の硬化用触媒を混合し、次いで(A)、(B)、(C)、(D)成分の混合後8時間以内にこの混合物に前記(A)成分の残り0.5〜5.0重量部および任意成分を所定の比率で配合して得られる艶消し状表面の硬化物を形成する建築用硬化性ポリオルガノシロキサン組成物である。
(Wherein R 1 represents a substituted or unsubstituted monovalent hydrocarbon group, R 2 represents the same or different monovalent hydrocarbon group, and m is 0, 1 or 2). 1 to 10 parts by weight of organosilane and / or its partial hydrolysis condensate,
(C) 5 to 20 parts by weight of untreated fine powder silica having a specific surface area of 100 to 300 m 2 / g, and (D) 0.01 to 5 parts by weight of a curing catalyst,
95.0-99.5 parts by weight of 100 parts by weight of the polyorganosiloxane of the component (A) and only the organosilane and / or its partial hydrolyzate of the component (B) are mixed in a predetermined ratio in a state where moisture is cut off in advance. In this mixture, the fine powder silica of component (C) and the curing catalyst of component (D) are mixed, and then within 8 hours after mixing of components (A), (B), (C), (D) A curable polyorganosiloxane composition for building which forms a cured product having a matte-like surface obtained by blending the mixture with the remaining 0.5 to 5.0 parts by weight of the component (A) and an optional component in a predetermined ratio.
尚、本願出願人は、先にポリオルガノシロキサンと架橋剤とを予め混合し、この後に他の成分と共にポリオルガノシロキサンの残りの一部を添加することによって、垂れ落ち性が改善された室温硬化性ポリオルガノシロキサン組成物が得られることを見出し、特許出願するに至った(特開2002−194216号公報)。本発明は、この研究を更に進めた結果、案出されたものであって、各成分の配合量をより規制すると共に、特定の未処理の微粉末シリカを使用し、特定の条件の混合によって、該公報には全く記載のない艶消し性が顕著に向上することを見出し、完成されたものである。 The applicant of the present application previously mixed the polyorganosiloxane and the crosslinking agent in advance, and then added the remaining part of the polyorganosiloxane together with the other components, thereby improving the dripping property at room temperature. The inventors have found that a functional polyorganosiloxane composition can be obtained and have filed a patent application (Japanese Patent Laid-Open No. 2002-194216). The present invention has been devised as a result of the further progress of this research, and further regulates the amount of each component, uses specific untreated fine powdered silica, and mixes under specific conditions. The present invention has been completed by finding that the matte property, which is not described in the publication, is remarkably improved.
以下、本発明を詳細に説明する。本発明における(A)成分のポリオルガノシロキサンは、本発明によって得られる組成物のベースポリマーとなるものであり、従来より縮合反応型液状ポリマーのベースとして用いられているものである。 Hereinafter, the present invention will be described in detail. The polyorganosiloxane of the component (A) in the present invention serves as a base polymer of the composition obtained by the present invention, and has been conventionally used as a base for condensation reaction type liquid polymers.
したがって、ケイ素原子に結合した水酸基を1分子中に少なくとも2個含有することが必要であり、また硬化後の組成物が良好な機械的特性を有するために、水酸基と結合するケイ素原子がポリオルガノシロキサンの末端にあるもの、すなわち一般式: Therefore, it is necessary to contain at least two hydroxyl groups bonded to silicon atoms in one molecule, and since the cured composition has good mechanical properties, the silicon atoms bonded to the hydroxyl groups are polyorgano What is at the end of the siloxane, ie the general formula:
(式中、Rは置換または非置換の1価の炭化水素基を示し、nは正の整数である)で実質的に表されるポリオルガノシロキサンが用いられる。 (Wherein, R represents a substituted or unsubstituted monovalent hydrocarbon group, and n is a positive integer).
