JP3970484B2 - Room temperature curable sealing material composition for automobiles - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は自動車用室温硬化性シール材組成物に関し、特に速硬化性、深部硬化性に優れ、未硬化時に加熱した際の気泡の発生が抑制された縮合硬化型の自動車用室温硬化性シール材組成物に関するものである。
【０００２】
【従来の技術】
縮合硬化型の室温速硬化性オルガノポリシロキサン組成物については、従来、ベースポリマーである両末端ヒドロキシオルガノポリシロキサンに対して架橋剤を極限まで減量して加水分解による架橋速度を向上させた１液タイプのもの、及びベースポリマーである両末端ヒドロキシオルガノポリシロキサンと架橋剤とを別梱包し使用時に混合する２液タイプのものが知られている。
【０００３】
【発明が解決しようとする課題】
しかし、１液タイプの前記組成物は、表面からの硬化速度は速いが、深部硬化にはどうしても一定の時間が必要である。２液タイプの前記組成物に於いては、深部硬化性には比較的優れているものの、２液混合する割合が１：１でないため取り扱いが複雑であり、また、自動混合機などに適合しにくいという欠点がある。更に、深部まで完全に硬化させるにはオルガノポリシロキサンの両末端ヒドロキシ量と架橋剤の添加量を厳密に規定するか、深部硬化剤として更に水を加えることが必要である。
【０００４】
一方、付加硬化型のオルガノポリシロキサン組成物に於いては、２液混合する割合が１：１であり作業性に優れるが、通常、硬化には加熱炉が必要である。また、付加毒の存在下で硬化触媒が被毒されるため、作業環境が限定されるという欠点があった。
【０００５】
そのため、特開平５−２７９５７０号では分子鎖両末端が加水分解性シリル基で封鎖されたジオルガノポリシロキサンに対し１分子中に少なくとも１個のＣ＝Ｏ基を有する有機化合物、及び１分子中に少なくとも１個のＮＨ2基を有する有機化合物を含有してなる組成物が提案されている。これはＣ＝Ｏ基とＮＨ2基によるケチミン生成反応から副生する水を利用して深部硬化性、速硬化性を改良したものであるが、深部硬化性、速硬化性には優れるものの、未硬化時に熱が加えられた場合、縮合反応生成物であるジアルキルケトオキシムが急速にガス化して硬化物中に気泡が発生し、シール性が大幅に低下し、特に自動車のオイルシール用途には問題があった。
【０００６】
本発明は、上記事情に鑑みなされたもので、速硬化性、深部硬化性に優れていると共に、未硬化状態での熱が加えられても気泡を生成することのない自動車用室温硬化性シール材組成物を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、上記成分（Ｃ）及び（Ｄ）のＣ＝Ｏ基とＮＨ2基との反応により生成する水により組成物の速硬化、深部硬化を促進しつつ、ベースポリマーとしてのジメチルポリシロキサン（成分（Ａ））の粘度を限定し、且つ架橋剤を一般式ＣＨ2＝ＣＨＳｉ（Ｏ−Ｎ＝ＣＲ1Ｒ2）3で示されるシラン化合物またはその部分加水分解物（式中、Ｒ1、Ｒ2は同一または異なってもよい炭素数１〜６の一価の炭化水素基）とし、その量を限定することにより、未硬化状態で加熱した場合の気泡の発生を抑えることができることを見出した。
【０００８】
従って、本発明は、下記の成分：
（Ａ）分子鎖両末端が水酸基で封鎖され、２５℃における粘度が３００００〜１０００００センチストークスであるジメチルポリシロキサン １００重量部；
（Ｂ）一般式：ＣＨ2＝ＣＨＳｉ（Ｏ−Ｎ＝ＣＲ1Ｒ2）3で示されるシラン化合物またはその部分加水分解物（式中Ｒ1、Ｒ2は同一または異なってもよい炭素数１〜６の一価の炭化水素基） ２〜１０重量部；
（Ｃ）ケトン化合物 上記成分（Ａ）１００重量部に対して０．００１〜１．０モルのカルボニル基が存在する量；
（Ｄ）一級アミノ基含有化合物 上記成分（Ａ）１００重量部に対して０．００１〜１．０モルの一級アミノ基が存在する量；及び、
（Ｅ）炭酸亜鉛、炭酸カルシウム、酸化亜鉛から選ばれる少なくとも一種の塩基性充填剤 ５〜１５０重量部、
を含有することを特徴とする自動車用室温硬化性シール材組成物を提供する。
前記成分（Ａ）〜（Ｅ）に加えて、成分（Ａ）１００重量部に対して０．０１〜２０重量部の硬化触媒を含有するのが好ましい。
【０００９】
本発明の自動車用室温硬化性シール材組成物の好ましい実施態様においては、前記成分のうち成分（Ａ），（Ｃ）を含有し、且つ成分（Ｄ）を含有しない第一液と、成分（Ａ），（Ｄ）を含有し、且つ成分（Ｃ）を含有しない第二液とに分離されており、成分（Ｂ），（Ｅ）は第一液と第二液の両方またはどちらか一方に含有されており、第一液と第二液を混合して使用される。
【００１０】
また、前記第一液と第二液は、それらを体積比で略１：１で混合した時にその混合物が請求項１記載の割合で成分（Ａ）〜（Ｅ）を含有するように調製されているのが好ましい。
【００１１】
また、前記第一液が前記成分（Ａ），（Ｂ），（Ｃ），（Ｅ）よりなり、第二液が前記成分（Ａ），（Ｂ），（Ｄ），（Ｅ）よりなるのが好ましい。
さらに、前記成分（Ａ）〜（Ｅ）に加えて、成分（Ｆ）煙霧質シリカを含有するのが好ましい。
【００１２】
【発明の実施の形態】
以下、本発明についてさらに詳しく説明する。
