JP4438937B2 - Room temperature curable organopolysiloxane composition - Google Patents

Room temperature curable organopolysiloxane composition Download PDF

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JP4438937B2
JP4438937B2 JP2004028990A JP2004028990A JP4438937B2 JP 4438937 B2 JP4438937 B2 JP 4438937B2 JP 2004028990 A JP2004028990 A JP 2004028990A JP 2004028990 A JP2004028990 A JP 2004028990A JP 4438937 B2 JP4438937 B2 JP 4438937B2
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calcium carbonate
room temperature
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正 荒木
恒雄 木村
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties

Description

本発明は、室温硬化性オルガノポリシロキサン組成物に関するものであり、特に保存安定性、樹脂接着性に優れ、かつ臭気（特にシラン臭）が著しく少ない室温硬化性オルガノポリシロキサン組成物に関するものである。   The present invention relates to a room temperature curable organopolysiloxane composition, and particularly to a room temperature curable organopolysiloxane composition that is excellent in storage stability and resin adhesion and has a very low odor (particularly silane odor). .

従来、空気中の水分と接触することにより室温で硬化する室温硬化性オルガノポリシロキサン組成物は種々のタイプのものが公知であるが、その中でもアルコールを放出して硬化するタイプのものは、金属類を腐食しないことから主に電気・電子機器等のシーリング用、接着用、コーティング用に好んで使用されている。このアルコールタイプの代表例としては、特公昭３９−２７６４３号公報（特許文献１）が挙げられ、ここには水酸基末端封鎖オルガノポリシロキサンとアルコキシシランと有機チタン化合物からなる組成物が開示されている。また、特開昭５５−４３１１９号公報（特許文献２）にはアルコキシシリル末端封鎖オルガノポリシロキサンとアルコキシシランとアルコキシチタンからなる組成物が開示されている。最近になって特公平７−３９５４７号公報（特許文献３）において密封状態での保存安定性に優れる組成物についての開示、また特開平１１−３３８０９０号公報（特許文献４）において接着耐久性に優れる組成物の開示がある。   Conventionally, various types of room temperature curable organopolysiloxane compositions that cure at room temperature by contact with moisture in the air are known, and among them, those that cure by releasing alcohol are metals. Since it does not corrode, it is mainly used for sealing, bonding, and coating of electrical and electronic equipment. A representative example of this alcohol type is JP-B-39-27643 (Patent Document 1), which discloses a composition comprising a hydroxyl-terminated organopolysiloxane, an alkoxysilane, and an organic titanium compound. . JP-A-55-43119 (Patent Document 2) discloses a composition comprising an alkoxysilyl end-capped organopolysiloxane, an alkoxysilane and an alkoxytitanium. Recently, Japanese Patent Publication No. 7-39547 (Patent Document 3) discloses a composition having excellent storage stability in a sealed state, and Japanese Patent Application Laid-Open No. 11-338090 (Patent Document 4) provides adhesion durability. There are disclosures of superior compositions.

特公昭３９−２７６４３号公報Japanese Examined Patent Publication No. 39-27643 特開昭５５−４３１１９号公報Japanese Patent Laid-Open No. 55-43119 特公平７−３９５４７号公報Japanese Examined Patent Publication No. 7-39547 特開平１１−３３８０９０号公報JP 11-338090 A

しかしながら、特公昭３９−２７６４３号公報（特許文献１）、特開昭５５−４３１１９号公報（特許文献２）は保存安定性において問題があり、特公平７−３９５４７号公報（特許文献３）、特開平１１−３３８０９０号公報（特許文献４）においては樹脂接着性において問題であり、低沸点のアルコキシシランを使用するとシラン臭による不快な臭気が確認されていた。 However, JP-B-39-27643 (Patent Document 1), JP 55-43119 (Patent Document 2) has a problem in storage stability, JP equitable 7-39547 (Patent Document 3) In Japanese Patent Application Laid-Open No. 11-338090 (Patent Document 4), there is a problem in resin adhesion, and when a low boiling point alkoxysilane is used, an unpleasant odor due to a silane odor has been confirmed.

本発明は、前記した欠点を解消し、保存安定性、樹脂接着性に優れ、かつ臭気（特にシラン臭）が少なく、使用中に不快にならない室温硬化性オルガノポリシロキサン組成物を提供することが目的である。   The present invention provides a room temperature curable organopolysiloxane composition that eliminates the above-mentioned drawbacks, has excellent storage stability and resin adhesion, has a low odor (particularly silane odor), and does not become uncomfortable during use. Is the purpose.

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、下記一般式（１）で示されるオルガノポリシロキサン、表面が脂肪酸で処理されたコロイド質炭酸カルシウム、表面がパラフィン系の処理剤で処理された重質炭酸カルシウム、ケイ素原子に結合した加水分解性基を１分子中に平均２個以上有し、かつ常圧での沸点が１５０℃以上であるアルコキシシラン化合物及び／又はその部分加水分解物、３級の炭素原子が酸素原子に結合しているオルガノキシ基を分子内に少なくとも２個有するオルガノキシチタンを用いることで、この目的を達成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that organopolysiloxane represented by the following general formula (1 ), colloidal calcium carbonate whose surface is treated with a fatty acid, and paraffin-based treatment on the surface Heavy calcium carbonate treated with an agent, an alkoxysilane compound having an average of two or more hydrolyzable groups bonded to silicon atoms in one molecule and a boiling point of 150 ° C. or higher at normal pressure and / or its This object was achieved by using a partially hydrolyzed product, an organoxytitanium having at least two organoxy groups in the molecule in which tertiary carbon atoms are bonded to oxygen atoms.