ポリオルガノシロキサンのケイ素原子に結合する有機基Rとしては、メチル基、エチル基、プロピル基、ブチル基、ビニル基、フェニル基などの1価の炭化水素基、クロロメチル基、シアノエチル基、3,3,3−トリフルオロプロピル基などの1価の置換炭化水素基が例示される。 Examples of the organic group R bonded to the silicon atom of the polyorganosiloxane include monovalent hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, vinyl group, and phenyl group, chloromethyl group, cyanoethyl group, 3, Examples thereof include monovalent substituted hydrocarbon groups such as 3,3-trifluoropropyl group.
適度の硬化速度を有すること、硬化前の流動性が適用に扱いやすいこと、また硬化後の物性、特にモジュラスが低いことから、Rはその85%以上がメチル基であることが好ましく、合成の容易さからRのすべてがメチル基であることが最もよいが、耐熱性や耐寒性などが特に要求される場合には、Rの一部としてフェニル基を用いるのがよい。 It is preferable that 85% or more of R is a methyl group because it has an appropriate curing speed, the fluidity before curing is easy to handle, and the physical properties after curing, especially the modulus is low. In view of easiness, it is best that all of R are methyl groups. However, when heat resistance, cold resistance, etc. are particularly required, a phenyl group is preferably used as a part of R.
また、nの範囲はRの種類とそのモル比によっても異なるが、取扱いの容易さ、組成物の流動性、硬化後の物性などから、(A)成分の粘度が25℃で100cP〜500000cPとなるように選ばれ、Rがすべてメチル基である場合にはnがほぼ20〜3000の範囲であることに相当する。 The range of n varies depending on the type of R and its molar ratio, but due to ease of handling, composition fluidity, physical properties after curing, etc., the viscosity of component (A) is 100 cP to 500000 cP at 25 ° C. When R is all methyl groups, n corresponds to the range of about 20 to 3000.
(A)成分の粘度が100cP未満であると低粘性によって良好な物性を得るのが困難となり、500000cPを越えると押出し作業性や硬化性が悪くなる傾向がある。 When the viscosity of the component (A) is less than 100 cP, it is difficult to obtain good physical properties due to low viscosity, and when it exceeds 500000 cP, the extrusion workability and curability tend to be poor.
本発明に用いられる(B)成分は、(A)成分を架橋して網状構造を与えるための架橋剤であり、そのためにケイ素原子に結合したケトオキシム基を1分子中に少なくとも2個含有するオルガノシランやその部分加水分解縮合物が用いられる。 The component (B) used in the present invention is a crosslinking agent for crosslinking the component (A) to give a network structure, and for this purpose, an organo group containing at least two ketoxime groups bonded to silicon atoms in one molecule. Silane and its partial hydrolysis condensate are used.
上記ケトオキシム基含有のオルガノシランは、具体的には一般式: Specifically, the ketoxime group-containing organosilane has the general formula:
(式中、R1は置換または非置換の1価の炭化水素基を、R2は同一または相異なる1価の炭化水素基を示し、mは0、1または2である)で表されるものである。 (Wherein R 1 represents a substituted or unsubstituted monovalent hydrocarbon group, R 2 represents the same or different monovalent hydrocarbon group, and m is 0, 1 or 2). Is.
また、ケイ素原子に結合したケトオキシム基以外の有機基R1としては、メチル基、エチル基、プロピル基、ブチル基、ビニル基、フェニル基などの1価の炭化水素基、クロロメチル基、シアノエチル基、3,3,3−トリフルオロプロピル基などの1価の置換炭化水素基が例示され、適度の硬化速度を与えることから、メチル基、フェニル基またはビニル基であることが好ましい。 The organic group R 1 other than the ketoxime group bonded to the silicon atom includes a monovalent hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, and a phenyl group, a chloromethyl group, and a cyanoethyl group. Monovalent substituted hydrocarbon groups such as 3,3,3-trifluoropropyl group are exemplified, and a methyl group, a phenyl group or a vinyl group is preferable because it gives an appropriate curing rate.