成分（Ａ）のジメチルポリシロキサンはベースポリマーであり、分子鎖両末端が水酸基で封鎖されていることが必要である。この水酸基と架橋剤である成分（Ｂ）が反応することにより、ゴム弾性体の硬化物を形成するからである。成分（Ａ）のジメチルポリシロキサンは、下記式で示され、２５℃における粘度が３００００〜１０００００センチストークスである。
【００１３】
【化１】
（式中、ｎは２５℃における粘度が３００００〜１０００００センチストークスとなる整数である）
粘度が３００００センチストークス未満であると、未硬化状態で熱を加えた際に発泡を抑制することが困難となり、１０００００センチストークスを超えると、発泡を抑制することが困難となる他、作業性が著しく低下する。これらは、１種を単独で用いても粘度の異なる２種以上を併用してもよい。
【００１５】
成分（Ｂ）は、一般式：ＣＨ2＝ＣＨＳｉ（Ｏ−Ｎ＝ＣＲ1Ｒ2）3で示されるビニルトリスジアルキルケトオキシムシランまたはその部分加水分解物であり、架橋剤として作用するものである。ここで、Ｒ1，Ｒ2は同一または異なってもよい炭素数１〜６の一価炭化水素基であり、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基等のアルキル基や、Ｒ1とＲ2が結合して環を形成したシクロペンチル基、シクロヘキシル基等のシクロアルキル基等が例示される。成分（Ｂ）の具体例としては、ビニルトリ（ブタノキシム）シラン、ビニルトリ（プロパノキシム）シラン、ビニルトリ（ペンタノキシム）シラン、ビニルトリ（イソペンタノキシム）シラン、ビニルトリ（シクロペンタノキシム）シラン、ビニルトリ（シクロヘキサノキシム）シラン等が例示される。これらは、１種を単独で用いても２種以上を併用して用いてもよい。
【００１６】
成分（Ｂ）の配合量は、成分（Ａ）１００重量部に対して、２〜１０重量部、好ましくは３〜１０重量部である。２重量部未満では弾性および機械的強度に優れた硬化物が得られず、１０重量部を超えると硬化物が硬く、脆いものになり、さらに縮合生成ガス量が多くなるため未硬化状態で熱が加えられた時に発泡を抑制することが困難となる。
【００１７】
成分（Ｃ）は、ケトン化合物であり、反応性のＣ＝Ｏ基を有するものであれば特に制限されないが、アセトン、メチルエチルケトン、メチルイソブチルケトン等の脂肪族ケトン、シクロペンタノン、シクロヘキサノン、２−メチルシクロペンタノン等の環状ケトン等が例示される。これらは、１種単独で用いても２種以上併用して用いてもよい。
【００１８】
成分（Ｃ）の配合量は、上記成分（Ａ）１００重量部に対して０．００１〜１．０モル、好ましくは０．０１〜０．１モルのカルボニル基が存在する量である。存在するカルボニル基が０．００１モル未満の場合、成分（Ｄ）の１級アミノ基含有化合物と反応して生成する水の量が少なく、十分な深部硬化性が発現せず、１．０モルを超えると得られる硬化物の特性が不十分となるからである。
【００１９】
成分（Ｄ）は、１級アミノ基含有化合物であり成分（Ｃ）のケトン化合物と反応して水を生成し、組成物の深部硬化性を著しく向上させるものである。（Ｄ）成分としては１級アミノ基を有するものであれば特に制限されないが、具体的にはメチルアミン、エチルアミン、ブチルアミン等脂肪族アミン類、エチレンジアミン、トリエチレンテトラミン等の脂肪族ポリアミン、アニリン、シクロペンチルアミン、シクロヘキシルアミン、２−エチルシクロヘキシルアミン等の環状アミン類、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン等の１級アミノ基含有シランカップリング剤、１級アミノ基含有ポリシロキサン等の１級アミノ基含有有機珪素化合物等が例示される。これらの化合物は１種または２種以上併用して用いてもよい。
【００２０】
成分（Ｄ）の配合量は、上記成分（Ａ）１００重量部に対して０．００１〜１．０モル、好ましくは０．０１〜０．１モルの一級アミノ基が存在する量である。存在する一級アミノ基が０．００１モル未満の場合、十分な深部硬化性が発現せず、１．０モルを超えると得られる硬化物の特性が不十分となるからである。
【００２１】
成分（Ｅ）は、炭酸亜鉛、炭酸カルシウム、酸化亜鉛から選ばれる少なくとも１種の塩基性充填剤である。成分（Ｅ）は、自動車エンジンオイル中に含まれる酸性成分の中和剤として作用しシール剤の耐油性を著しく向上させるものである。
【００２２】
成分（Ｅ）の配合量は、成分（Ａ）１００重量部に対して５〜１５０重量部、好ましくは１０〜１００重量部である。５重量部未満では十分な中和効果が得られないためシール剤の耐油性が充分でなく、１５０重量部を超えると、得られる弾性体硬化物の硬さが高くなり、伸びが低下し、シール性が不十分となる。
【００２３】
本発明の組成物には、必要に応じ（Ａ）〜（Ｅ）の必須成分の他種々の配合剤を添加することができる。特に、硬化触媒を添加することが好ましく、硬化触媒としては公知のものを使用することができ、有機錫エステル、有機錫キレート錯体等の有機錫系触媒、有機チタン酸エステル、有機チタンキレート錯体等の有機チタン系触媒等が例示され、有機錫系触媒が好ましい。硬化触媒の添加量は、成分（Ａ）１００重量部に対して０．０１〜２０重量部、特に０．０２〜１０重量部である。
【００２４】
