JP2009292914A - Room temperature-curable silicone rubber composition - Google Patents

Room temperature-curable silicone rubber composition Download PDF

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JP2009292914A
JP2009292914A JP2008146992A JP2008146992A JP2009292914A JP 2009292914 A JP2009292914 A JP 2009292914A JP 2008146992 A JP2008146992 A JP 2008146992A JP 2008146992 A JP2008146992 A JP 2008146992A JP 2009292914 A JP2009292914 A JP 2009292914A
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JP5155024B2 (en
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Isao Iida
勲 飯田
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Momentive Performance Materials Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To enhance curability and adhesiveness of a condensation reaction type room temperature-curable silicone rubber composition that is cured at room temperature to produce a rubbery elastic material. <P>SOLUTION: The room temperature-curable silicone rubber composition contains: 10 to 90 parts by mass of polyorganosiloxane having viscosity of 0.02 to 100 Pa s, in which both molecular chain terminals are sequestered by hydroxy groups; 90 to 10 parts by mass of polyorgaosiloxane having viscosity of 0.02 to 100 Pa s, in which only one molecular chain terminal is sequestered by a hydroxy group; 0.1 to 10 parts by mass of a partial hydrolyzed condensate of a silane compound expressed by formula:R<SP>1</SP><SB>a</SB>Si(OR<SP>2</SP>)<SB>4-a</SB>(wherein R<SP>1</SP>and R<SP>2</SP>may be identical with or different from each other and represent substituted or unsubstituted monovalent hydrocarbon groups, and (a) represents an average number satisfying 0≤a≤0.2); and 0.1 to 10 parts by mass of an amine functional silane compound expressed by formula:(R<SP>3</SP>O)<SB>3</SB>Si-R<SP>4</SP>-NH-R<SP>5</SP>(wherein a plurality of R<SP>3</SP>may be identical or mutually different and represent substituted or unsubstituted monovalent hydrocarbon groups, R<SP>4</SP>represents a substituted or unsubstituted divalent organic group, and R<SP>5</SP>represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, or an aminoalkyl group). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、室温で硬化してゴム状弾性体を生じる縮合反応型の室温硬化性シリコーンゴム組成物に関する。   The present invention relates to a condensation reaction type room temperature curable silicone rubber composition which is cured at room temperature to produce a rubbery elastic body.

自動車部品、電気・電子機器部品等の接着・シール材、ポッティング材、FIPGシール材等の用途に、室温で硬化してゴム状弾性体を生じる縮合反応型のシリコーンゴム組成物が広く用いられている。   Condensation reaction type silicone rubber compositions that cure at room temperature to produce rubber-like elastic bodies are widely used in applications such as adhesives / sealants, potting materials, FIPG sealants for automobile parts, electrical / electronic equipment parts, etc. Yes.

この縮合反応型の室温硬化性シリコーンゴム組成物は、基本的に空気中の水分との接触により硬化反応が生起されるものであり、かかる硬化反応を促進する触媒として、錫等の金属の有機酸塩、ジアルキル錫ジ脂肪酸塩、ジアルキル錫ジアルコキシド、ジアルキル錫オキシド、チタンテトラアルコキシドおよびその部分加水分解生成物、チタンキレート化合物、ジルコニウムキレート化合物、アルミニウムトリアルコキシドおよびその部分加水分解縮合物、並びに、アルミニウムキレート化合物等の、分子中に金属原子を有する有機化合物が一般に使用されている。   This condensation reaction type room temperature curable silicone rubber composition basically undergoes a curing reaction by contact with moisture in the air. As a catalyst for promoting the curing reaction, an organic metal such as tin is used. Acid salts, dialkyltin dialkoxides, dialkyltin dialkoxides, dialkyltin oxides, titanium tetraalkoxides and partial hydrolysis products thereof, titanium chelate compounds, zirconium chelate compounds, aluminum trialkoxides and partial hydrolysis condensates thereof, and An organic compound having a metal atom in the molecule, such as an aluminum chelate compound, is generally used.

しかしながら、このような金属原子含有有機化合物を触媒として用いた室温硬化性シリコーンゴム組成物は、硬化時間が長く、特に深部硬化性が不良であるという問題があった。   However, the room temperature curable silicone rubber composition using such a metal atom-containing organic compound as a catalyst has a problem that the curing time is long and the deep part curability is particularly poor.

一方、金属原子含有有機化合物に代えてアミン官能性シラン化合物を触媒として用いることにより、硬化速度を速め、深部硬化性を向上させたものが提案されている(例えば、特許文献1参照。)。   On the other hand, what improved the cure rate and improved deep part sclerosis | hardenability by using an amine functional silane compound as a catalyst instead of a metal atom containing organic compound is proposed (for example, refer patent document 1).

しかしながら、このアミン官能性シラン化合物を触媒として用いた組成物は、硬化速度、深部硬化性が改善されるものの、接着性については未だ改善すべき余地があった。
特表平07−020019号公報
However, although the composition using this amine functional silane compound as a catalyst has improved curing speed and deep part curability, there is still room for improvement in adhesiveness.
Japanese National Publication No. 07-020019

本発明はこのような従来技術の課題を解決するためになされたもので、硬化性が良好で、かつ、各種基材に対する接着性に優れる室温硬化性シリコーンゴム組成物を提供することを目的とする。   The present invention was made to solve such problems of the prior art, and aims to provide a room temperature curable silicone rubber composition having good curability and excellent adhesion to various substrates. To do.

本発明者は、前記した従来技術の問題を解決すべく鋭意研究を重ねた結果、分子鎖両末端が水酸基で封鎖されたポリオルガノシロキサンと、分子鎖の片末端のみが水酸基で封鎖されたポリオルガノシロキサンをベースポリマーとして使用するとともに、アミン官能シラン化合物およびテトラアルコキシシランの部分加水分解縮合物をそれぞれ硬化触媒および架橋剤として使用することにより、硬化性が良好で、かつ、各種基材に対する接着性に優れる室温硬化性シリコーンゴム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。   As a result of intensive studies to solve the problems of the prior art described above, the present inventor has found that polyorganosiloxane in which both molecular chain ends are blocked with a hydroxyl group and a polyorganosiloxane in which only one end of the molecular chain is blocked with a hydroxyl group. Uses organosiloxane as a base polymer, and uses a partially hydrolyzed condensate of an amine functional silane compound and tetraalkoxysilane as a curing catalyst and a crosslinking agent, respectively. It has been found that a room temperature curable silicone rubber composition having excellent properties can be obtained, and the present invention has been completed.