このようなオルガノシランとしては、メチルトリス(ジエチルケトオキシム)シラン、メチルトリス(メチルエチルケトオキシム)シラン、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(ジエチルケトオキシム)シランなどのシラン化合物、あるいはこれらの部分加水分解縮合物が例示される。 Such organosilanes include silane compounds such as methyltris (diethylketoxime) silane, methyltris (methylethylketoxime) silane, vinyltris (methylethylketoxime) silane, phenyltris (diethylketoxime) silane, or partial hydrolysis condensation thereof. Things are illustrated.
この(B)成分は、上記(A)成分100重量部に対して1〜10重量部の範囲で使用する。(B)成分の配合量が1重量部未満であると弾性および機械的特性にすぐれた硬化物を得ることができず、10重量部を越えると艶消しされた表面を有する硬化物を得ることができない。 This (B) component is used in 1-10 weight part with respect to 100 weight part of said (A) component. When the blending amount of component (B) is less than 1 part by weight, a cured product having excellent elasticity and mechanical properties cannot be obtained, and when it exceeds 10 parts by weight, a cured product having a matte surface is obtained. I can't.
本発明に用いられる(C)成分の微粉末シリカは、硬化後のゴム弾性体に機械的強度を与える補強性の充填剤である。このような微粉末シリカとしては、煙霧質シリカ、焼成シリカ、沈澱シリカ等が挙げられるが、比表面積100〜300m2/gであること、並びに未処理のものであることが本発明の目的である艶消し性向上のために必須である。比表面積が上記範囲を外れるシリカや、一般的な表面処理剤であるオルガノクロロシラン類、ポリオルガノシロキサン類およびヘキサメチルジシラザンなどで疎水化したシリカを使用したのでは、艶消し性に優れた表面状態を得ることができない。使用する微粉末シリカの粒径は特に制限されないが、一般的に5〜20nm程度である。 The fine powder silica of the component (C) used in the present invention is a reinforcing filler that gives mechanical strength to the rubber elastic body after curing. Examples of such finely divided silica include fumed silica, calcined silica, precipitated silica, and the like. For the purpose of the present invention, the specific surface area is 100 to 300 m 2 / g, and the silica is untreated. It is essential for improving the matteness. Surfaces with excellent matting properties when silica with a specific surface area outside the above range or silica hydrophobized with organochlorosilanes, polyorganosiloxanes and hexamethyldisilazane, which are general surface treatment agents, are used. Can't get state. The particle size of the fine powder silica to be used is not particularly limited, but is generally about 5 to 20 nm.
この(C)成分は、(A)成分100重量部に対して5〜20重量部、好ましくは7〜18重量部の範囲で使用する。(C)成分の配合量が5重量部未満であると艶消しされた表面を有する硬化物を得ることができない。加えて、機械的強度が十分に得られない。また、20重量部を超えると混合が困難となり、コンパウンドが硬くなりすぎて、たとえばシーリング材としての適正な粘度が得られなくなる。 The component (C) is used in an amount of 5 to 20 parts by weight, preferably 7 to 18 parts by weight per 100 parts by weight of the component (A). When the blending amount of the component (C) is less than 5 parts by weight, a cured product having a matte surface cannot be obtained. In addition, sufficient mechanical strength cannot be obtained. On the other hand, when the amount exceeds 20 parts by weight, mixing becomes difficult, the compound becomes too hard, and for example, an appropriate viscosity as a sealing material cannot be obtained.
本発明に用いられる(D)成分の硬化用触媒は、(A)成分と(B)成分との縮合反応を促進させるものである。 The curing catalyst for component (D) used in the present invention promotes the condensation reaction between component (A) and component (B).