また、組成物の粘度を調整する場合や強度を向上させる必要がある場合には、（Ｆ）煙霧質シリカを配合することが好ましい。煙霧質シリカとしては表面未処理の煙霧質シリカ、表面ジメチルシリル基処理、トリメチルシリル基処理等の表面疎水化処理煙霧質シリカが好適に使用され、その配合量は、成分（Ａ）１００重量部に対し、０〜２０重量部、好ましくは１〜１０重量部である。２０重量部を超えると組成物の粘度が高くなりすぎ、組成物の作業性が悪くなる。
【００２５】
その他沈降性シリカ、石英粉末、炭素粉末、タルクおよびベントナイトなどの補強性充填剤、顔料、染料などの着色剤、γーグリシドキシプロピルトリメトキシシラン、メタクリリキシプロピルトリメトキシシランなどの接着性向上剤、トリメチルシロキシ単位およびＳｉＯ2単位よりなる網状ポリシロキサンなどの液状補強剤などを必要に応じて添加してもよい。
【００２６】
本発明の組成物は上記した成分（Ａ）〜（Ｅ）を好ましくは乾燥（無水）雰囲気中で均一に混合することにより一液型の室温速硬化性組成物として得られる。また、保存性を確保するために、成分（Ａ），（Ｃ）と成分（Ａ），（Ｄ）を別々に混合しておき、使用時にこれを混合する方式とすることも可能である。この場合成分（Ｂ），（Ｅ）はどちらに混合されてもよい。例えば、第一液は前記成分（Ａ），（Ｂ），（Ｃ），（Ｅ）よりなり、第二液は、前記成分（Ａ），（Ｂ），（Ｄ），（Ｅ）よりなる。
【００２７】
前記第一液と第二液を、それらを体積比で略１：１で混合した時にその混合物が成分（Ａ）〜（Ｅ）を上記の割合で含有するように調製することにより、作業性、取扱性を向上することができる。
【００２８】
本発明の組成物は、空気中の水分の存在により硬化すると共に、その深部で成分（Ｃ）及び（Ｄ）により水が生成するため、表面からの硬化のみならず、その内部からも硬化を生じるため、速硬化性及び深部硬化性が向上する。また、ベースポリマーである成分（Ａ）の粘度を及び硬化剤としての成分（Ｂ）の構造及び添加量を特定することにより、未硬化状態で熱が加えられた時の気泡の発生を抑えることができると共に、得られた硬化物は優れた機械的性質を有するため、優れた性質のシール材を提供することができる。また、充填剤の種類及び量を規定することにより、耐油性等の性質を向上することができる。従って、本発明の組成物は、特に自動車用のオイルシール材として好適である。
【００２９】
【実施例】
以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記実施例に制限されるものではない。なお、粘度は２５℃における測定値である。
【００３０】
比較例１
分子鎖両末端が水酸基で封鎖された、粘度が２００００ｃｓのジメチルポリシロキサン １００重量部
炭酸亜鉛粉末 ５０重量部
煙霧質シリカ ５重量部
ビニルトリスブタノキシムシラン ７重量部
ジブチルスズオクトエート ０．１重量部
アセトン ２重量部
ブチルアミン ４重量部
を無水の状態で混合して硬化性シリコーンゴム組成物を調製した。
【００３１】
この組成物を用いてオイルパンの接着シールを行い、３０分後に１２０℃で３０分間加熱した後、室温で放置冷却し、２４時間後にオイルパンを剥がして硬化物の外観を確認したところ気泡の発生が見られた。
【００３２】
【表１】
また、表１に示す処方で比較例１と同様の方法により、比較例２〜６、実施例１〜４の組成物を調製し、オイルパンの接着シールを行い、３０分後に１２０℃で３０分間加熱した後、室温放置冷却し、２４時間後にオイルパンを剥がして硬化物の外観を確認したところ、表に示すように、実施例１〜４においては、気泡の発生は見られなかったが、比較例１、３、４、５においては気泡が発生し、比較例２及び６は調製不能であった。
【００３４】
実施例５
下記の組成を有する第一液用組成物：
分子鎖両末端が水酸基で封鎖された、粘度が３００００ｃｓのジメチルポリシロキサン ５０重量部；
炭酸カルシウム ５０重量部；
煙霧質シリカ ２．５重量部；
ビニルトリスブタノキシムシラン ７重量部；
ジブチルスズオクトエート ０．１重量部；及び、
シクロヘキシルアミン ３重量部と、
下記の組成を有する第二液用組成物：
分子鎖両末端が水酸基で封鎖された、粘度が３００００ｃｓのジメチルポリシロキサン ５０重量部；
炭酸カルシウム ５０重量部；
煙霧質シリカ ２．５重量部；及び、
シクロヘキサノン ３重量部；
を各々無水の状態で混合して、第一液及び第二液を調製した。これらを密閉容器に入れ、４０℃の雰囲気下で７日間保存した。その後、２液を同量計量して混合した。これを実施例１と同様の条件下で硬化させ、同様の方法により硬化物の外観を確認したところ、硬化状態は良好であり、気泡は発生しなかった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a room temperature curable sealing material composition for automobiles, and more particularly, a condensation curable room temperature curable sealing material for automobiles, which is excellent in rapid curing and deep part curing, and suppresses the generation of bubbles when heated when uncured. It relates to a composition.
[0002]
[Prior art]