従って、本発明は、
（Ａ）下記一般式（１）

Figure 0004438937
（式中、Ｒはメチル基又はエチル基であり、Ｒ1は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であり、Ｘは１０以上の整数である。Ｙは炭素原子数１〜５のアルキレン基であり、Ｎは独立に０又は１の整数である。）
で示されるオルガノポリシロキサン １００質量部、
（Ｂ）表面が脂肪酸で処理されたコロイド質炭酸カルシウム ５０〜１５０質量部、
（Ｃ）表面がパラフィン系の処理剤で処理された平均粒径が０．７〜２．５μｍである重質炭酸カルシウム １０〜５０質量部、
（Ｄ）ケイ素原子に結合した加水分解性基を１分子中に平均２個以上有し、かつ常圧での沸点が１５０℃以上であるアルコキシシラン化合物、その部分加水分解物又はこれらの混合物 ０．１〜２０質量部、
（Ｅ）下記一般式（４）
Figure 0004438937
 （式中、Ｒ3は酸素原子に結合する炭素原子が３級である炭素原子数４〜１０の３級炭化水素基であり、Ｒ4は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であるが、３級炭素原子を有さない。ａは０〜２の整数である。）
で示されるオルガノキシチタン １〜１５質量部、
（Ｆ）シランカップリング剤 ０〜１０質量部
を必須成分としてなる、保存安定性、樹脂接着性に優れ、かつ臭気（特にシラン臭）が著しく少ない樹脂との接着用の室温硬化性オルガノポリシロキサン組成物を提供するものである。 Therefore, the present invention
(A) The following general formula (1)
Figure 0004438937
 Wherein R is a methyl group or an ethyl group, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
100 parts by mass of an organopolysiloxane represented by
(B) co surface-treated with a fatty acid Lloyd calcium carbonate 50 to 150 parts by weight,
(C) 10-50 parts by weight of heavy calcium carbonate having an average particle size of 0.7-2.5 μm, the surface of which has been treated with a paraffinic treatment agent,
(D) An alkoxysilane compound, a partially hydrolyzed product thereof, or a mixture thereof, having an average of two or more hydrolyzable groups bonded to a silicon atom and having a boiling point of 150 ° C. or higher at normal pressure .1-20 parts by mass,
(E) The following general formula (4)
Figure 0004438937
 (Wherein R 3 is a tertiary hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the oxygen atom is tertiary, and R 4 is a substituted or unsubstituted one having 1 to 10 carbon atoms. (It is a valent hydrocarbon group but has no tertiary carbon atom. A is an integer of 0 to 2.)
1 to 15 parts by mass of organoxytitanium represented by
(F) Silane Coupling Agents Room temperature-curable organopolysiloxane for adhesion to a resin having 0 to 10 parts by mass as an essential component, excellent storage stability and resin adhesion, and extremely low odor (especially silane odor) A composition is provided.

本発明によれば、保存安定性、樹脂接着性に優れ、かつ臭気（特にシラン臭）が少なく、使用中に不快にならない室温硬化性オルガノポリシロキサン組成物を提供することができる。   According to the present invention, it is possible to provide a room temperature-curable organopolysiloxane composition that is excellent in storage stability and resin adhesion, has little odor (particularly silane odor), and does not become uncomfortable during use.

本発明に使用される（Ａ）成分は、本組成物のベースポリマーとなるものであり、保存安定性を得るために、下記一般式（１）

Figure 0004438937
（式中、Ｒはメチル基又はエチル基であり、Ｒ1は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であり、Ｘは１０以上の整数である。Ｙは炭素原子数１〜５のアルキレン基であり、Ｎは独立に０又は１の整数である。）
で示されるオルガノポリシロキサンであることが必要である。 The component (A) used in the present invention is a base polymer of the present composition, and in order to obtain storage stability, the following general formula (1)
Figure 0004438937
 Wherein R is a methyl group or an ethyl group, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
It is necessary that in a organopolysiloxane emissions represented.

（Ａ）成分の好ましい粘度は、２５℃の条件下において１００〜１，０００，０００ｍＰａ・ｓである。これは１００ｍＰａ・ｓより小さいと硬化後のエラストマーに優れた物理的性質、特に柔軟性と高い伸びを与えることができないおそれがあるためであり、また、１，０００，０００ｍＰａ・ｓより大きいと組成物の粘度が高くなり、施工する際の吐出性が著しく低下するおそれがあるためである。そのため、より好ましくは５，０００〜１００，０００ｍＰａ・ｓである。なお、この粘度は回転粘度計による測定値である。   (A) The preferable viscosity of a component is 100-1,000,000 mPa * s on 25 degreeC conditions. This is because if it is less than 100 mPa · s, the cured elastomer may not be able to give excellent physical properties, particularly flexibility and high elongation, and if it exceeds 1,000,000 mPa · s, the composition This is because the viscosity of the product is increased, and the dischargeability during construction may be significantly reduced. Therefore, it is more preferably 5,000 to 100,000 mPa · s. This viscosity is a value measured by a rotational viscometer.

上記一般式（１）中、Ｒはメチル基又はエチル基であり、メチル基が好ましい。Ｒ1は炭素原子数１〜１０、特に１〜６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シクロアルキル基及びこれらの基の水素結合が部分的にハロゲン原子などで置換された基、例えば３，３，３−トリフルオロプロピル基等が挙げられ、メチル基、エチル基、ビニル基、フェニル基、３，３，３−トリフルオロプロピル基が好ましく、メチル基が特に好ましい。上記一般式（１）中の複数のＲ1は同一の基であっても異種の基であってもよい。
また、Ｙは炭素原子数１〜５のアルキレン基であり、アルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられ、エチレン基が好ましい。
Ｙが酸素原子であるポリマーもよく知られているが、本発明においてはＹが酸素原子であると保存性が不十分となる。 In said general formula (1 ) , R is a methyl group or an ethyl group, and a methyl group is preferable. R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group or a propyl group, or a cycloalkyl group such as a cyclohexyl group. And a group in which the hydrogen bond of these groups is partially substituted with a halogen atom, for example, 3,3,3-trifluoropropyl group, etc., methyl group, ethyl group, vinyl group, phenyl group, 3, A 3,3-trifluoropropyl group is preferred, and a methyl group is particularly preferred. The plurality of R 1 in the general formula (1 ) may be the same group or different groups.
Y is an alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group, and an ethylene group is preferable.
A polymer in which Y is an oxygen atom is also well known, but in the present invention, if Y is an oxygen atom, the storage stability is insufficient.

本発明に使用される（Ｂ）成分である表面が脂肪酸で処理されたコロイド質炭酸カルシウム、（Ｃ）成分である表面がパラフィン系の処理剤で処理された重質炭酸カルシウムは、本組成物に保存安定性、良好な作業性を与えるとともに、樹脂接着性及び適度なゴム物性を付与するための必須成分である。   The composition (B) used in the present invention is a colloidal calcium carbonate whose surface is treated with a fatty acid, and the surface (C) component is a heavy calcium carbonate treated with a paraffinic treatment agent. It is an essential component for imparting storage stability and good workability to the resin, and imparting resin adhesion and appropriate rubber properties.