すなわち、本発明は、
(A)分子鎖両末端が水酸基で封鎖された23℃における粘度が0.02〜100Pa・sであるポリオルガノシロキサン 10〜90質量部、
(B)分子鎖片末端のみが水酸基で封鎖された23℃における粘度が0.02〜100Pa・sであるポリオルガノシロキサン 90〜10質量部、
(C)一般式:
Si(OR4−a …(1)
(式中、RおよびRは同一であっても異なっていてもよい置換もしくは非置換の1価の炭化水素基であり、aは平均値として0≦a≦0.2の数である。)で示されるシラン化合物の部分加水分解縮合物 0.1〜10質量部、および
(D)一般式:
(RO)Si−R−NH−R …(2)
(式中、Rは互いに同一であっても異なっていてもよい置換もしくは非置換の1価の炭化水素基であり、Rは置換もしくは非置換の2価の有機基であり、Rは水素原子、置換もしくは非置換の1価の炭化水素基またはアミノアルキル基である。)で示されるアミン官能シラン化合物 0.1〜10質量部、
を含有することを特徴とする室温硬化性シリコーンゴム組成物である。
That is, the present invention
(A) 10 to 90 parts by mass of a polyorganosiloxane having a viscosity at 23 ° C. of 0.02 to 100 Pa · s at which both ends of the molecular chain are blocked with hydroxyl groups,
(B) 90-10 parts by mass of a polyorganosiloxane having a viscosity at 23 ° C. of 0.02 to 100 Pa · s in which only one molecular chain end is blocked with a hydroxyl group,
(C) General formula:
R 1 a Si (OR 2 ) 4-a (1)
(In the formula, R 1 and R 2 are substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different, and a is an average value of 0 ≦ a ≦ 0.2. .) 0.1 to 10 parts by mass of a partially hydrolyzed condensate of the silane compound represented by the formula:
(R 3 O) 3 Si- R 4 -NH-R 5 ... (2)
(Wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other, R 4 is a substituted or unsubstituted divalent organic group, and R 5 Is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group or aminoalkyl group.) 0.1 to 10 parts by mass of an amine functional silane compound represented by
Is a room temperature curable silicone rubber composition characterized by comprising:

本発明の室温硬化性シリコーンゴム組成物は、硬化性が良好で、かつ、各種基材に対する接着性にも優れている。   The room temperature curable silicone rubber composition of the present invention has good curability and excellent adhesion to various substrates.

以下、本発明の実施形態について説明する。   Hereinafter, embodiments of the present invention will be described.

本発明の室温硬化性シリコーンゴム組成物の(A)成分であるポリオルガノシロキサンは、分子鎖両末端が水酸基で封鎖されたもので、代表的には、下記一般式(3)で表される実質的に直鎖状のポリオルガノシロキサンである。

Figure 2009292914
The polyorganosiloxane that is the component (A) of the room temperature curable silicone rubber composition of the present invention is one in which both ends of the molecular chain are blocked with hydroxyl groups, and is typically represented by the following general formula (3). It is a substantially linear polyorganosiloxane.
Figure 2009292914

式(3)中、複数のRはそれぞれ互いに同一であっても異なっていてもよい置換または非置換の1価の炭化水素基である。Rとしては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基のようなアルキル基;シクロヘキシル基のようなシクロアルキル基;ビニル基、アリル基のようなアルケニル基;フェニル基、トリル基、キシリル基のようなアリール基;ベンジル基、2−フェニルエチル基、2−フェニルプロピル基のようなアラルキル基、さらにこれらの炭化水素基の水素原子の一部がハロゲン原子やシアノ基等の他の原子または基で置換された、例えばクロロメチル基、3−クロロプロピル基、3,3,3−トリフルオロプロピル基のようなハロゲン化アルキル基;3−シアノプロピル基のようなシアノアルキル基、p−クロロフェニル基のようなハロゲン化アリール基等が例示される。これらのうち、合成が容易で、(A)成分が分子量の割に低い粘度を有し、硬化前の組成物に良好な押出し性を与えることと、硬化後の組成物に良好な物理的性質を与えることから、全有機基の85%以上がメチル基であることが好ましく、実質的にすべての有機基がメチル基であることがより好ましい。 In formula (3), a plurality of R 6 are each a substituted or unsubstituted monovalent hydrocarbon group which may be the same as or different from each other. R 6 includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group; a cycloalkyl group such as a cyclohexyl group; a vinyl group and an allyl group An alkenyl group such as a group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; an aralkyl group such as a benzyl group, a 2-phenylethyl group and a 2-phenylpropyl group; and a hydrogen atom of these hydrocarbon groups A halogenated alkyl group such as a chloromethyl group, a 3-chloropropyl group, or a 3,3,3-trifluoropropyl group, a part of which is substituted with another atom or group such as a halogen atom or a cyano group; Examples include cyanoalkyl groups such as 3-cyanopropyl group, halogenated aryl groups such as p-chlorophenyl group, and the like. Among these, the synthesis is easy, the component (A) has a low viscosity for the molecular weight, gives good extrudability to the composition before curing, and good physical properties to the composition after curing. Therefore, 85% or more of all organic groups are preferably methyl groups, and substantially all organic groups are more preferably methyl groups.

一方、特に、耐熱性、耐放射線性、耐寒性または透明性を付与する場合は、Rの一部として必要量のアリール基を、耐油性、耐溶剤性を付与する場合は、Rの一部として3,3,3−トリフルオロプロピル基や3−シアノプロピル基を、また塗装適性を有する表面を付与する場合は、Rの一部として長鎖アルキル基やアラルキル基を、それぞれメチル基と併用するなど、目的に応じて任意に選択することができる。 On the other hand, in particular, when imparting heat resistance, radiation resistance, cold resistance or transparency, a necessary amount of an aryl group as a part of R 6 , and when imparting oil resistance and solvent resistance, R 6 When a 3,3,3-trifluoropropyl group or a 3-cyanopropyl group is added as a part, or a surface having paintability is imparted, a long-chain alkyl group or an aralkyl group is a methyl group as a part of R 6. It can be arbitrarily selected depending on the purpose, for example, in combination with a group.