このような硬化用触媒としては、鉄オクトエート、コバルトオクトエート、マンガンオクトエート、亜鉛オクトエート、スズナフテネート、スズカプリレート、スズオレエートのようなカルボン酸金属塩;ジブチルスズジアセテート、ジブチルスズジオクトエート、ジブチルスズジラウレート、ジブチルスズオレエート、ジフェニルスズジアセテート、酸化ジブチルスズ、ジブチルスズジメトキシド、ジブチルビス(トリエトキシシロキシ)スズ、ジオクチルスズジラウレートのような有機スズ化合物;テトラブチルチタネート、テトラ−2−エチルヘキシルチタネート、トリエタノールアミンチタネート、テトラ(イソプロペニルオキシ)チタネートなどの有機チタン酸エステル;オルガノシロキシチタン、β−カルボニルチタンなどの有機チタン化合物;アルコキシアルミニウム化合物などが例示される。 Such curing catalysts include iron octoate, cobalt octoate, manganese octoate, zinc octoate, tin naphthenate, tin caprylate, tin oleate, carboxylic acid metal salts; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, Organotin compounds such as dibutyltin oleate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dioctyltin dilaurate; tetrabutyl titanate, tetra-2-ethylhexyl titanate, triethanolamine titanate, tetra Organic titanates such as (isopropenyloxy) titanate; organic siloxy titanium, β-carbonyl titanium, etc. Titanium compounds; and alkoxy aluminum compounds.
この(D)成分は、(A)成分100重量部に対して0.01〜5重量部の範囲で使用する。硬化用触媒の配合量が5重量部を越えると硬化性が速くなりずぎるのみならず、硬化後のシーリング材の機械的特性に悪影響を及ぼす。 This (D) component is used in 0.01-5 weight part with respect to 100 weight part of (A) component. If the blending amount of the curing catalyst exceeds 5 parts by weight, not only the curability becomes fast, but also the mechanical properties of the cured sealing material are adversely affected.
本発明における組成物は、上記(A)〜(D)の各成分を基本成分とし、これらに必要に応じてその他公知の充填剤、可塑剤、着色剤、耐熱向上剤、難燃性付与剤、防カビ剤、接着付与剤などを本発明の効果を損わない範囲で配合してもよい。 The composition according to the present invention comprises the components (A) to (D) as basic components, and other known fillers, plasticizers, colorants, heat improvers, and flame retardants as necessary. In addition, an antifungal agent, an adhesion-imparting agent and the like may be blended within a range not impairing the effects of the present invention.
そして、本発明は上記(A)〜(D)の必須成分、および上述した任意成分を配合・混合するにあたって、まずベースポリマーである(A)成分のポリオルガノシロキサン100重量部のうち、95.0〜99.5重量部と架橋剤である(B)成分のオルガノシランおよび/またはその部分加水分解縮合物とを、予め前述した配合比のもとでミキサ、ニーダなどでブレンド配合し、均一になるように混合する。 In the present invention, in blending and mixing the essential components (A) to (D) and the optional components described above, first, among 100 parts by weight of the polyorganosiloxane of the component (A) which is a base polymer, 95.0 to 99.5 parts by weight and the (B) component organosilane and / or its partially hydrolyzed condensate as a cross-linking agent are blended and blended with a mixer, kneader, etc. in advance under the aforementioned blending ratio so as to be uniform. Mix.
この混合は、湿気を断った状態で行う。次に、その混合体に補強性充填剤である(C)成分の微粉末シリカと(D)成分の硬化用触媒を混合した後、(A)成分の残り0.5〜5.0重量部、さらに必要に応じて前述した任意成分を、同じく湿気を断った状態で配合し、均一になるように混合する。 This mixing is performed in a state where moisture is turned off. Next, the mixture is mixed with fine powdered silica of component (C), which is a reinforcing filler, and curing catalyst of component (D), and then the remaining 0.5 to 5.0 parts by weight of component (A) is further required. Correspondingly, the optional components described above are blended in a state where moisture is cut off, and mixed so as to be uniform.