ここで、（Ｂ），（Ｃ）成分を併用する理由としては、（Ｂ）成分のみでは難接着といわれる樹脂被着体（ＰＰＳ、アクリル樹脂等）に対して良好な接着性が得られず、（Ｃ）成分を必要量添加することでこれら難接着樹脂被着体に対する接着性も良好となり、適度な作業性が得られるからである。また、（Ｃ）成分のみでは樹脂接着性が著しく悪くなるだけでなく、組成物のたれ落ち、作業性が悪くなってしまう。   Here, the reason why the components (B) and (C) are used in combination is that good adhesion to a resin adherend (PPS, acrylic resin, etc.), which is said to be difficult to adhere only with the component (B), cannot be obtained. This is because, by adding the necessary amount of the component (C), the adhesion to these hardly-adhesive resin adherends becomes good, and an appropriate workability can be obtained. In addition, the component (C) alone not only significantly deteriorates the resin adhesiveness, but also causes the composition to fall and the workability to deteriorate.

（Ｂ）成分は表面が脂肪酸で処理されていることが必須であり、他の処理剤（樹脂酸等）で処理されたコロイド質炭酸カルシウム、又は表面が無処理であるコロイド質炭酸カルシウムを使用した組成物では難接着樹脂に対する接着性及び作業性等も低下する。また、（Ｃ）成分は表面がパラフィン系で処理されていることが必須であり、他の処理剤（脂肪酸、樹脂酸等）で処理された重質炭酸カルシウム、又は表面が無処理である重質炭酸カルシウムを使用した組成物では難接着樹脂に対する接着性及び作業性等も低下する。   (B) It is essential that the surface of the component is treated with a fatty acid, and colloidal calcium carbonate treated with other treatment agents (resin acid, etc.) or colloidal calcium carbonate whose surface is untreated is used. With such a composition, the adhesiveness and workability to difficult-to-adhere resin also decrease. In addition, it is essential that the component (C) has a paraffinic surface, heavy calcium carbonate treated with other treating agents (fatty acid, resin acid, etc.), or heavy untreated surface. In the composition using quality calcium carbonate, the adhesiveness and workability with respect to difficult-to-adhere resin also decrease.

この場合、（Ｂ）成分のコロイド質炭酸カルシウムとしては、電子顕微鏡による測定法での平均粒径が０．０１〜０．１μｍ、特に０．０３〜０．０６μｍであるものが好ましい。また、コロイド質炭酸カルシウムの空気透過法比表面積が３ｍ2／ｇ以上、特に４〜７ｍ2／ｇであることが好ましい。このコロイド質炭酸カルシウムを処理する脂肪酸としては、炭素原子数が１０〜２０、特に１２〜１８のものが挙げられ、混合脂肪酸であってもよい。脂肪酸は、飽和脂肪酸でも不飽和脂肪酸でもよいが、飽和脂肪酸が好ましい。具体的には、オレイン酸、パルミチン酸、ステアリン酸等が挙げられ、その１種又は２種以上を使用し得る。その処理量は炭酸カルシウムに対して０．５〜５質量％、特に２．０〜４．０質量％であることが好ましい。 In this case, the colloidal calcium carbonate as the component (B) is preferably one having an average particle diameter of 0.01 to 0.1 μm, particularly 0.03 to 0.06 μm as measured by an electron microscope. The air permeability method specific surface area of the colloidal calcium carbonate is 3m 2 / g or more, particularly preferably 4~7m 2 / g. Examples of the fatty acid for treating the colloidal calcium carbonate include those having 10 to 20 carbon atoms, particularly 12 to 18 carbon atoms, and may be mixed fatty acids. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, but is preferably a saturated fatty acid. Specific examples include oleic acid, palmitic acid, stearic acid, and the like, and one or more of them can be used. The treatment amount is preferably 0.5 to 5% by mass, particularly 2.0 to 4.0% by mass with respect to calcium carbonate.

一方、（Ｃ）成分の重質炭酸カルシウムとしては、電子顕微鏡による測定法での平均粒径が０．７〜２．５μｍであり、また、重質炭酸カルシウムの空気透過法比表面積が０．５〜２．５ｍ2／ｇ、特に０．８〜２．０ｍ2／ｇであることが好ましい。重質炭酸カルシウムを処理するパラフィン系処理剤としては、直鎖状又は分岐状パラフィンであれば特に制限されないが、炭素原子数２０〜３０のものが好ましく、これらを１種又は２種以上用いることが好ましい。その処理量は、炭酸カルシウムに対して０．１〜５質量％、特に１．０〜２．５質量％であることが好ましい。
なお、上記炭酸カルシウムの表面処理は、公知の方法によって行うことができる。
On the other hand, the heavy calcium carbonate as the component (C) has an average particle size of 0 . 7~2.5μm der is, also, it is preferable air permeability method specific surface area of calcium carbonate is 0.5 to 2.5 m 2 / g, especially 0.8~2.0m 2 / g. The paraffin-based treating agent for treating heavy calcium carbonate is not particularly limited as long as it is a linear or branched paraffin, but those having 20 to 30 carbon atoms are preferable, and one or more of these are used. Is preferred. The treatment amount is preferably 0.1 to 5% by mass, particularly 1.0 to 2.5% by mass with respect to calcium carbonate.
The surface treatment of the calcium carbonate can be performed by a known method.

（Ｂ），（Ｃ）成分は、予め処理された炭酸カルシウムを使用してもよく、また本組成物の製造時に処理してもよい。本組成物の保存安定性を大幅に改善するためには表面処理剤、処理時の副生成物及び触媒などが本組成物中に実質的に残留しないようにすることが重要である。このためには、予め処理された炭酸カルシウムを使用することが好ましい。   (B) and (C) component may use the calcium carbonate processed beforehand, and may process it at the time of manufacture of this composition. In order to significantly improve the storage stability of the composition, it is important that the surface treatment agent, the by-products during the treatment, the catalyst, and the like do not substantially remain in the composition. For this purpose, it is preferable to use pretreated calcium carbonate.

