JP2003073553A - Room temperature-curable organopolysiloxane composition - Google Patents
Room temperature-curable organopolysiloxane compositionInfo
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- JP2003073553A JP2003073553A JP2001262794A JP2001262794A JP2003073553A JP 2003073553 A JP2003073553 A JP 2003073553A JP 2001262794 A JP2001262794 A JP 2001262794A JP 2001262794 A JP2001262794 A JP 2001262794A JP 2003073553 A JP2003073553 A JP 2003073553A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】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し、特に自動車エンジン周
りに使用される、耐油性、耐ＬＬＣ性に優れた硬化物を
与える室温硬化性オルガノポリシロキサン組成物に関す
る。TECHNICAL FIELD The present invention relates to a room-temperature-curable organopolysiloxane composition, and particularly to a room-temperature-curable organopolysiloxane composition which is used around an automobile engine and gives a cured product excellent in oil resistance and LLC resistance. Regarding things.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
空気中の水分と接触することにより室温でエラストマー
状に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、とりわけアルコ
ールを放出して硬化するタイプのものは不快臭がないこ
と、金属類を腐食しないことが特徴となって、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。かかるタイプの代表例としては、
特公昭３９−２７６４３号公報に記載のものが挙げら
れ、これ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
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。更に、特公平７−３９５４７号公
報にはシルエチレン基を含む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。2. Description of the Related Art Conventionally, the problems to be solved by the invention
Various types of room-temperature-curable organopolysiloxane compositions that cure into an elastomer at room temperature when contacted with moisture in the air are known, but those of the type that cures by releasing alcohol release an unpleasant odor. It is characterized by its lack of corrosion and corrosion of metals, and is favorably used for sealing, bonding and coating of electric and electronic devices. A typical example of this type is
Japanese Patent Publication No. 39-27643 discloses a composition comprising a hydroxyl-terminated organopolysiloxane, an alkoxysilane and an organic titanium compound. Further, JP-A-55-43119 discloses a composition comprising an alkoxysilyl endblocked organopolysiloxane, an alkoxysilane and an alkoxytitanium. Further, JP-B-7-39547 discloses a composition comprising an alkoxysilyl end-capped organopolysiloxane containing a silethylene group, an alkoxysilane and an alkoxytitanium.
【０００３】しかしながら、これら組成物は自動車エン
ジン周りに使用される場合に必要となる、耐油性、耐Ｌ
ＬＣ性が不十分であった。However, these compositions require oil resistance and L resistance, which are required when they are used around automobile engines.
The LC property was insufficient.
【０００４】本発明は、前記した欠点を解消し、自動車
エンジン周りという過酷な条件下でも殆ど物性値の変化
の少ないエラストマー状硬化物を与え、密封条件下での
保存安定性にも優れる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を目的とするものである。The present invention solves the above-mentioned drawbacks, provides an elastomeric cured product with little change in physical properties even under severe conditions such as around an automobile engine, and has room temperature curing which is excellent in storage stability under sealed conditions. The purpose of the present invention is to provide a functional organopolysiloxane composition.
【０００５】[0005]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記目的を達成するため鋭意検討を行った結
果、基材となる成分として酸素原子又は二価炭化水素基
を介してオルガノオキシ基結合のケイ素原子を１分子中
に少なくとも２個有するオルガノポリシロキサンを使用
し、これに充填剤としてカーボンブラック、特定のオル
ガノオキシシラン又はその部分加水分解縮合物、好まし
くは更に架橋密度向上剤としてＲ4 3ＳｉＯ1/2単位及び
ＳｉＯ4 /2単位から本質的になるオルガノシロキサン、
触媒としてチタンキレート化合物を使用することによっ
て、従来の１液型脱アルコールタイプの室温硬化性オル
ガノポリシロキサン組成物に比べ、密封条件下での保存
安定性にも優れ、自動車エンジン周りという過酷な条件
下でも殆ど物性値の変化の少ないエラストマー状硬化物
を与える室温硬化性オルガノポリシロキサン組成物が得
られることを知見し、本発明をなすに至った。Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that a component serving as a base material is mediated by an oxygen atom or a divalent hydrocarbon group. An organopolysiloxane having at least two silicon atoms bonded with an organooxy group in one molecule is used, and carbon black as a filler, a specific organooxysilane or a partially hydrolyzed condensate thereof, preferably a crosslink density is further improved. organosiloxane consisting essentially of R 4 3 SiO 1/2 units and SiO 4/2 units as agents,
By using a titanium chelate compound as a catalyst, the storage stability under sealed conditions is superior to the conventional one-pack dealcohol type room temperature curable organopolysiloxane composition, and the severe conditions around the automobile engine The inventors have found that a room-temperature-curable organopolysiloxane composition that gives an elastomer-like cured product with little change in the physical properties even under the above conditions can be obtained, and completed the present invention.