また、(A)成分であるポリオルガノシロキサンは、23℃における粘度が0.02〜100Pa・sであり、したがって、式(3)中のnは、(A)成分の23℃における粘度が前記範囲になる数(整数)である。(A)成分の23℃における粘度が0.02Pa・s未満では、硬化後のゴム状弾性体の伸びが不十分となり、逆に100Pa・sを超えると、吐出性等の作業性および流動特性が低下する。(A)成分の好ましい粘度は、硬化前および硬化後の組成物に要求される性質を調和させることから、0.1〜100Pa・sの範囲であり、より好ましくは0.5〜50Pa・sの範囲である。   In addition, the polyorganosiloxane as the component (A) has a viscosity at 23 ° C. of 0.02 to 100 Pa · s. Therefore, n in the formula (3) is the viscosity of the component (A) at 23 ° C. A number (integer) in the range. If the viscosity of the component (A) at 23 ° C. is less than 0.02 Pa · s, the rubber-like elastic body after curing is insufficiently stretched. Conversely, if the viscosity exceeds 100 Pa · s, workability such as discharge properties and flow characteristics are obtained. Decreases. The preferred viscosity of the component (A) is in the range of 0.1 to 100 Pa · s, more preferably 0.5 to 50 Pa · s, because the properties required for the composition before and after curing are harmonized. Range.

本発明の室温硬化性シリコーンゴム組成物の(B)成分であるポリオルガノシロキサンは、分子鎖の片末端のみが水酸基で封鎖されたもので、代表的には、下記一般式(4)で表される実質的に直鎖状のポリオルガノシロキサンである。

Figure 2009292914
The polyorganosiloxane that is the component (B) of the room temperature curable silicone rubber composition of the present invention is one in which only one end of the molecular chain is blocked with a hydroxyl group, and is typically represented by the following general formula (4). Substantially linear polyorganosiloxane.
Figure 2009292914

式(4)中、複数のRはそれぞれ互いに同一であっても異なっていてもよい置換または非置換の1価の炭化水素基であり、前述したRと同様のものが例示される。また、Rに関する前記記載は全てRにも適用される。 In formula (4), a plurality of R 7 are each a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and examples thereof are the same as those for R 6 described above. Also, the description of R 6 are all applied to R 7.

この(B)成分のポリオルガノシロキサンは、23℃における粘度が0.02〜100Pa・sであり、したがって、式(4)中のnは、(B)成分の23℃における粘度が前記範囲になる数(整数)である。(B)成分の23℃における粘度が0.02Pa・s未満では、硬化後のゴム状弾性体の伸びが不十分となり、逆に100Pa・sを超えると、吐出性等の作業性および流動特性が低下する。(B)成分の好ましい粘度は、硬化前および硬化後の組成物に要求される性質を調和させることから、0.1〜100Pa・sの範囲であり、より好ましくは0.5〜50Pa・sの範囲である。   The (B) component polyorganosiloxane has a viscosity at 23 ° C. of 0.02 to 100 Pa · s. Therefore, n in the formula (4) indicates that the viscosity of the (B) component at 23 ° C. is within the above range. It is a number (integer). When the viscosity of the component (B) at 23 ° C. is less than 0.02 Pa · s, the rubber-like elastic body after curing is insufficiently stretched. Conversely, when the viscosity exceeds 100 Pa · s, workability such as discharge properties and flow characteristics are obtained. Decreases. The preferred viscosity of the component (B) is in the range of 0.1 to 100 Pa · s, more preferably 0.5 to 50 Pa · s, because the properties required for the composition before and after curing are harmonized. Range.

上記(A)成分と(B)成分の混合比は、質量比で10:90〜90:10、好ましくは20:80〜80:20、より好ましくは30:70〜70:30である。(B)成分の量が前記範囲より少ないと接着性を向上させることができず、また、前記範囲より多いと硬化後の機械的強度が弱くなる。   The mixing ratio of the component (A) and the component (B) is 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30 in terms of mass ratio. When the amount of the component (B) is less than the above range, the adhesiveness cannot be improved, and when it is more than the above range, the mechanical strength after curing becomes weak.

本発明の室温硬化性シリコーンゴム組成物の(C)成分は、上記(A)および(B)成分の架橋剤として作用する成分であり、一般式:
Si(OR4−a …(1)
で示されるシラン化合物の部分加水分解縮合物である。
The component (C) of the room temperature curable silicone rubber composition of the present invention is a component that acts as a crosslinking agent for the components (A) and (B), and has the general formula:
R 1 a Si (OR 2 ) 4-a (1)
It is a partial hydrolysis-condensation product of the silane compound shown by these.

式(1)中、RおよびRは互いに同一であっても異なっていてもよい置換または非置換の1価の炭化水素基であり、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基のようなアルキル基;シクロヘキシル基のようなシクロアルキル基;ビニル基、アリル基のようなアルケニル基;フェニル基、トリル基、キシリル基のようなアリール基;ベンジル基、2−フェニルエチル基、2−フェニルプロピル基のようなアラルキル基、さらにこれらの炭化水素基の水素原子の一部がハロゲン原子等の他の原子または基で置換された、例えばクロロメチル基、3−クロロプロピル基、3,3,3−トリフルオロプロピル基のようなハロゲン化アルキル基;3−シアノプロピル基のようなシアノアルキル基等の置換炭化水素基が例示される。また、aは平均値として0≦a≦0.2の数であり、好ましくは0≦a≦0.1の数である。 In the formula (1), R 1 and R 2 are substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different from each other, and are methyl group, ethyl group, propyl group, butyl group, pentyl Group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group; cycloalkyl group such as cyclohexyl group; alkenyl group such as vinyl group, allyl group; phenyl group, tolyl group, xylyl group, etc. An aryl group; an aralkyl group such as a benzyl group, a 2-phenylethyl group, and a 2-phenylpropyl group, and a part of hydrogen atoms of these hydrocarbon groups is substituted with another atom or group such as a halogen atom, For example, a halogenated alkyl group such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group; Substituted hydrocarbon groups such as Noarukiru groups. Further, a is an average value of 0 ≦ a ≦ 0.2, and preferably 0 ≦ a ≦ 0.1.

この(C)成分の部分加水分解縮合物は、1分子中のSi数が3〜20であることが好ましく、4〜15であるとより好ましい。Si数が3未満では、十分な硬化性が得られず、また、20を超えると、硬化性や硬化後の機械的特性が低下する。   In the partially hydrolyzed condensate of component (C), the number of Si in one molecule is preferably 3-20, and more preferably 4-15. When the number of Si is less than 3, sufficient curability cannot be obtained, and when it exceeds 20, curability and mechanical properties after curing are deteriorated.