（Ｂ）成分の添加量は、通常（Ａ）成分１００質量部に対し５０〜１５０質量部であるが、好ましくは７０〜１２０質量部である。多すぎると樹脂接着性の低下及び組成物の粘度が上昇し、混合及び施工時の吐出性が悪くなり、また、少なすぎると硬化後のゴム物性が悪くなる。   (B) Although the addition amount of a component is 50-150 mass parts normally with respect to 100 mass parts of (A) component, Preferably it is 70-120 mass parts. If the amount is too large, the resin adhesiveness decreases and the viscosity of the composition increases, resulting in poor ejection properties during mixing and construction. If the amount is too small, the physical properties of the rubber after curing are degraded.

（Ｃ）成分の添加量は、通常（Ａ）成分１００質量部に対し１０〜５０質量部であるが、好ましくは１５〜３５質量部である。多すぎると樹脂接着性及びゴム物性の低下、混合及び施工時の吐出性が悪くなり、また、少なすぎると難接着樹脂被着体に対する接着性が低下してしまう。   (C) Although the addition amount of a component is 10-50 mass parts normally with respect to 100 mass parts of (A) component, Preferably it is 15-35 mass parts. If the amount is too large, the resin adhesive property and rubber physical properties are deteriorated, and the discharge property during mixing and construction is deteriorated.

本発明における（Ｄ）成分は、ケイ素原子に結合した加水分解性基（アルコキシ基）を１分子中に平均２個以上、特に３個以上有し、かつ常圧での沸点が１５０℃以上であるアルコキシシラン化合物及び／又はその部分加水分解物である。加水分解性基以外のケイ素原子に結合した残余の基は、炭素原子数１〜１０の一価炭化水素基であれば特に限定されるものではないが、具体的にはメチル基、エチル基、プロピ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が例示されるが、満たされる条件としては常圧での沸点が１５０℃以上有することである。メチルトリメトキシシラン（ｂ．ｐ．１０２℃）、メチルトリエトキシシラン（ｂ．ｐ．１４３℃）、ビニルトリメトキシシラン（ｂ．ｐ．１２３℃）のような沸点が１５０℃未満のものでは強い臭気が残る場合がある。   The component (D) in the present invention has an average of 2 or more, particularly 3 or more hydrolyzable groups (alkoxy groups) bonded to a silicon atom, and has a boiling point of 150 ° C. or higher at normal pressure. A certain alkoxysilane compound and / or a partial hydrolyzate thereof. The remaining group bonded to the silicon atom other than the hydrolyzable group is not particularly limited as long as it is a monovalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, Illustrative examples include alkyl groups such as propyl groups, alkenyl groups such as vinyl groups, and aryl groups such as phenyl groups. The conditions to be satisfied include a boiling point of 150 ° C. or higher at normal pressure. Strong when the boiling point is less than 150 ° C, such as methyltrimethoxysilane (bp 102 ° C), methyltriethoxysilane (bp 143 ° C), vinyltrimethoxysilane (bp 123 ° C) Odor may remain.

（Ｄ）成分の具体例としては、テトラエトキシシラン、メチルセロソルブオルソシリケートなどの４官能アルコキシシラン類、エチルトリエトキシシラン（ｂ．ｐ．１６０℃）、ビニルトリエトキシシラン（ｂ．ｐ．１５８℃）、ｎ−ブチルトリメトキシシラン（ｂ．ｐ．１６４．８℃）、プロピルトリメトキシシラン、フェニルトリメトキシシラン（ｂ．ｐ．１３０℃／４５ｍｍＨｇ）、ブチルトリメトキシエトキシシランなどの３官能アルコキシシラン類及びその部分加水分解縮合物などが挙げられる。上記した沸点が１５０℃未満のシランであっても加水分解縮合したダイマーやトリマーであれば使用することができる。これらは単独で用いてもよく、２種以上を混合してもよい。また、硬化後のゴム弾性体に低モジュラス性を付与するために、ジフェニルジメトキシシランなどの２官能アルコキシシラン類を付加的に添加してもよい。   Specific examples of the component (D) include tetrafunctional alkoxysilanes such as tetraethoxysilane and methyl cellosolv orthosilicate, ethyltriethoxysilane (bp 160 ° C), vinyltriethoxysilane (bp 158 ° C). ), N-butyltrimethoxysilane (bp 164.8 ° C.), propyltrimethoxysilane, phenyltrimethoxysilane (bp 130 ° C./45 mmHg), trifunctional alkoxysilane such as butyltrimethoxyethoxysilane And partially hydrolyzed condensates thereof. Even a silane having a boiling point of less than 150 ° C. can be used as long as it is a hydrolyzed dimer or trimer. These may be used alone or in combination of two or more. In addition, bifunctional alkoxysilanes such as diphenyldimethoxysilane may be additionally added in order to impart low modulus to the rubber elastic body after curing.

（Ｄ）成分の配合量は、（Ａ）成分１００質量部に対して０．１〜２０質量部の範囲、好ましくは、１〜１０質量部の範囲で使用される。０．１質量部未満では十分な架橋が得られず、目的とするゴム弾性を有する組成物が得難く、２０質量部を超えると得られる硬化物は機械特性が低下する上、組成物の臭気が悪化する。   (D) The compounding quantity of a component is 0.1-20 mass parts with respect to 100 mass parts of (A) component, Preferably, it is used in the range of 1-10 mass parts. If the amount is less than 0.1 parts by mass, sufficient crosslinking cannot be obtained, and it is difficult to obtain a composition having the desired rubber elasticity. If the amount exceeds 20 parts by mass, the resulting cured product has reduced mechanical properties and the odor of the composition. Gets worse.