後から配合する(A)成分が0.5重量部未満であると艶消し効果が不十分であり、5.0重量部を超えると組成物をカートリッジ状の容器から押し出す際に組成物の粘りが強くなり、押し出し難くなる。 If the component (A) to be blended later is less than 0.5 parts by weight, the matting effect is insufficient, and if it exceeds 5.0 parts by weight, the composition becomes more viscous when the composition is extruded from a cartridge-like container, It becomes difficult to extrude.
このように予め(A)成分と(B)成分を混合し、更に(C)成分および(D)成分とを混合した後、(A)成分の残りを混合することによって、艶消し性が大幅に改善された室温硬化性ポリオルガノシロキサン組成物が得られる。 In this way, (A) component and (B) component are mixed in advance, and (C) component and (D) component are further mixed, and then the remainder of (A) component is mixed, thereby greatly increasing the matte properties. An improved room temperature curable polyorganosiloxane composition is obtained.
また、(A)成分と(B)成分とを混合した後、更に(C)成分と(D)成分を混合し、最後に(A)成分の残りを混合するに際しては、(A)成分と(B)成分と(C)成分と(D)成分の混合後8時間以内に行う必要がある。 In addition, after mixing the component (A) and the component (B), the component (C) and the component (D) are further mixed, and finally the remainder of the component (A) is mixed. It is necessary to carry out within 8 hours after mixing of the component (B), the component (C) and the component (D).
本発明によって得られる室温硬化性ポリオルガノシロキサン組成物は、たとえば建築用シーリング材のような各種シーリング材として使用した際の作業性などに極めて優れると共に、特別な艶消し向上剤を用いることなく艶消し性に優れ、また、その製造コストが安価であることから、工業用シーリング材として非常に有用なものが得られる。 The room temperature curable polyorganosiloxane composition obtained by the present invention is extremely excellent in workability when used as various sealing materials such as architectural sealing materials, and has no gloss without using a special matting improver. Since it is excellent in erasability and its manufacturing cost is low, it is possible to obtain a very useful industrial sealing material.
以下、本発明を実施の形態によってさらに詳細に説明する。なお、実施例および比較例中の部は、すべて重量部を示すものとする。また、粘度などの特性値はことわらない限り、25℃における測定値を示す。
実施例1〜4
表1に示した配合比(重量部)でベースポリマーと架橋剤(オキシムシラン)を湿気を遮断した混合器に投入し、この状態で混合して均一にした。
Hereinafter, the present invention will be described in more detail with reference to embodiments. In addition, all the parts in an Example and a comparative example shall show a weight part. In addition, unless otherwise specified, such as viscosity, measured values at 25 ° C. are shown.
Examples 1-4
The base polymer and the cross-linking agent (oxime silane) were added to a mixer in which moisture was blocked at the blending ratio (parts by weight) shown in Table 1, and mixed in this state to be uniform.
上記混合物に表1に示した配合比で微粉末シリカ、硬化用触媒を投入し、湿気を遮断した状態で均一になるように混合した。上記混合の0.1時間後に、表1に示した配合比でベースポリマーの残りを投入し、湿気を遮断した状態で均一になるように混合した。
実施例5
後配合のタイミングを4.0時間後に変更した以外は実施例1と同様にして組成物を得た。
Fine powdered silica and a curing catalyst were added to the above mixture at the blending ratio shown in Table 1, and the mixture was mixed so as to be uniform while moisture was blocked. After 0.1 hour of the above mixing, the rest of the base polymer was added at the compounding ratio shown in Table 1 and mixed so as to be uniform while moisture was cut off.
Example 5
A composition was obtained in the same manner as in Example 1 except that the timing of post-mixing was changed after 4.0 hours.