Condensation-curing room-temperature fast-curing organopolysiloxane compositions are conventionally one solution in which the crosslinking agent is reduced to the utmost to improve the crosslinking rate by hydrolysis with respect to the both-end hydroxyorganopolysiloxane as the base polymer. There are known a type and a two-component type in which both terminal hydroxyorganopolysiloxane as a base polymer and a crosslinking agent are separately packaged and mixed at the time of use.
[0003]
[Problems to be solved by the invention]
However, although the one-component type composition has a high curing rate from the surface, a certain amount of time is inevitably required for deep curing. The two-component type composition is relatively excellent in deep-part curability, but is difficult to handle because the mixing ratio of the two components is not 1: 1, and is suitable for automatic mixers. There is a drawback that it is difficult. Further, in order to completely cure to the deep part, it is necessary to strictly define the amount of hydroxy at both ends of the organopolysiloxane and the addition amount of the crosslinking agent, or to add water as a deep part curing agent.
[0004]
On the other hand, in the addition-curing type organopolysiloxane composition, the ratio of mixing two liquids is 1: 1 and excellent in workability, but usually a heating furnace is required for curing. Further, since the curing catalyst is poisoned in the presence of an additional poison, there is a disadvantage that the working environment is limited.
[0005]
Therefore, in JP-A-5-279570, an organic compound having at least one C═O group in one molecule with respect to a diorganopolysiloxane having both molecular chain ends blocked with hydrolyzable silyl groups, and one molecule A composition comprising an organic compound having at least one NH 2 group has been proposed. This is an improvement of the deep curability and fast curability using water by-produced from the ketimine formation reaction by C═O group and NH 2 group, but it is excellent in deep curability and fast curability, When heat is applied when uncured, the dialkylketoxime, which is a condensation reaction product, rapidly gasifies and bubbles are generated in the cured product, resulting in a significant decrease in sealing performance, especially for automotive oil seal applications. There was a problem.