本発明に使用される（Ｅ）成分は、本組成物を硬化するための触媒で、下記一般式（４）

Figure 0004438937
（式中、Ｒ3は酸素原子に結合する炭素原子が３級である炭素原子数４〜１０の３級炭化水素基であり、Ｒ4は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であるが、３級炭素原子を有さない。ａは０〜２の整数である。）
で示される酸素原子に結合した３級炭素原子を少なくとも２個有するオルガノキシチタンである。Ｒ4の炭素原子数１〜１０の一価炭化水素基としては、３級炭化水素基を有さないものであり、特に直鎖状又は１個の分岐鎖を有するアルキル基が好ましく、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等が挙げられ、炭素原子数１〜４のものが好ましい。Ｒ3は炭素原子数４〜１０の３級炭化水素基であり、ｔ−ブチル基が好ましい。上記オルガノキシチタンの具体例としては、テトラ−ｔｅｒｔ−ブトキシチタン、イソプロポキシ−トリ−ｔｅｒｔ−ブトキシチタン、ブトキシ−トリ−ｔｅｒｔ−ブトキシチタン、ジイソプロポキシ−トリ−ｔｅｒｔ−ブトキシチタンなどが例示される。 The component (E) used in the present invention is a catalyst for curing the present composition, and the following general formula (4)
Figure 0004438937
 (Wherein R 3 is a tertiary hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the oxygen atom is tertiary, and R 4 is a substituted or unsubstituted one having 1 to 10 carbon atoms. (It is a valent hydrocarbon group but has no tertiary carbon atom. A is an integer of 0 to 2.)
An organoxytitanium having at least two tertiary carbon atoms bonded to an oxygen atom represented by The monovalent hydrocarbon group having 1 to 10 carbon atoms of R 4 is a group having no tertiary hydrocarbon group, particularly preferably a linear or alkyl group having one branched chain, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group and the like, and those having 1 to 4 carbon atoms are preferable. R 3 is a tertiary hydrocarbon group having 4 to 10 carbon atoms, preferably a t-butyl group. Specific examples of the organoxytitanium include tetra-tert-butoxytitanium, isopropoxy-tri-tert-butoxytitanium, butoxy-tri-tert-butoxytitanium, diisopropoxy-tri-tert-butoxytitanium and the like. The

（Ｅ）成分の添加量は、（Ａ）成分１００質量部に対して１〜１５質量部の範囲であり、好ましくは３〜１０質量部の範囲である。添加量が少ないと良好な保存安定性が得られず、かつ本組成物の硬化物が得られる時間が長くなる。逆に多すぎると表面硬化性が速すぎたり、深部硬化性が悪くなったり、保存安定性が悪くなるためである。   (E) The addition amount of a component is the range of 1-15 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 3-10 mass parts. If the amount added is small, good storage stability cannot be obtained, and the time for obtaining a cured product of the present composition becomes longer. On the contrary, if the amount is too large, the surface curability is too fast, the deep portion curability is deteriorated, or the storage stability is deteriorated.

（Ｆ）成分のシランカップリング剤は、本発明の室温硬化性オルガノポリシロキサン組成物において接着性付与成分としての作用を有する成分である。シランカップリング剤としては公知のものが好適に使用され、（メタ）アクリルシランカップリング剤、エポキシシランカップリング剤、アミノシランカップリング剤、メルカプトシランカップリング剤等が例示され、具体的には、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−グリシドキプロピルトリメトキシシラン、γ−グリシドキプロピルメチルトリエトキシシラン、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、γ−メルカプトプロピルトリメトキシシラン等が例示される。   The silane coupling agent of (F) component is a component which has an effect | action as an adhesive provision component in the room temperature curable organopolysiloxane composition of this invention. Known silane coupling agents are preferably used, and examples include (meth) acryl silane coupling agents, epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, and the like. γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, N-β- (aminoethyl) )-[Gamma] -aminopropyltrimethoxysilane, [gamma] -aminopropyltriethoxysilane, [gamma] -mercaptopropyltrimethoxysilane and the like are exemplified.

このシランカップリング剤の配合量は（Ａ）成分１００質量部当たり０〜１０質量部、好ましくは０．１〜５質量部使用される。充填剤及び被着体によりシランカップリング剤を使用しなくても接着するときは、シランカップリング剤を使用しなくてもよく、使用する場合、１０質量部を超えると価格的に不利となる。   The amount of the silane coupling agent used is 0 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). When adhering without using a silane coupling agent with a filler and an adherend, it is not necessary to use a silane coupling agent. .

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には、（Ｇ）非反応性のシリコーンオイル、好ましくは両末端がトリメチルシリル基で封鎖されたポリジメチルシロキサンを配合することが好ましい。この成分を配合することにより、作業性、糸切れ性等の特性が向上すると共に、硬化後のゴム物性を調整することができる。
この粘度（２５℃）は５〜５０，０００ｍＰａ・ｓ、特に５０〜５，０００ｍＰａ・ｓであることが好ましい。配合量は、（Ａ）成分１００質量部に対して０〜１００質量部、特に５〜８０質量部であることが好ましい。 The room temperature-curable organopolysiloxane composition of the present invention preferably contains (G) a non-reactive silicone oil, preferably polydimethylsiloxane having both ends blocked with trimethylsilyl groups. By blending this component, properties such as workability and thread breakage are improved, and rubber properties after curing can be adjusted.
The viscosity (25 ° C.) is preferably 5 to 50,000 mPa · s, particularly 50 to 5,000 mPa · s. It is preferable that a compounding quantity is 0-100 mass parts with respect to 100 mass parts of (A) component, especially 5-80 mass parts.

本発明の室温硬化性オルガノポリシロキサン組成物は、前記した（Ａ）〜（Ｆ）成分の他に、更に必要に応じて、硬化前の流れ特性を改善し、硬化後のゴム状弾性体に必要な機械的性質を付与するために、微粉末状の無機質充填剤を添加することもできる。無機質充填剤としては石英微粉末、煙霧質シリカ、沈降性シリカ、煙霧質二酸化チタン、珪藻土、水酸化アルミニウム、微粒子状アルミナ、マグネシア、酸化亜鉛、炭酸亜鉛及びこれらをシラン類、シラザン類、低重合度シロキサン類、有機化合物などで表面処理したものなどが例示される。   In addition to the components (A) to (F) described above, the room temperature curable organopolysiloxane composition of the present invention can further improve the flow characteristics before curing as necessary to form a rubber-like elastic body after curing. In order to impart necessary mechanical properties, a fine powdery inorganic filler may be added. Inorganic fillers include quartz fine powder, fumed silica, precipitated silica, fumed titanium dioxide, diatomaceous earth, aluminum hydroxide, particulate alumina, magnesia, zinc oxide, zinc carbonate and their silanes, silazanes, and low polymerization. Examples thereof include those that have been surface-treated with siloxanes and organic compounds.