得られた組成物が付着しない様にテフロン(登録商標)板に、同様にテフロン(登録商標)板でできた厚さ2mmの型枠を置き、得られた組成物を泡が入らない様に充填し、へらを用いて表面を平らにならした。その後、23℃、50%RHの条件で3日間静置して硬化させ、150mm×300mm×2mmの試料を作成した。得られた硬化物についてゴム物性・光沢度を測定した。 Place a 2 mm thick mold made of Teflon (registered trademark) on the Teflon (registered trademark) board so that the obtained composition does not adhere, and prevent the foam from entering the resulting composition. Filled and leveled surface with spatula. Thereafter, the sample was allowed to stand for 3 days under conditions of 23 ° C. and 50% RH, and cured to prepare a sample of 150 mm × 300 mm × 2 mm. Rubber properties and glossiness of the obtained cured product were measured.
結果を表1に示す。艶消し性の指標である光沢度は、JIS Z-8741に基づき60°鏡面光沢を光沢度計IG-310(堀場製作所製)を用いて測定した。数値が小さいほど光沢が少なくなることを意味する。他の特性は、JIS A-5758およびK-6301に従って測定した。
比較例1
後配合のベースポリマーの投入がないこと以外は実施例1と同様にして組成物を得て評価した。
比較例2
後配合のタイミングを10.0時間後に変更した以外は実施例1と同様にして組成物を得て評価した。
比較例3
微粉末シリカとしてオクタメチルシクロテトラシロキサンで表面処理した処理粉末を用いた以外は実施例1と同様にして組成物を得て評価した。
The results are shown in Table 1. The glossiness, which is an index of matting properties, was measured using a gloss meter IG-310 (Horiba Seisakusho) based on JIS Z-8741 for 60 ° specular gloss. A smaller value means less gloss. Other properties were measured according to JIS A-5758 and K-6301.
Comparative Example 1
A composition was obtained and evaluated in the same manner as in Example 1 except that no post-base polymer was added.
Comparative Example 2
A composition was obtained and evaluated in the same manner as in Example 1 except that the timing of post-mixing was changed after 10.0 hours.
Comparative Example 3
A composition was obtained and evaluated in the same manner as in Example 1 except that the treated powder surface-treated with octamethylcyclotetrasiloxane was used as the fine powdered silica.
Claims (1)
(B)一般式:
(C)比表面積100〜300m2/gの未処理の微粉末シリカ5〜20重量部、および
(D)硬化用触媒0.01〜5重量部を構成成分とし、
前記(A)成分のポリオルガノシロキサン100重量部のうち95.0〜99.5重量部と(B)成分のオルガノシランおよび/またはその部分加水分解縮合物のみを湿気を断った状態で混合し、この混合物に(C)成分の微粉末シリカと(D)成分の硬化用触媒を湿気を断った状態で混合し、次いで(A)、(B)、(C)、(D)成分の混合後8時間以内にこの混合物に前記(A)成分の残り0.5〜5.0重量部および任意成分を湿気を断った状態で混合して得られる艶消し状表面の硬化物を形成する建築用硬化性ポリオルガノシロキサン組成物。 Basically (A) General formula:
(B) General formula:
(C) 5 to 20 parts by weight of untreated fine powder silica having a specific surface area of 100 to 300 m 2 / g, and (D) 0.01 to 5 parts by weight of a curing catalyst,
Wherein (A) were mixed in a state refused air humidity only organosilane and / or partial hydrolysis condensate thereof and 95.0 to 99.5 parts by weight (B) component of the polyorganosiloxane 100 parts by weight of component, the mixture (C) Component fine powder silica and (D) component curing catalyst are mixed in a state where moisture is cut off, and then 8 hours after mixing of components (A), (B), (C) and (D) A curable polyorganosiloxane composition for building which forms a hardened product with a matte surface obtained by mixing the mixture with the remaining 0.5 to 5.0 parts by weight of the component (A) and optional components in a state where moisture is cut off. object.
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JP2002194216A (en) * | 2000-12-26 | 2002-07-10 | Ge Toshiba Silicones Co Ltd | Process for producing room temperature curing polyorganosiloxane composition |
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