(C)成分のシラン化合物の部分加水分解縮合物は、1種を単独で使用してもよく、2種以上を混合して使用してもよい。   (C) The partial hydrolysis-condensation product of the silane compound of a component may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(C)成分の配合量は、(A)および(B)成分の合計量100質量部に対して0.1〜10質量部、好ましくは0.5〜5質量部である。0.1質量部未満では、架橋が十分に行われず、硬度の低い硬化物しか得られないばかりでなく、架橋剤を配合した組成物の保存安定性が不良となる。逆に、10質量部を超えると、硬化の際の収縮率が大きくなり、硬化後の弾性等の物性が低下する。   (C) The compounding quantity of a component is 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A) and (B) component, Preferably it is 0.5-5 mass parts. If the amount is less than 0.1 part by mass, crosslinking is not sufficiently performed and not only a cured product having low hardness is obtained, but also the storage stability of the composition containing the crosslinking agent becomes poor. On the contrary, if it exceeds 10 parts by mass, the shrinkage rate at the time of curing is increased, and physical properties such as elasticity after curing are lowered.

本発明の室温硬化性シリコーンゴム組成物の(D)成分は、上記(A)および(B)成分と上記(C)成分との反応を促進する硬化触媒として作用する成分であり、一般式:
(RO)Si−R−NH−R …(2)
で示されるアミン官能シラン化合物である。
The component (D) of the room temperature curable silicone rubber composition of the present invention is a component that acts as a curing catalyst for promoting the reaction between the components (A) and (B) and the component (C).
(R 3 O) 3 Si- R 4 -NH-R 5 ... (2)
Is an amine functional silane compound.

式(2)中、Rは互いに同一であっても異なっていてもよい置換または非置換の1価の炭化水素基であり、前記した(C)成分のRおよびRと同様の基が例示される。また、Rは置換もしくは非置換の2価の有機基であり、例えばメチレン基、エチレン基、プロピレン基、テトラメチレン基、ヘキサメチレン基、メチルエチレン基等のアルキレン基、フェニレン基、トリレン基等のアリーレン基、メチレンフェニレン基、メチレンフェニレン基等のアルキレンアリーレン基等が例示される。さらに、Rは、水素原子、メチル基、エチル基、プロピル基、ブチル基等のアルキル基等の置換もしくは非置換の1価の炭化水素基、またはアミノエチル基、N−アミノエチルアミノエチル基等のアミノアルキル基である。 In formula (2), R 3 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same as or different from each other, and is the same group as R 1 and R 2 in the component (C) described above. Is exemplified. R 4 is a substituted or unsubstituted divalent organic group such as an alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, a hexamethylene group, or a methylethylene group, a phenylene group, or a tolylene group. And an arylene group such as an arylene group, a methylenephenylene group, and a methylenephenylene group. Further, R 5 represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aminoethyl group or an N-aminoethylaminoethyl group. And the like.

(D)成分の具体例としては、下記に示すものが例示される。

Figure 2009292914
Specific examples of the component (D) include those shown below.
Figure 2009292914

(D)成分のアミン官能シラン化合物は、また、下記一般式(5)で表されるアクリル酸エステルまたはメタクリル酸エステルとの付加物であってもよい。

Figure 2009292914
(式中、RおよびRは前記と同様の基であり、Rは水素原子またはアルキル基であり、複数のRは同一であっても異なっていてもよい水素原子またはメチル基であり、R10は前記のRおよびRと同様の1価の炭化水素基またはこれらの基の水素原子の一部が‐Si(ORで置換された基であり、mは0、1または2である。) The amine functional silane compound of component (D) may also be an adduct with an acrylic ester or methacrylic ester represented by the following general formula (5).
Figure 2009292914
(Wherein R 3 and R 4 are the same groups as described above, R 8 is a hydrogen atom or an alkyl group, and a plurality of R 9 is a hydrogen atom or a methyl group which may be the same or different. R 10 is a monovalent hydrocarbon group similar to R 1 and R 2 described above, or a group in which a part of hydrogen atoms of these groups is substituted with —Si (OR 3 ) 3 , and m is 0 1 or 2.)

そのような化合物の例としては、下記に示すものが例示される。

Figure 2009292914
Examples of such compounds include those shown below.
Figure 2009292914

このような(D)成分のアミン官能シラン化合物は、1種を単独で使用してもよく、2種以上を混合して使用してもよい。(D)成分としては、なかでも、(CHO)SiCNHCNH、(CO)SiCNHが好ましい。 Such amine functional silane compounds as component (D) may be used alone or in combination of two or more. As the component (D), (CH 3 O) 3 SiC 3 H 6 NHC 2 H 4 NH 2 and (C 2 H 5 O) 3 SiC 3 H 6 NH 2 are particularly preferable.

この(D)成分の配合量は、(A)および(B)成分の合計量100質量部に対して0.1〜10質量部、好ましくは1〜5質量部である。0.1質量部未満では、十分な硬化速度が得られず、逆に10質量部を超えると、硬化後の物性が低下することがある。   The compounding amount of the component (D) is 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). If the amount is less than 0.1 parts by mass, a sufficient curing rate cannot be obtained. Conversely, if the amount exceeds 10 parts by mass, the physical properties after curing may decrease.

本発明の室温硬化性シリコーンゴム組成物は、接着性、硬化性等の観点から、(A)および(B)成分中の水酸基と(C)および(D)成分中のアルコキシ基とのモル比が、2〜50であることが好ましい。モル比は、より好ましくは3〜30であり、よりいっそう好ましくは5〜30である。   The room temperature curable silicone rubber composition of the present invention has a molar ratio of hydroxyl groups in the components (A) and (B) to alkoxy groups in the components (C) and (D) from the viewpoints of adhesiveness, curability and the like. Is preferably 2 to 50. The molar ratio is more preferably 3 to 30, and even more preferably 5 to 30.