更に、本発明の室温硬化性オルガノポリシロキサン組成物には有機溶剤、防カビ剤、難燃剤、耐熱剤、可塑剤、チクソ性付与剤、接着促進剤、硬化促進剤、顔料などを添加することができる。   Furthermore, an organic solvent, an antifungal agent, a flame retardant, a heat resistance agent, a plasticizer, a thixotropic agent, an adhesion promoter, a curing accelerator, a pigment, and the like are added to the room temperature curable organopolysiloxane composition of the present invention. Can do.

本発明の室温硬化性オルガノポリシロキサン組成物は、（Ａ）〜（Ｆ）成分及び必要に応じて各種添加剤を、湿気を遮断した状態で混合することにより得られる。得られた組成物は密閉容器中でそのまま保存し、使用時に空気中の水分に晒すことによりゴム状弾性体に硬化する、いわゆる１包装型室温硬化性オルガノポリシロキサン組成物として用いることができる。   The room temperature-curable organopolysiloxane composition of the present invention can be obtained by mixing the components (A) to (F) and various additives as necessary while blocking moisture. The obtained composition can be used as a so-called one-packaging room temperature curable organopolysiloxane composition that is stored as it is in a closed container and is cured into a rubber-like elastic body by being exposed to moisture in the air during use.

本発明の室温硬化性オルガノポリシロキサン組成物は、建築用シーリング材として、電気・電子部品の封止材、接着剤や防湿用コート剤として、繊維製品、ガラス製品、金属製品、プラスチック製品等のコーティング剤や接着剤としての用途に適用することができる。
この場合、本発明の室温硬化性オルガノポリシロキサン組成物は、難接着性樹脂、例えばアクリル樹脂、ポリカーボネート樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂、ポリスチロール、ＡＢＳ樹脂、塩化ビニル樹脂等との接着に有効に用いられる。 The room temperature curable organopolysiloxane composition of the present invention is used as a sealing material for buildings, as a sealing material for electrical and electronic parts, as an adhesive or a moisture-proof coating agent, as a textile product, glass product, metal product, plastic product, etc. It can be applied to applications as a coating agent or an adhesive.
In this case, the room temperature curable organopolysiloxane composition of the present invention is suitable for adhesion to hard-to-adhere resins such as acrylic resin, polycarbonate resin, polybutylene terephthalate (PBT) resin, polystyrene, ABS resin, and vinyl chloride resin. Used effectively.

以下、合成例及び実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において部は質量部を示し、粘度は２５℃での回転粘度計による測定法の測定値を示したものである。   EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part and a viscosity shows the measured value of the measuring method with a rotational viscometer at 25 degreeC.

［合成例１］
温度計、撹拌機、冷却器を備えた内容積２リットルの三つ口フラスコに、粘度が３０，０００ｍＰａ・ｓのα，ω−ジメチルビニル−ジメチルポリシロキサン２，５００ｇと、トルエン４００ｇ、トリメトキシシラン１１．９ｇ及び触媒として塩化白金酸の５０％トルエン溶液１．０ｇを添加し、Ｎ2気流下で室温で９時間混合した。その後１０ｍｍＨｇの減圧下で１００℃に加熱して、希釈剤のトルエンと余剰のトリメトキシシランを留去し、粘度が４０，０００ｍＰａ・ｓ、不揮発分９９．９％の無色透明液体を２，３５０ｇ得た。得られた液体にテトラプロピルチタネートと１００：１の比率（質量比）で混合したところ、直ちには増粘せず、１日後には硬化した。このことからポリマー末端のビニル基にメチルトリメトキシシランが付加したことが確認できる。このポリマーをポリマーＡとする。 [Synthesis Example 1]
In a three-necked flask with an internal volume of 2 liters equipped with a thermometer, stirrer and cooler, 2500 g of α, ω-dimethylvinyl-dimethylpolysiloxane having a viscosity of 30,000 mPa · s, 400 g of toluene, and trimethoxy 11.9 g of silane and 1.0 g of 50% toluene solution of chloroplatinic acid as a catalyst were added and mixed for 9 hours at room temperature under N 2 stream. Thereafter, the mixture was heated to 100 ° C. under a reduced pressure of 10 mmHg to distill off the diluent toluene and excess trimethoxysilane, and 2,350 g of a colorless transparent liquid having a viscosity of 40,000 mPa · s and a nonvolatile content of 99.9%. Obtained. When the obtained liquid was mixed with tetrapropyl titanate at a ratio of 100: 1 (mass ratio), it did not immediately thicken and was cured after one day. From this, it can be confirmed that methyltrimethoxysilane was added to the vinyl group at the end of the polymer. This polymer is referred to as polymer A.

［合成例２］
温度計、撹拌機、冷却器を備えた内容積２リットルの三つ口フラスコに、粘度が３０，０００ｍＰａ・ｓの側鎖に２個ビニル基を有するα，ω−ジメチルビニル−ジメチルポリシロキサン２，５００ｇと、トルエン４００ｇ、トリメトキシシラン１５ｇ及び触媒として塩化白金酸の５０％トルエン溶液１．０ｇを添加し、Ｎ2気流下で室温で９時間混合した。その後１０ｍｍＨｇの減圧下で１００℃に加熱して、希釈剤のトルエンと余剰のトリメトキシシランを留去し、粘度が５２，０００ｍＰａ・ｓ、不揮発分９９．９％の無色透明液体を２，２５０ｇ得た。得られた液体にテトラブチルチタネートと１００：１の比率（質量比）で混合したところ、直ちには増粘せず、１日後には硬化した。このことからポリマー中に含まれるビニル基にメチルトリメトキシシランが付加したことが確認できる。このポリマーをポリマーＢとする。 [Synthesis Example 2]
Α, ω-dimethylvinyl-dimethylpolysiloxane 2 having two vinyl groups in the side chain with a viscosity of 30,000 mPa · s in a three-necked flask having an internal volume of 2 liters equipped with a thermometer, a stirrer and a condenser , 500 g, 400 g of toluene, 15 g of trimethoxysilane and 1.0 g of a 50% toluene solution of chloroplatinic acid as a catalyst were added and mixed for 9 hours at room temperature under a N 2 stream. Thereafter, the mixture was heated to 100 ° C. under a reduced pressure of 10 mmHg to distill off the diluent toluene and excess trimethoxysilane, and 2,250 g of a colorless transparent liquid having a viscosity of 52,000 mPa · s and a non-volatile content of 99.9%. Obtained. When the obtained liquid was mixed with tetrabutyl titanate at a ratio of 100: 1 (mass ratio), it did not immediately thicken and was cured after one day. This confirms that methyltrimethoxysilane has been added to the vinyl group contained in the polymer. This polymer is referred to as polymer B.