[0006]
The present invention has been made in view of the above circumstances, and is excellent in rapid curing and deep curing, and does not generate bubbles even when heat is applied in an uncured state. An object is to provide a material composition.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventor has rapidly cured the composition with water generated by the reaction of the C═O group and the NH 2 group of the components (C) and (D). Limiting the viscosity of dimethylpolysiloxane (component (A)) as the base polymer while promoting deep curing, and the cross-linking agent is represented by the general formula CH 2 ═CHSi (O—N═CR 1 R 2 ) 3 Silane compound or a partial hydrolyzate thereof (wherein R 1 and R 2 are the same or different monovalent hydrocarbon groups having 1 to 6 carbon atoms) and the amount thereof is uncured. It was found that the generation of bubbles when heated in a state can be suppressed.
[0008]
Accordingly, the present invention comprises the following components:
(A) 100 parts by weight of dimethylpolysiloxane having both ends of the molecular chain blocked with hydroxyl groups and a viscosity at 25 ° C. of 30,000 to 100,000 centistokes;
(B) Silane compound represented by the general formula: CH 2 ═CHSi (O—N═CR 1 R 2 ) 3 or a partial hydrolyzate thereof (wherein R 1 and R 2 may be the same or different and have 1 carbon atom) To 6 monovalent hydrocarbon groups) 2 to 10 parts by weight;
(C) Ketone compound An amount in which 0.001 to 1.0 mol of a carbonyl group is present per 100 parts by weight of the component (A);
(D) Primary amino group-containing compound An amount in which 0.001 to 1.0 mole of primary amino group is present with respect to 100 parts by weight of component (A); and
(E) 5 to 150 parts by weight of at least one basic filler selected from zinc carbonate, calcium carbonate, and zinc oxide;
A room temperature curable sealing material composition for automobiles is provided.
In addition to the components (A) to (E), it is preferable to contain 0.01 to 20 parts by weight of a curing catalyst with respect to 100 parts by weight of the component (A).
[0009]
In a preferred embodiment of the room temperature curable sealing material composition for automobiles of the present invention, a first liquid containing the components (A) and (C) and not containing the component (D) among the components, A) and (D) are separated into a second liquid that does not contain component (C), and components (B) and (E) are either or both of the first liquid and the second liquid. The first liquid and the second liquid are mixed and used.
[0010]
Further, the first liquid and the second liquid are prepared so that the mixture contains the components (A) to (E) in the ratio according to claim 1 when they are mixed at a volume ratio of approximately 1: 1. It is preferable.
[0011]
The first liquid is composed of the components (A), (B), (C), and (E), and the second liquid is composed of the components (A), (B), (D), and (E). Is preferred.
Furthermore, in addition to the said components (A)-(E), it is preferable to contain a component (F) fumed silica.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The dimethylpolysiloxane of component (A) is a base polymer, and it is necessary that both ends of the molecular chain are blocked with hydroxyl groups. This is because a cured product of a rubber elastic body is formed by the reaction between the hydroxyl group and the component (B) as a crosslinking agent. The dimethylpolysiloxane of the component (A) is represented by the following formula and has a viscosity at 25 ° C. of 30,000 to 100,000 centistokes.
[0013]
[Chemical 1]
(In the formula, n is an integer having a viscosity at 25 ° C. of 30,000 to 100,000 centistokes)
When the viscosity is less than 30000 centistokes, it is difficult to suppress foaming when heat is applied in an uncured state, and when it exceeds 100000 centistokes, it is difficult to suppress foaming and workability is improved. It drops significantly. These may be used alone or in combination of two or more having different viscosities.
[0015]
Component (B) is a vinyl trisdialkylketoxime silane represented by the general formula: CH 2 ═CHSi (O—N═CR 1 R 2 ) 3 or a partial hydrolyzate thereof, and acts as a crosslinking agent. . Here, R 1 and R 2 are monovalent hydrocarbon groups having 1 to 6 carbon atoms which may be the same or different, and specifically include methyl group, ethyl group, propyl group, butyl group, pentyl group and the like. Examples include an alkyl group and a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group in which R 1 and R 2 are bonded to form a ring. Specific examples of component (B) include vinyltri (butanoxime) silane, vinyltri (propanoxime) silane, vinyltri (pentanoxime) silane, vinyltri (isopentanoxime) silane, vinyltri (cyclopentanoxime) silane, vinyltri (cyclohexano). Xime) silane and the like are exemplified. These may be used alone or in combination of two or more.