本発明の室温硬化性シリコーンゴム組成物には、必要な物理的特性を付与するために、(E)成分として各種充填剤を、本発明の効果を阻害しない範囲で必要に応じて配合することができる。用いられる充填剤としては、煙霧質シリカ、シリカエアロゲル、沈澱シリカ、珪藻土、溶融シリカ、石英粉末、酸化鉄、酸化亜鉛、酸化チタン等の酸化物;これらの表面をトリメチルクロロシラン、ジメチルジクロロシラン、ヘキサメチルジシラザン、オクタメチルシクロテトラシロキサン等の疎水化剤で処理したもの;炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛等の炭酸塩;グラスウール、マイカ微粉末等の複合酸化物;カーボンブラック、銅粉、ニッケル粉等の導電性充填剤;ポリメチルシルセスキオキサン、ポリスチレン、ポリ塩化ビニル、ポリプロピレン等の合成樹脂粉末等が例示される。   In the room temperature curable silicone rubber composition of the present invention, various fillers as the component (E) are blended as necessary as long as the effects of the present invention are not impaired in order to impart necessary physical characteristics. Can do. Fillers used include fumed silica, silica aerogel, precipitated silica, diatomaceous earth, fused silica, quartz powder, oxides such as iron oxide, zinc oxide and titanium oxide; these surfaces are coated with trimethylchlorosilane, dimethyldichlorosilane, hexa Treated with hydrophobizing agents such as methyldisilazane and octamethylcyclotetrasiloxane; carbonates such as calcium carbonate, magnesium carbonate and zinc carbonate; complex oxides such as glass wool and mica fine powder; carbon black, copper powder and nickel Examples include conductive fillers such as powder; synthetic resin powders such as polymethylsilsesquioxane, polystyrene, polyvinyl chloride, and polypropylene.

これらの(E)成分の充填剤の配合量は、(A)および(B)成分の合計量100質量部に対して1〜200質量部であることが好ましく、5〜100質量部であることがより好ましい。1質量部未満では、添加により効果が十分に得られず、100質量部を超えると、吐出性等の作業性および流動特性が低下する。   It is preferable that the compounding quantity of the filler of these (E) components is 1-200 mass parts with respect to 100 mass parts of total amounts of (A) and (B) component, and is 5-100 mass parts. Is more preferable. If it is less than 1 part by mass, the effect cannot be sufficiently obtained by addition, and if it exceeds 100 parts by mass, workability such as dischargeability and flow characteristics are deteriorated.

また、本発明の室温硬化性シリコーンゴム組成物は、ベースポリマーとして上記(A)および(B)成分を併用したことにより、各種基材に対し優れた接着性を示すが、接着性をさらに高めるために従来より知られる各種接着性向上剤を配合することができる。用いられる接着性向上剤としては、1,3,5−トリス(3−トリメトキシシリルプロピル)イソシアヌレート等のイソシアヌル環含有ケイ素化合物、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン等のエポキシ基含有シラン等が例示される。   In addition, the room temperature curable silicone rubber composition of the present invention exhibits excellent adhesion to various substrates by using the components (A) and (B) in combination as a base polymer, but further increases the adhesion. Therefore, conventionally known various adhesion improvers can be blended. Examples of the adhesion improver used include isocyanuric ring-containing silicon compounds such as 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl. An epoxy group-containing silane such as methyldimethoxysilane is exemplified.

これらの接着性向上剤の配合量は、(A)および(B)成分の合計量100質量部に対して0.1〜10質量部であることが好ましく、0.5〜5質量部であることがより好ましい。   The compounding amount of these adhesion improvers is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B). It is more preferable.

本発明の室温硬化性シリコーンゴム組成物には、さらにこの種の組成物に一般に配合されている各種添加剤を、本発明の効果を阻害しない範囲で、必要に応じて配合することができる。そのような添加剤としては、顔料、染料、チクソトロピー性付与剤、押出作業性を改良するための粘度調整剤、紫外線吸収剤、防かび剤、耐熱性向上剤等が挙げられる。   In the room temperature curable silicone rubber composition of the present invention, various additives generally blended in this type of composition can be blended as necessary within a range not inhibiting the effects of the present invention. Examples of such additives include pigments, dyes, thixotropic agents, viscosity modifiers for improving extrusion workability, ultraviolet absorbers, fungicides, and heat resistance improvers.

但し、本発明の室温硬化性シリコーンゴム組成物においては、金属原子を含有する硬化触媒、すなわち、上記(A)および(B)成分の架橋反応に基づく硬化を促進する硬化触媒として機能する金属原子含有有機化合物を実質的に配合しないことが好ましい。このような硬化触媒の具体例としては、鉄オクトエート、マンガンオクトエート、亜鉛オクトエート、スズナフテート、スズカプリレート、スズオレ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、ジブチルスズジオレート、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サイド、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;テトラエトキシチタン、テトラプロポキシチタン、テトラブトキシチタン、1,3−プロポキシチタンビス(エチルアセチルアセテート)のようなアルコキシチタン類;アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、ジイソプロポキシアルミニウムエチルアセトアセテート、トリエトキシアルミニウムのような有機アルミニウム;ジルコニウムテトラアセチルアセトナート、テトライソプロポキシジルコニウム、テトラブトキシジルコニウム、トリブトキシジルコニウムアセチルアセトネート、トリブトキシジルコニウムステアレートのような有機ジルコニウム化合物等が挙げられる。   However, in the room temperature curable silicone rubber composition of the present invention, a metal atom that functions as a curing catalyst containing a metal atom, that is, a curing catalyst that promotes curing based on the crosslinking reaction of the components (A) and (B). It is preferable that substantially no organic compound is contained. Specific examples of such curing catalysts include carboxylic acid metal salts such as iron octoate, manganese octoate, zinc octoate, tin naphthate, tin caprylate, tin oleate; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diiolate Organic tin compounds such as dirate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dioctyltin dilaurate; tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, 1,3-propoxytitaniumbis Alkoxy titaniums such as (ethyl acetyl acetate); aluminum tris acetyl acetonate, aluminum tris ethyl acetoacetate Organoaluminum compounds such as diisopropoxyaluminum ethyl acetoacetate, triethoxyaluminum; organozirconium compounds such as zirconium tetraacetylacetonate, tetraisopropoxyzirconium, tetrabutoxyzirconium, tributoxyzirconium acetylacetonate, tributoxyzirconium stearate Etc.

本発明の室温硬化性シリコーンゴム組成物は、上記(A)〜(D)成分および必要に応じて配合される各種成分を、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曝すことによってはじめて硬化する、いわゆる1包装型室温硬化性組成物として使用することができる。また、本発明の組成物を、例えば架橋剤と硬化触媒を分けた組成物として調製し、適宜2〜3個の別々の容器に分けて保存し、使用時にこれらを混合する、いわゆる多包装型室温硬化性組成物として使用することもできる。本発明の室温硬化性ポリオルガノシロキサン組成物は、上記(A)、(B)、(E)成分および必要に応じて配合される各種成分を含む組成物(主剤成分)と、上記(C)、(D)成分および必要に応じて配合される各種成分を含む組成物(硬化剤成分)がそれぞれ調製され、湿気を遮断した状態で別々に保存し、使用時にこれらを混合する2成分型が好ましい。   The room temperature curable silicone rubber composition of the present invention is obtained by mixing the above components (A) to (D) and various components blended as necessary in a state where moisture is blocked. The obtained composition can be used as a so-called one-packaging room temperature curable composition that is stored as it is in a closed container and cured only by exposure to moisture in the air during use. In addition, the composition of the present invention is prepared as a composition in which, for example, a crosslinking agent and a curing catalyst are separated, and is stored in two or three separate containers as appropriate, and these are mixed at the time of use. It can also be used as a room temperature curable composition. The room temperature curable polyorganosiloxane composition of the present invention is a composition (main component) containing the above components (A), (B), (E) and various components blended as necessary, and the above (C). , (D) and a component (curing agent component) containing various components to be blended as necessary are prepared, stored separately in a state where moisture is blocked, and a two-component type in which these are mixed at the time of use. preferable.