［実施例１］
ポリマーＡ１００部と粘度が１００ｍＰａ・ｓの両末端メチル基封鎖ポリジメチルシロキサン４５部、脂肪酸で表面処理されたコロイド質炭酸カルシウム（カーレックス３００、丸尾カルシウム（株）製）９０部、パラフィンで表面処理された重質炭酸カルシウム（ＭＣコート Ｐ−１０、丸尾カルシウム（株）製）３０部を均一に混合し、これにフェニルトリメトキシシラン（ｂ．ｐ．１３０℃／４５ｍｍＨｇ）９部とテトラ−ｔｅｒｔ−ブトキシチタン９部を湿気遮断下で均一になるまで混合して組成物を調製した。 [Example 1]
100 parts of polymer A, 45 parts of polydimethylsiloxane blocked with methyl groups at both ends with a viscosity of 100 mPa · s, 90 parts of colloidal calcium carbonate surface-treated with fatty acid (Carlex 300, manufactured by Maruo Calcium Co., Ltd.), surface treatment with paraffin 30 parts of heavy calcium carbonate (MC coat P-10, manufactured by Maruo Calcium Co., Ltd.) was mixed uniformly, and 9 parts of phenyltrimethoxysilane (bp 130 ° C./45 mmHg) and tetra-tert. -A composition was prepared by mixing 9 parts of butoxytitanium until uniform under moisture barrier.

［実施例２］
ポリマーＢ１００部と粘度が１００ｍＰａ・ｓの両末端メチル基封鎖ポリジメチルシロキサン４５部、脂肪酸で表面処理されたコロイド質炭酸カルシウム（カーレックス３００、丸尾カルシウム（株）製）９０部、パラフィンで表面処理された重質炭酸カルシウム（ＭＣコート Ｐ−１０、丸尾カルシウム（株）製）３０部を均一に混合し、これにフェニルトリメトキシシラン９部とテトラ−ｔｅｒｔ−ブトキシチタン９部を湿気遮断下で均一になるまで混合して組成物を調製した。 [Example 2]
100 parts of polymer B, 45 parts of polydimethylsiloxane blocked with methyl groups at both ends with a viscosity of 100 mPa · s, 90 parts of colloidal calcium carbonate surface-treated with fatty acid (Carlex 300, manufactured by Maruo Calcium Co., Ltd.), surface treatment with paraffin 30 parts of heavy calcium carbonate (MC Coat P-10, manufactured by Maruo Calcium Co., Ltd.) were uniformly mixed, and 9 parts of phenyltrimethoxysilane and 9 parts of tetra-tert-butoxytitanium were then blocked under moisture. A composition was prepared by mixing until uniform.

［実施例３］
ポリマーＡ１００部と粘度が１００ｍＰａ・ｓの両末端メチル基封鎖ポリジメチルシロキサン４５部、脂肪酸で表面処理されたコロイド質炭酸カルシウム（カーレックス３００、丸尾カルシウム（株）製）９０部、パラフィンで表面処理された重質炭酸カルシウム（ＭＣコート Ｐ−１０、丸尾カルシウム（株）製）３０部を均一に混合し、これにフェニルトリメトキシシラン９部とイソプロポキシ−トリ−ｔｅｒｔ−ブトキシチタン９部を湿気遮断下で均一になるまで混合して組成物を調製した。 [Example 3]
100 parts of polymer A, 45 parts of polydimethylsiloxane blocked with methyl groups at both ends with a viscosity of 100 mPa · s, 90 parts of colloidal calcium carbonate surface-treated with fatty acid (Carlex 300, manufactured by Maruo Calcium Co., Ltd.), surface treatment with paraffin 30 parts of heavy calcium carbonate (MC Coat P-10, manufactured by Maruo Calcium Co., Ltd.) were mixed uniformly, and 9 parts of phenyltrimethoxysilane and 9 parts of isopropoxy-tri-tert-butoxytitanium were moistened. A composition was prepared by mixing under blockage until uniform.

［実施例４］
ポリマーＡ１００部と粘度が１００ｍＰａ・ｓの両末端メチル基封鎖ポリジメチルシロキサン４５部、脂肪酸で表面処理されたコロイド質炭酸カルシウム（カーレックス３００、丸尾カルシウム（株）製）９０部、パラフィンで表面処理された重質炭酸カルシウム（ＭＣコート Ｐ−１０、丸尾カルシウム（株）製）３０部を均一に混合し、これにフェニルトリメトキシシラン９部とジイソプロポキシ−ジ−ｔｅｒｔ−ブトキシチタン９部を湿気遮断下で均一になるまで混合して組成物を調製した。 [Example 4]
100 parts of polymer A, 45 parts of polydimethylsiloxane blocked with methyl groups at both ends with a viscosity of 100 mPa · s, 90 parts of colloidal calcium carbonate surface-treated with fatty acid (Carlex 300, manufactured by Maruo Calcium Co., Ltd.), surface treatment with paraffin 30 parts of heavy calcium carbonate (MC Coat P-10, manufactured by Maruo Calcium Co., Ltd.) were mixed uniformly, and 9 parts of phenyltrimethoxysilane and 9 parts of diisopropoxy-di-tert-butoxytitanium were added thereto. A composition was prepared by mixing under moisture block until uniform.

［比較例１］
実施例１において、脂肪酸で表面処理されたコロイド質炭酸カルシウムの代わりに樹脂酸で処理されたコロイド質炭酸カルシウム（ＭＴ−１００、丸尾カルシウム（株）製）を用いた以外は実施例１と同様の手法で組成物を調製した。 [Comparative Example 1]
In Example 1, colloidal calcium carbonate treated with resin acid (MT-100, manufactured by Maruo Calcium Co., Ltd.) was used instead of colloidal calcium carbonate surface-treated with fatty acid, as in Example 1. The composition was prepared by the method.