【０００６】即ち、本発明は、（Ａ）下記一般式（１）That is, the present invention provides (A) the following general formula (1)
【化２】
（式中、Ｒ1は一価炭化水素基、Ｒ2は一価炭化水素基又
はアルコキシ基置換一価炭化水素基、Ｒ3は非置換又は
置換の一価炭化水素基、Ｙは酸素原子又は二価炭化水素
基、ｂは１〜３の整数、好適には２又は３、ｎは２５℃
における粘度が２０〜１，０００，０００センチポイズ
となるような整数である。）で表されるオルガノオキシ
シリル基を末端に有する直鎖状オルガノポリシロキサン
１００重量部
（Ｂ）カーボンブラック０．５〜５０重量部
（Ｃ）下記一般式（２）
Ｒ1 aＳｉ（ＯＲ2）4-a （２）
（式中、Ｒ1は一価炭化水素基、Ｒ2は一価炭化水素基又
はアルコキシ基置換一価炭化水素基、ａは０又は１であ
る。）で表されるオルガノオキシシラン又はその部分加
水分解縮合物０．５〜１５重量部、好ましくは、（Ｄ）
Ｒ4 3ＳｉＯ1/2単位（式中、Ｒ4は炭素数１〜６の非置換
又は置換の一価炭化水素基を表す。）及びＳｉＯ4/2単
位から本質的になり、ＳｉＯ4/2単位に対するＲ4 3Ｓｉ
Ｏ1/2単位のモル比が０．６〜１．２であって、ヒドロ
キシシリル基の含有量が０．７重量％未満であるオルガ
ノシロキサン１〜５０重量部、（Ｅ）チタンキレート触
媒０．１〜１０重量部を含有してなる室温硬化性オルガ
ノポリシロキサン組成物を提供する。[Chemical 2] (In the formula, R 1 is a monovalent hydrocarbon group, R 2 is a monovalent hydrocarbon group or an alkoxy group-substituted monovalent hydrocarbon group, R 3 is an unsubstituted or substituted monovalent hydrocarbon group, Y is an oxygen atom or Divalent hydrocarbon group, b is an integer of 1 to 3, preferably 2 or 3, n is 25 ° C.
Is an integer such that the viscosity at 20 to 1,000,000 centipoise. ) Organooxysilyl group-terminated linear organopolysiloxane 100 parts by weight (B) Carbon black 0.5 to 50 parts by weight (C) The following general formula (2) R 1 a Si (OR 2 ) 4-a (2) (in the formula, R 1 is a monovalent hydrocarbon group, R 2 is a monovalent hydrocarbon group or an alkoxy group-substituted monovalent hydrocarbon group, and a is 0 or 1). Organooxysilane or its partial hydrolysis-condensation product 0.5 to 15 parts by weight, preferably (D)
R 4 3 SiO 1/2 units (wherein, R 4 is. Represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) consisting essentially of and SiO 4/2 units, SiO 4 / R 4 3 Si for 2 units
1 to 50 parts by weight of organosiloxane having a molar ratio of O 1/2 units of 0.6 to 1.2 and a hydroxysilyl group content of less than 0.7% by weight, (E) titanium chelate catalyst 0 A room temperature curable organopolysiloxane composition containing 1 to 10 parts by weight is provided.
【０００７】以下、本発明につき更に詳しく説明する。
本発明に使用される（Ａ）成分は、本組成物の基材とな
るものであり、改善された保存安定性を得るために、酸
素原子又は二価炭化水素基を介して、オルガノオキシ
基、特にアルコキシ基結合のケイ素原子を１分子中に少
なくとも２個有するオルガノポリシロキサンであること
が必要であり、（Ａ）成分は、下記一般式（１）The present invention will be described in more detail below.