本発明により得られる室温硬化性シリコーンゴム組成物は、湿気の存在しない密封条件下では安定であり、空気中の水分と接触することにより、室温で硬化してゴム状弾性体を生じる。特に本発明によれば、従来の金属原子含有有機化合物を触媒として用いた室温硬化性シリコーンゴム組成物と比較して、硬化速度が速く、深部硬化性に優れる上に、各種基材に対し優れた接着性を示す室温硬化性シリコーンゴム組成物を得ることができる。したがって、本発明の組成物は、自動車部品、電気・電子機器用の弾性接着剤、コーティング材、ポッティング材、FIPGシール材等として有用であり、また、現場形成ガスケット、建築用シーリング材等としても有用である。   The room temperature curable silicone rubber composition obtained according to the present invention is stable under sealed conditions where moisture is not present, and is cured at room temperature upon contact with moisture in the air to produce a rubber-like elastic body. In particular, according to the present invention, compared with a room temperature curable silicone rubber composition using a conventional metal atom-containing organic compound as a catalyst, the curing speed is fast and the deep part curability is excellent, and it is excellent for various substrates. A room temperature curable silicone rubber composition exhibiting excellent adhesion can be obtained. Accordingly, the composition of the present invention is useful as an elastic adhesive for automobile parts, electrical / electronic devices, coating materials, potting materials, FIPG sealing materials, etc., and also as a field forming gasket, a building sealing material, etc. Useful.

以下、本発明を実施例によりさらに具体的に説明するが、これらの実施例は本発明の範囲を何ら限定するものではない。なお、実施例中、「部」とあるのはいずれも「質量部」を表し、粘度等の物性値は全て23℃、相対湿度50%での値を示す。   EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the scope of the present invention. In Examples, “part” means “part by mass”, and all physical properties such as viscosity are values at 23 ° C. and relative humidity 50%.

実施例1
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン(粘度:0.5Pa・s、水酸基量0.1mmol/g)40部、分子鎖両末端がそれぞれ水酸基および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(粘度:0.5Pa・s、水酸基量0.05mmol/g)60部および粉砕石英20部からなる主剤成分と、式:Si(OCで示されるシラン化合物の部分加水分解縮合物(Si数5)3部および式:HNCNHCSi(OCHで示されるアミン官能シラン化合物1部からなる硬化剤成分を均一に混合し、ポリオルガノシロキサン組成物を得た。
Example 1
40 parts of polydimethylsiloxane blocked with hydroxyl groups at both ends of the molecular chain (viscosity: 0.5 Pa · s, hydroxyl content 0.1 mmol / g), polydimethylsiloxane blocked at both ends of the molecular chain with hydroxyl groups and trimethylsilyl groups, respectively (Viscosity: 0.5 Pa · s, hydroxyl group content 0.05 mmol / g) Partial hydrolysis-condensation of a main component composed of 60 parts and 20 parts of pulverized quartz and a silane compound represented by the formula: Si (OC 2 H 5 ) 4 A polyorganosiloxane is uniformly mixed with a hardener component consisting of 3 parts of a product (5 Si number) and 1 part of an amine functional silane compound represented by the formula: H 2 NC 2 H 4 NHC 3 H 6 Si (OCH 3 ) 3 A composition was obtained.

実施例2
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン(粘度:0.5Pa・s、水酸基量0.1mmol/g)30部、分子鎖両末端がそれぞれ水酸基および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(粘度:0.5Pa・s、水酸基量0.05mmol/g)70部および粉砕石英20部からなる主剤成分と、式:Si(OCで示されるシラン化合物の部分加水分解縮合物(Si数7)3部および式:HNCNHCSi(OCHで示されるアミン官能シラン化合物1部からなる硬化剤成分を均一に混合し、ポリオルガノシロキサン組成物を得た。
Example 2
30 parts of polydimethylsiloxane blocked with hydroxyl groups at both ends of the molecular chain (viscosity: 0.5 Pa · s, hydroxyl content 0.1 mmol / g), polydimethylsiloxane blocked at both ends of the molecular chain with hydroxyl groups and trimethylsilyl groups, respectively (Viscosity: 0.5 Pa · s, hydroxyl group amount 0.05 mmol / g) Partial hydrolysis condensation of a main component composed of 70 parts and 20 parts of pulverized quartz and a silane compound represented by the formula: Si (OC 2 H 5 ) 4 A polyorganosiloxane was uniformly mixed with a hardener component consisting of 3 parts of a product (Si number 7) and 1 part of an amine functional silane compound represented by the formula: H 2 NC 2 H 4 NHC 3 H 6 Si (OCH 3 ) 3 A composition was obtained.

実施例3
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン(粘度:0.5Pa・s、水酸基量0.1mmol/g)50部、分子鎖両末端がそれぞれ水酸基および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(粘度:0.5Pa・s、水酸基量0.05mmol/g)50部および粉砕石英20部からなる主剤成分と、式:Si(OCで示されるシラン化合物の部分加水分解縮合物(Si数5)3部、式:HNCNHCSi(OCHで示されるアミン官能シラン化合物1部および1,3,5−トリス(3−トリメトキシシリルプロピル)イソシアヌレート0.5部からなる硬化剤成分を均一に混合し、ポリオルガノシロキサン組成物を得た。
Example 3
50 parts of polydimethylsiloxane blocked with hydroxyl groups at both ends of molecular chain (viscosity: 0.5 Pa · s, hydroxyl content 0.1 mmol / g), polydimethylsiloxane with both ends of molecular chain blocked with hydroxyl and trimethylsilyl groups, respectively (Viscosity: 0.5 Pa · s, hydroxyl group amount 0.05 mmol / g) Partial hydrolysis-condensation of a main component composed of 50 parts and 20 parts of pulverized quartz and a silane compound represented by the formula: Si (OC 2 H 5 ) 4 3 parts of product (Si number 5), 1 part of amine functional silane compound represented by the formula: H 2 NC 2 H 4 NHC 3 H 6 Si (OCH 3 ) 3 and 1,3,5-tris (3-trimethoxysilyl) A curing agent component comprising 0.5 part of propyl) isocyanurate was uniformly mixed to obtain a polyorganosiloxane composition.