[0016]
The compounding quantity of a component (B) is 2-10 weight part with respect to 100 weight part of a component (A), Preferably it is 3-10 weight part. If the amount is less than 2 parts by weight, a cured product excellent in elasticity and mechanical strength cannot be obtained. If the amount exceeds 10 parts by weight, the cured product becomes hard and brittle, and further, the amount of condensation product gas increases, so that heat is generated in an uncured state. When is added, it becomes difficult to suppress foaming.
[0017]
Component (C) is a ketone compound and is not particularly limited as long as it has a reactive C═O group, but aliphatic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2- Examples include cyclic ketones such as methylcyclopentanone. These may be used alone or in combination of two or more.
[0018]
The amount of component (C) is 0.001 to 1.0 mol, preferably 0.01 to 0.1 mol, of carbonyl group per 100 parts by weight of component (A). When the carbonyl group present is less than 0.001 mol, the amount of water produced by reacting with the primary amino group-containing compound of component (D) is small, sufficient deep curability does not develop, and 1.0 mol It is because the characteristic of the cured | curing material obtained will become inadequate when exceeding.
[0019]
Component (D) is a primary amino group-containing compound, which reacts with the ketone compound of component (C) to produce water, thereby significantly improving the deep curability of the composition. The component (D) is not particularly limited as long as it has a primary amino group. Specifically, aliphatic amines such as methylamine, ethylamine and butylamine, aliphatic polyamines such as ethylenediamine and triethylenetetramine, aniline, 1 such as cyclic amines such as cyclopentylamine, cyclohexylamine and 2-ethylcyclohexylamine, primary amino group-containing silane coupling agents such as aminopropyltrimethoxysilane and aminopropyltriethoxysilane, and primary amino group-containing polysiloxanes Illustrative examples include secondary amino group-containing organosilicon compounds. These compounds may be used alone or in combination of two or more.
[0020]
The amount of component (D) is 0.001 to 1.0 mol, preferably 0.01 to 0.1 mol of primary amino group present per 100 parts by weight of component (A). This is because if the primary amino group present is less than 0.001 mol, sufficient deep-part curability will not be exhibited, and if it exceeds 1.0 mol, the properties of the resulting cured product will be insufficient.
[0021]
Component (E) is at least one basic filler selected from zinc carbonate, calcium carbonate, and zinc oxide. Component (E) acts as a neutralizing agent for acidic components contained in automobile engine oil, and remarkably improves the oil resistance of the sealing agent.
[0022]
The compounding quantity of a component (E) is 5-150 weight part with respect to 100 weight part of a component (A), Preferably it is 10-100 weight part. If less than 5 parts by weight, a sufficient neutralizing effect cannot be obtained, so the oil resistance of the sealant is not sufficient, and if it exceeds 150 parts by weight, the hardness of the resulting elastic cured product is increased, and the elongation is reduced. The sealing performance is insufficient.
[0023]
In addition to the essential components (A) to (E), various compounding agents can be added to the composition of the present invention as necessary. In particular, a curing catalyst is preferably added, and a known catalyst can be used as the curing catalyst, such as an organic tin catalyst such as an organic tin ester or an organic tin chelate complex, an organic titanic acid ester or an organic titanium chelate complex. And an organic tin-based catalyst is preferable. The addition amount of the curing catalyst is 0.01 to 20 parts by weight, particularly 0.02 to 10 parts by weight with respect to 100 parts by weight of the component (A).
[0024]
Moreover, when adjusting the viscosity of a composition or when it is necessary to improve intensity | strength, it is preferable to mix | blend (F) fumed silica. As the fumed silica, surface-untreated fumed silica, surface hydrophobized fumed silica such as surface dimethylsilyl group treatment, trimethylsilyl group treatment, etc. are preferably used, and the blending amount is 100 parts by weight of component (A). On the other hand, it is 0 to 20 parts by weight, preferably 1 to 10 parts by weight. When it exceeds 20 parts by weight, the viscosity of the composition becomes too high, and the workability of the composition becomes worse.
[0025]
Other adhesive properties such as precipitating silica, quartz powder, carbon powder, reinforcing fillers such as talc and bentonite, colorants such as pigments and dyes, γ-glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane An agent, a liquid reinforcing agent such as a reticulated polysiloxane composed of trimethylsiloxy units and SiO 2 units may be added as necessary.