［比較例２］
実施例１において、パラフィンで表面処理された重質炭酸カルシウムの代わりに脂肪酸で処理された重質炭酸カルシウム（スノーライト、丸尾カルシウム（株）製）を用いた以外は実施例１と同様の手法で組成物を調製した。 [Comparative Example 2]
In Example 1, the same method as in Example 1 was used except that heavy calcium carbonate treated with a fatty acid (Snowlite, manufactured by Maruo Calcium Co., Ltd.) was used instead of heavy calcium carbonate surface-treated with paraffin. A composition was prepared.

［比較例３］
実施例１において、フェニルトリメトキシシランの代わりにメチルトリメトキシシラン（ｂ．ｐ．１０２℃）を用いた以外は実施例１と同様の手法で組成物を調製した。 [Comparative Example 3]
A composition was prepared in the same manner as in Example 1 except that methyltrimethoxysilane (bp 102 ° C.) was used instead of phenyltrimethoxysilane.

［比較例４］
実施例１において、テトラ−ｔｅｒｔ−ブトキシチタンの代わりにテトライソプロポキシチタンを用いた以外は実施例１と同様の手法で組成物を調製した。 [Comparative Example 4]
In Example 1, a composition was prepared in the same manner as in Example 1, except that tetraisopropoxytitanium was used instead of tetra-tert-butoxytitanium.

これらの実施例、比較例の組成物は２ｍｍ厚のシート状に成形し、２３±２℃、５０±５％ＲＨの雰囲気で７日間硬化してそのゴム物性（硬さ、伸び、引張強さ）をＪＩＳ Ｋ６２４９に準じて測定した。その際、組成物の臭気を嗅ぎ、不快な気分がするかどうかの確認を行った。また同時に、２５×１００×２ｍｍ厚の樹脂被着体に作製した組成物を塗布し、室温下に放置してゴム弾性体としたのち、得られた硬化物を引っ張ることで被着体の接着性を目視にて確認した。ここで樹脂被着体は建築用材料として比較的使用されやすい硬質塩化ビニル樹脂、ポリスチロール、ポリカーボネート、アクリル樹脂を選定した。保存安定性試験は、未硬化の組成物をカートリッジの荷姿で７０℃の乾燥機中で加熱し、その後、２３±２℃、５０±５％ＲＨの雰囲気下で７日硬化させ、初期の組成物と同様にゴム物性及び接着性の測定を行った。実施例１〜４の結果を表１、実施例１及び比較例の結果を表２に示す。   The compositions of these examples and comparative examples were molded into a sheet having a thickness of 2 mm and cured for 7 days in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH, and their rubber properties (hardness, elongation, tensile strength) ) Was measured according to JIS K6249. At that time, the smell of the composition was sniffed, and it was confirmed whether or not it felt uncomfortable. At the same time, the prepared composition is applied to a resin adherend having a thickness of 25 × 100 × 2 mm, left at room temperature to form a rubber elastic body, and then the resulting cured product is pulled to bond the adherend. The property was confirmed visually. Here, hard vinyl chloride resin, polystyrene, polycarbonate, and acrylic resin, which are relatively easy to use as building materials, were selected as the resin adherend. In the storage stability test, the uncured composition was heated in a dryer at 70 ° C. in the form of a cartridge, and then cured for 7 days in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH. Rubber properties and adhesiveness were measured in the same manner as the composition. The results of Examples 1 to 4 are shown in Table 1, and the results of Example 1 and Comparative Example are shown in Table 2.

Figure 0004438937
Figure 0004438937

Figure 0004438937
Figure 0004438937

Claims (2)

（Ａ）下記一般式（１）
Figure 0004438937
 （式中、Ｒはメチル基又はエチル基であり、Ｒ1は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であり、Ｘは１０以上の整数である。Ｙは炭素原子数１〜５のアルキレン基であり、Ｎは独立に０又は１の整数である。）
で示されるオルガノポリシロキサン １００質量部、
（Ｂ）表面が脂肪酸で処理されたコロイド質炭酸カルシウム ５０〜１５０質量部、
（Ｃ）表面がパラフィン系の処理剤で処理された平均粒径が０．７〜２．５μｍである重質炭酸カルシウム １０〜５０質量部、
（Ｄ）ケイ素原子に結合した加水分解性基を１分子中に平均２個以上有し、かつ常圧での沸点が１５０℃以上であるアルコキシシラン化合物、その部分加水分解物又はこれらの混合物 ０．１〜２０質量部、
（Ｅ）下記一般式（４）
Figure 0004438937
 （式中、Ｒ3は酸素原子に結合する炭素原子が３級である炭素原子数４〜１０の３級炭化水素基であり、Ｒ4は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であるが、３級炭素原子を有さない。ａは０〜２の整数である。）
で示されるオルガノキシチタン １〜１５質量部、
（Ｆ）シランカップリング剤 ０〜１０質量部
を必須成分としてなることを特徴とする樹脂との接着用の室温硬化性オルガノポリシロキサン組成物。 (A) The following general formula (1)
Figure 0004438937
 Wherein R is a methyl group or an ethyl group, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
100 parts by mass of an organopolysiloxane represented by
(B) co surface-treated with a fatty acid Lloyd calcium carbonate 50 to 150 parts by weight,
(C) 10-50 parts by weight of heavy calcium carbonate having an average particle size of 0.7-2.5 μm, the surface of which has been treated with a paraffinic treatment agent,
(D) an alkoxysilane compound, a partially hydrolyzed product thereof, or a mixture thereof, having an average of two or more hydrolyzable groups bonded to a silicon atom and having a boiling point of 150 ° C. or higher at normal pressure .1-20 parts by mass,
(E) The following general formula (4)
Figure 0004438937
 (In the formula, R 3 is a tertiary hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the oxygen atom is tertiary, and R 4 is a substituted or unsubstituted one having 1 to 10 carbon atoms. (It is a valent hydrocarbon group but has no tertiary carbon atom. A is an integer of 0 to 2.)
1 to 15 parts by mass of organoxytitanium represented by
(F) Silane coupling agent A room temperature-curable organopolysiloxane composition for adhesion to a resin , characterized by comprising 0 to 10 parts by mass as an essential component. 更に、（Ｇ）非反応性シリコーンオイルを含有することを特徴とする請求項１記載の室温硬化性オルガノポリシロキサン組成物。   Furthermore, (G) non-reactive silicone oil is contained, The room temperature curable organopolysiloxane composition of Claim 1 characterized by the above-mentioned.
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