実施例4
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン(粘度:0.5Pa・s、水酸基量0.1mmol/g)40部、分子鎖両末端がそれぞれ水酸基および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(粘度:0.5Pa・s、水酸基量0.05mmol/g)60部および粉砕石英20部からなる主剤成分と、式:Si(OCで示されるシラン化合物の部分加水分解縮合物(Si数5)3部および式:HNCSi(OCHで示されるアミン官能シラン化合物1部からなる硬化剤成分を均一に混合し、ポリオルガノシロキサン組成物を得た。
Example 4
40 parts of polydimethylsiloxane blocked with hydroxyl groups at both ends of the molecular chain (viscosity: 0.5 Pa · s, hydroxyl content 0.1 mmol / g), polydimethylsiloxane blocked at both ends of the molecular chain with hydroxyl groups and trimethylsilyl groups, respectively (Viscosity: 0.5 Pa · s, hydroxyl group content 0.05 mmol / g) Partial hydrolysis-condensation of a main component composed of 60 parts and 20 parts of pulverized quartz and a silane compound represented by the formula: Si (OC 2 H 5 ) 4 A polyorganosiloxane composition is obtained by uniformly mixing 3 parts of a product (5 Si) and 1 part of an amine functional silane compound represented by the formula: H 2 NC 3 H 6 Si (OCH 3 ) 3. It was.

実施例5
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン(粘度:0.5Pa・s、水酸基量0.1mmol/g)30部、分子鎖両末端がそれぞれ水酸基および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(粘度:0.5Pa・s、水酸基量0.1mmol/g)70部および粉砕石英20部からなる主剤成分と、式:Si(OCで示されるシラン化合物の部分加水分解縮合物(Si数7)3部および式:HNCSi(OCHで示されるアミン官能シラン化合物1部からなる硬化剤成分を均一に混合し、ポリオルガノシロキサン組成物を得た。
Example 5
30 parts of polydimethylsiloxane blocked with hydroxyl groups at both ends of the molecular chain (viscosity: 0.5 Pa · s, hydroxyl content 0.1 mmol / g), polydimethylsiloxane blocked at both ends of the molecular chain with hydroxyl groups and trimethylsilyl groups, respectively (Viscosity: 0.5 Pa · s, hydroxyl group content 0.1 mmol / g) Partial hydrolysis condensation of a main component composed of 70 parts and 20 parts of pulverized quartz and a silane compound represented by the formula: Si (OC 2 H 5 ) 4 A curing agent component consisting of 3 parts of a product (Si number 7) and 1 part of an amine functional silane compound represented by the formula: H 2 NC 3 H 6 Si (OCH 3 ) 3 is uniformly mixed to obtain a polyorganosiloxane composition. It was.

比較例1
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン(粘度:0.5Pa・s、水酸基量0.1mmol/g)100部および粉砕石英20部からなる主剤成分と、式:Si(OCで示されるシラン化合物の部分加水分解縮合物(Si数5)3部および式:HNCNHCSi(OCHで示されるアミン官能シラン化合物1部からなる硬化剤成分を均一に混合し、ポリオルガノシロキサン組成物を得た。
Comparative Example 1
A main component composed of 100 parts of polydimethylsiloxane (viscosity: 0.5 Pa · s, hydroxyl group content 0.1 mmol / g) and 20 parts of pulverized quartz, both ends of which are blocked with hydroxyl groups, and a formula: Si (OC 2 H 5 ) From 3 parts of a partially hydrolyzed condensate (Si number 5) of a silane compound represented by 4 and 1 part of an amine functional silane compound represented by the formula: H 2 NC 2 H 4 NHC 3 H 6 Si (OCH 3 ) 3 The resulting curing agent component was uniformly mixed to obtain a polyorganosiloxane composition.

比較例2
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン(粘度:0.5Pa・s、水酸基量0.1mmol/g)100部および粉砕石英20部からなる主剤成分と、式:Si(OCで示されるシラン化合物3部および式:HNCNHCSi(OCHで示されるアミン官能シラン化合物1部からなる硬化剤成分を均一に混合し、ポリオルガノシロキサン組成物を得た。
Comparative Example 2
A main component composed of 100 parts of polydimethylsiloxane (viscosity: 0.5 Pa · s, hydroxyl group content 0.1 mmol / g) and 20 parts of pulverized quartz, both ends of which are blocked with hydroxyl groups, and a formula: Si (OC 2 H 5) 4 in indicated by a silane compound 3 parts of formula: H 2 NC 2 H 4 NHC 3 H 6 Si (OCH 3) a curing agent component were uniformly mixed consisting of amine-functional silane compound, 1 part represented by 3, poly An organosiloxane composition was obtained.

比較例3
分子鎖両末端が水酸基で封鎖されたポリジメチルシロキサン(粘度:0.5Pa・s、水酸基量0.1mmol/g)100部および粉砕石英20部からなる主剤成分と、式:Si(OCで示されるシラン化合物の部分加水分解縮合物(Si数5)3部、式:HNCNHCSi(OCHで示されるアミン官能シラン化合物1部および1,3,5−トリス(3−トリメトキシシリルプロピル)イソシアヌレート0.5部からなる硬化剤成分を均一に混合し、ポリオルガノシロキサン組成物を得た。
Comparative Example 3
A main component composed of 100 parts of polydimethylsiloxane (viscosity: 0.5 Pa · s, hydroxyl group content 0.1 mmol / g) and 20 parts of pulverized quartz, both ends of which are blocked with hydroxyl groups, and a formula: Si (OC 2 H 5 ) 3 parts of a partially hydrolyzed condensate (Si number 5) of the silane compound represented by 4, 1 part of an amine functional silane compound represented by the formula: H 2 NC 2 H 4 NHC 3 H 6 Si (OCH 3 ) 3 and A curing agent component consisting of 0.5 part of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate was uniformly mixed to obtain a polyorganosiloxane composition.