[0026]
The composition of the present invention can be obtained as a one-component room temperature rapid-curable composition by uniformly mixing the components (A) to (E) described above, preferably in a dry (anhydrous) atmosphere. In order to ensure storage stability, it is possible to mix components (A), (C) and components (A), (D) separately, and mix them at the time of use. In this case, components (B) and (E) may be mixed in either. For example, the first liquid is composed of the components (A), (B), (C), (E), and the second liquid is composed of the components (A), (B), (D), (E). .
[0027]
By preparing the first liquid and the second liquid so that the mixture contains the components (A) to (E) in the above ratio when they are mixed at a volume ratio of approximately 1: 1, the workability is improved. , Handling can be improved.
[0028]
The composition of the present invention is cured by the presence of moisture in the air, and water is generated by the components (C) and (D) in the deep part thereof, so that not only curing from the surface but also curing from the inside. As a result, fast curability and deep part curability are improved. In addition, by specifying the viscosity of the component (A) as the base polymer and the structure and amount of the component (B) as a curing agent, it is possible to suppress the generation of bubbles when heat is applied in an uncured state. In addition, since the obtained cured product has excellent mechanical properties, a sealing material having excellent properties can be provided. In addition, by defining the type and amount of the filler, properties such as oil resistance can be improved. Therefore, the composition of the present invention is particularly suitable as an oil seal material for automobiles.
[0029]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. The viscosity is a measured value at 25 ° C.
[0030]
Comparative Example 1
Dimethylpolysiloxane having a viscosity of 20000 cs with both ends of the molecular chain blocked with hydroxyl groups 100 parts by weight Zinc carbonate powder 50 parts by weight Fumed silica 5 parts by weight Vinyl trisbutanoxime silane 7 parts by weight Dibutyltin octoate 0.1 parts by weight A curable silicone rubber composition was prepared by mixing 2 parts by weight of acetone and 4 parts by weight of butylamine in an anhydrous state.
[0031]
Using this composition, an oil pan was adhered and sealed, and after 30 minutes, heated at 120 ° C. for 30 minutes, allowed to cool at room temperature, and after 24 hours, the oil pan was peeled off and the appearance of the cured product was confirmed. Occurrence was seen.
[0032]
[Table 1]
Moreover, the composition of Comparative Examples 2-6 and Examples 1-4 was prepared by the same method as Comparative Example 1 with the formulation shown in Table 1, and the oil pan was adhesively sealed, and 30 minutes later at 120 ° C. After heating for a minute, the mixture was allowed to cool at room temperature, and after 24 hours, the oil pan was peeled off to confirm the appearance of the cured product. As shown in the table, no bubbles were observed in Examples 1-4. In Comparative Examples 1, 3, 4, and 5, bubbles were generated, and Comparative Examples 2 and 6 could not be prepared.
[0034]
Example 5
First liquid composition having the following composition:
50 parts by weight of dimethylpolysiloxane having a viscosity of 30000 cs and having both molecular chain ends blocked with hydroxyl groups;
50 parts by weight of calcium carbonate;
2.5 parts by weight of fumed silica;
7 parts by weight of vinyl trisbutanoxime silane;
0.1 part by weight of dibutyltin octoate; and
3 parts by weight of cyclohexylamine,
Second liquid composition having the following composition:
50 parts by weight of dimethylpolysiloxane having a viscosity of 30000 cs and having both molecular chain ends blocked with hydroxyl groups;
50 parts by weight of calcium carbonate;
2.5 parts by weight of fumed silica; and
3 parts by weight of cyclohexanone;
Were mixed in an anhydrous state to prepare a first liquid and a second liquid. These were put in a sealed container and stored for 7 days in an atmosphere of 40 ° C. Thereafter, the two liquids were weighed and mixed in the same amount. When this was cured under the same conditions as in Example 1 and the appearance of the cured product was confirmed by the same method, the cured state was good and no bubbles were generated.