上記各実施例および各比較例で調製したポリオルガノシロキサン組成物について、下記に示す方法で各種特性を評価した。結果を表1に示す。
[硬化性]
23℃、50%RHの雰囲気下、組成物を金型に厚さ6mmに流し込み、2時間、4時間および8時間後の性状(硬化状態)を調べた。
[接着性]
各種基材(PBT(ポリブチレンテレフタレート)、PPE(ポリフェニレンエーテル)、PPS(ポリフェニレンサルファイド))に、室温硬化性シリコーンゴム組成物を、長さ50mm、幅10mmで、厚さ1mmになるように塗布し、23℃、50%RHの雰囲気中に3日間放置し硬化させて試験体を作製し、これらの試験体について、凝集破壊率を測定した。
Various characteristics of the polyorganosiloxane compositions prepared in the above Examples and Comparative Examples were evaluated by the methods described below. The results are shown in Table 1.
[Curing property]
Under an atmosphere of 23 ° C. and 50% RH, the composition was poured into a mold to a thickness of 6 mm, and properties (cured state) after 2 hours, 4 hours and 8 hours were examined.
[Adhesiveness]
A room temperature curable silicone rubber composition is applied to various base materials (PBT (polybutylene terephthalate), PPE (polyphenylene ether), PPS (polyphenylene sulfide)) so as to have a length of 50 mm, a width of 10 mm, and a thickness of 1 mm. Then, the specimens were allowed to stand for 3 days in an atmosphere of 23 ° C. and 50% RH to be cured, and the cohesive failure rate of these specimens was measured.

Figure 2009292914
Figure 2009292914

表1から明らかなように、実施例1〜5で調製されたポリオルガノシロキサン組成物は、比較例1〜3で得られたポリオルガノシロキサン組成物に比べ、硬化性および接着性に優れており、なかでも接着性が大幅に改善されている。   As is clear from Table 1, the polyorganosiloxane compositions prepared in Examples 1 to 5 are superior in curability and adhesiveness compared to the polyorganosiloxane compositions obtained in Comparative Examples 1 to 3. In particular, the adhesion is greatly improved.

Claims (7)

(A)分子鎖両末端が水酸基で封鎖された23℃における粘度が0.02〜100Pa・sであるポリオルガノシロキサン 10〜90質量部、
(B)分子鎖片末端のみが水酸基で封鎖された23℃における粘度が0.02〜100Pa・sであるポリオルガノシロキサン 90〜10質量部、
(C)一般式:
Si(OR4−a …(1)
(式中、RおよびRは同一であっても異なっていてもよい置換もしくは非置換の1価の炭化水素基であり、aは平均値として0≦a≦0.2の数である。)で示されるシラン化合物の部分加水分解縮合物 0.1〜10質量部、および
(D)一般式):
(RO)Si−R−NH−R …(2)
(式中、Rは互いに同一であっても異なっていてもよい置換もしくは非置換の1価の炭化水素基であり、Rは置換もしくは非置換の2価の有機基であり、Rは水素原子、置換もしくは非置換の1価の炭化水素基またはアミノアルキル基である。)で示されるアミン官能シラン化合物 0.1〜10質量部、
を含有することを特徴とする室温硬化性シリコーンゴム組成物。
(A) 10 to 90 parts by mass of a polyorganosiloxane having a viscosity at 23 ° C. of 0.02 to 100 Pa · s at which both ends of the molecular chain are blocked with hydroxyl groups,
(B) 90-10 parts by mass of a polyorganosiloxane having a viscosity at 23 ° C. of 0.02 to 100 Pa · s in which only one molecular chain end is blocked with a hydroxyl group,
(C) General formula:
R 1 a Si (OR 2 ) 4-a (1)
(In the formula, R 1 and R 2 are substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different, and a is an average value of 0 ≦ a ≦ 0.2. .) 0.1 to 10 parts by mass of a partially hydrolyzed condensate of a silane compound represented by ()) and (D) a general formula):
(R 3 O) 3 Si- R 4 -NH-R 5 ... (2)
(Wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other, R 4 is a substituted or unsubstituted divalent organic group, and R 5 Is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group or aminoalkyl group.) 0.1 to 10 parts by mass of an amine functional silane compound represented by
A room temperature curable silicone rubber composition comprising:
前記(A)および(B)成分中の水酸基と前記(C)および(D)成分中のアルコキシ基とのモル比が、2〜50であることを特徴とする請求項1記載の室温硬化性シリコーンゴム組成物。   2. The room temperature curing property according to claim 1, wherein the molar ratio of the hydroxyl groups in the components (A) and (B) to the alkoxy groups in the components (C) and (D) is 2-50. Silicone rubber composition. 前記(A)成分の23℃における粘度が0.1〜100Pa・sであることを特徴とする請求項1または2記載の室温硬化性シリコーンゴム組成物。   The room temperature curable silicone rubber composition according to claim 1 or 2, wherein the viscosity at 23 ° C of the component (A) is 0.1 to 100 Pa · s. 前記(B)成分の23℃における粘度が0.1〜100Pa・sであることを特徴とする請求項1乃至3のいずれか1項記載の室温硬化性シリコーンゴム組成物。   The room temperature curable silicone rubber composition according to any one of claims 1 to 3, wherein the viscosity of the component (B) at 23 ° C is 0.1 to 100 Pa · s. 金属原子を含有する硬化触媒を実質的に含有しないことを特徴とする請求項1乃至4のいずれか1項記載の室温硬化性シリコーンゴム組成物。   The room temperature curable silicone rubber composition according to any one of claims 1 to 4, which is substantially free of a curing catalyst containing a metal atom. 前記(A)および(B)成分の合計量100質量部に対して、(E)充填剤1〜200質量部をさらに含有することを特徴とする請求項1乃至5のいずれか1項記載の室温硬化性シリコーンゴム組成物。   6. The filler according to claim 1, further comprising (E) 1 to 200 parts by mass of a filler with respect to 100 parts by mass of the total amount of the components (A) and (B). Room temperature curable silicone rubber composition. 少なくとも前記(A)および(B)成分を含み、前記(C)および(D)成分を含まない組成物と、少なくとも前記(C)および(D)成分を含み、前記(A)および(B)成分を含まない組成物からなる2成分型室温硬化性シリコーンゴム組成物であることを特徴とする請求項1乃至6のいずれか1項記載の室温硬化性シリコーンゴム組成物。   A composition containing at least the components (A) and (B) and not containing the components (C) and (D), and containing at least the components (C) and (D), and (A) and (B) The room temperature curable silicone rubber composition according to any one of claims 1 to 6, which is a two-component room temperature curable silicone rubber composition comprising a composition containing no components.
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