Claims (6)
（Ｂ）一般式：ＣＨ２＝ＣＨＳｉ（Ｏ−Ｎ＝ＣＲ１Ｒ２）３で示されるシラン化合物、又はその部分加水分解物（式中Ｒ１、Ｒ２は同一、又は異なってもよい炭素原子数１〜６の一価の炭化水素基である。）２〜１０重量部；
（Ｃ）ケトン化合物が、上記成分（Ａ）１００重量部に対して０．００１〜１．０モルのカルボニル基が存在する量；
（Ｄ）一級アミノ基含有化合物が、上記成分（Ａ）１００重量部に対して０．００１〜１．０モルの一級アミノ基が存在する量；及び、
（Ｅ）炭酸亜鉛、炭酸カルシウム、及び酸化亜鉛から選ばれる少なくとも一種の塩基性充填剤５〜１５０重量部、を含有する自動車用室温硬化性シール材組成物であって、
使用前は、成分（Ａ）、及び（Ｃ）を含有し、かつ成分（Ｄ）を含有しない第一液と、成分（Ａ）、及び（Ｄ）を含有し、かつ成分（Ｃ）を含有しない第二液とに分離されており、成分（Ｂ）、及び（Ｅ）は第一液と第二液の両方、又はどちらか一方に含有されている、前記室温硬化性シール材組成物。(A) 100 parts by weight of dimethylpolysiloxane having both ends of the molecular chain blocked with hydroxyl groups and a viscosity at 25 ° C. of 30,000 to 100,000 centistokes;
(B) A silane compound represented by the general formula: CH 2 ═CHSi (O—N═CR 1 R 2 ) 3 or a partial hydrolyzate thereof (wherein R 1 and R 2 may be the same or different carbons) A monovalent hydrocarbon group having 1 to 6 atoms) 2 to 10 parts by weight;
(C) An amount of the ketone compound in which 0.001 to 1.0 mol of a carbonyl group is present with respect to 100 parts by weight of the component (A);
(D) the primary amino group-containing compound is present in an amount of 0.001 to 1.0 mole of primary amino group based on 100 parts by weight of the component (A); and
(E) A room temperature curable sealing material composition for automobiles containing 5 to 150 parts by weight of at least one basic filler selected from zinc carbonate, calcium carbonate, and zinc oxide,
Before use, the first liquid containing components (A) and (C) and not containing component (D), containing components (A) and (D), and containing component (C) The room temperature-curable sealing material composition, wherein the composition is separated into a second liquid that is not contained, and the components (B) and (E) are contained in both or one of the first liquid and the second liquid.
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| DE102005005634A1 (en) * | 2005-02-08 | 2006-08-24 | Wacker Chemie Ag | Crosslinkable compositions based on organosilicon compounds |
| US7993754B2 (en) * | 2007-03-27 | 2011-08-09 | Momentive Performance Materials Inc. | Architectural unit possessing rapid deep-section cure silicone rubber component |
| JP5902574B2 (en) * | 2012-07-18 | 2016-04-13 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition and automotive oil seal using the composition |
| WO2023234084A1 (en) * | 2022-05-30 | 2023-12-07 | 信越化学工業株式会社 | Two-pack type room temperature curable organopolysiloxane composition and various articles containing said composition |
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| DE3212008A1 (en) * | 1982-03-31 | 1983-10-06 | Wacker Chemie Gmbh | EXCLUDING WATER STORAGE CROSS-LINKABLE DIMENSIONS WHEN THE WATER ACCESSES AT ROOM TEMPERATURE |
| GB8401016D0 (en) * | 1984-01-14 | 1984-02-15 | Hagen Perennatorwerk | Organopolysiloxane compositions |
| JP2531516B2 (en) * | 1987-02-13 | 1996-09-04 | 株式会社 スリ−ボンド | Sealing material |
| US5112885A (en) * | 1989-04-28 | 1992-05-12 | Shin-Etsu Chemical Co., Ltd. | Room temperature vulcanizable silicon rubber composition |
| JP2534135B2 (en) * | 1989-07-18 | 1996-09-11 | 株式会社スリーボンド | Method for forming seal material mainly composed of organopolysiloxane |
| JPH0449177A (en) * | 1990-06-14 | 1992-02-18 | Yamatogawa Shiko Kk | Paper pipe manufacturing device |
| JP2811134B2 (en) * | 1992-03-30 | 1998-10-15 | 信越化学工業株式会社 | Room temperature fast-curing organopolysiloxane composition and method for curing the same |
| JP2707029B2 (en) * | 1992-08-04 | 1998-01-28 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition |
| JPH0733984A (en) * | 1993-07-16 | 1995-02-03 | Shin Etsu Chem Co Ltd | Room temperature curing organopolysiloxane composition |
| JP2841155B2 (en) * | 1993-09-13 | 1998-12-24 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition |
| JP2966257B2 (en) * | 1993-10-25 | 1999-10-25 | 信越化学工業株式会社 | Room temperature fast-curing organopolysiloxane composition |
| JP2891625B2 (en) * | 1993-12-27 | 1999-05-17 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition |
| JPH07258550A (en) * | 1994-03-18 | 1995-10-09 | Three Bond Co Ltd | Room-temperature-curable organosiloxane composition |
| JPH0873745A (en) * | 1994-08-31 | 1996-03-19 | Three Bond Co Ltd | Liquid silicone composition for gasket |
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