The component (A) used in the present invention serves as a base material of the present composition, and in order to obtain improved storage stability, an organooxy group is introduced through an oxygen atom or a divalent hydrocarbon group. In particular, it is necessary that the organopolysiloxane has at least two silicon atoms bonded with an alkoxy group in one molecule, and the component (A) is represented by the following general formula (1):
【化３】
（式中、Ｒ1は一価炭化水素基、Ｒ2は一価炭化水素基又
はアルコキシ基置換一価炭化水素基、Ｒ3は非置換又は
置換の一価炭化水素基、Ｙは酸素原子又は二価炭化水素
基、ｂは１〜３の整数、好適には２又は３、ｎは２５℃
における粘度が２０〜１，０００，０００センチポイズ
となるような整数である。）で表されるオルガノオキシ
シリル基を末端に有する直鎖状オルガノポリシロキサン
である。なお、直鎖状を基本構造とし、これに分岐状、
環状又は網状部分を有するオルガノポリシロキサンも使
用できる。[Chemical 3] (In the formula, R 1 is a monovalent hydrocarbon group, R 2 is a monovalent hydrocarbon group or an alkoxy group-substituted monovalent hydrocarbon group, R 3 is an unsubstituted or substituted monovalent hydrocarbon group, Y is an oxygen atom or Divalent hydrocarbon group, b is an integer of 1 to 3, preferably 2 or 3, n is 25 ° C.
Is an integer such that the viscosity at 20 to 1,000,000 centipoise. ) Is a linear organopolysiloxane having an organooxysilyl group at the end. In addition, a linear structure is used as a basic structure, and a branched structure is
Organopolysiloxanes having a cyclic or network portion can also be used.
【０００８】一般式（１）で表されるオルガノポリシロ
キサンにおいて、Ｒ1及びＲ3の一価炭化水素基の例とし
ては、炭素数１〜１２、特に１〜１０のものが好まし
く、メチル、エチル、プロピル、ブチル、ヘキシル、オ
クチル、デシル、オクタデシルなどのアルキル基、シク
ロペンチル、シクロヘキシルなどのシクロアルキル基、
ビニル、アリルなどのアルケニル基、フェニル、トリ
ル、ナフチルなどのアリール基、ベンジル、フェニルエ
チル、フェニルプロピルなどのアラルキル基や、これら
の基の水素原子の一部又は全部がハロゲン原子やシアノ
基で置換された基などが挙げられ、ハロゲン化炭化水素
基としてはクロロメチル、トリフロロメチル、クロロプ
ロピル、３，３，３−トリフロロプロピル、クロロフェ
ニル、ジブロモフェニル、テトラクロロフェニル、ジフ
ルオロフェニル基などが例示され、シアノアルキル基と
してはβ−シアノエチル、γ−シアノプロピル、β−シ
アノプロピル基などが例示される。また、Ｒ2としては
炭素数１〜８のものが好ましく、メチル、エチル、プロ
ピル、ブチル、ヘキシル、オクチルなどのアルキル基、
メトキシエチル、エトキシエチル、メトキシプロピル、
メトキシブチルなどのアルコキシ基置換アルキル基が例
示される。Ｒ1、Ｒ2、Ｒ3はそれぞれ炭素原子数１〜３
を持つことが好適であり、更に好適にはメチル基であ
る。Ｙは酸素原子又は二価炭化水素基であり、二価炭化
水素基としては−ＣＨ2ＣＨ2−、−ＣＨ2ＣＨ2ＣＨ
2−、−ＣＨ2Ｃ（ＣＨ3）Ｈ−などの炭素数１〜８、特
に２〜６のアルキレン基が例示され、−ＣＨ2ＣＨ2−が
好ましい。In the organopolysiloxane represented by the general formula (1), examples of the monovalent hydrocarbon group of R 1 and R 3 are those having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, such as methyl, Alkyl groups such as ethyl, propyl, butyl, hexyl, octyl, decyl and octadecyl, cycloalkyl groups such as cyclopentyl and cyclohexyl,
Substitution of alkenyl groups such as vinyl and allyl, aryl groups such as phenyl, tolyl and naphthyl, aralkyl groups such as benzyl, phenylethyl and phenylpropyl, and some or all of the hydrogen atoms of these groups with halogen atoms or cyano groups. Examples of the halogenated hydrocarbon group include chloromethyl, trifluoromethyl, chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, dibromophenyl, tetrachlorophenyl and difluorophenyl groups. Examples of the cyanoalkyl group include β-cyanoethyl, γ-cyanopropyl and β-cyanopropyl groups. R 2 preferably has 1 to 8 carbon atoms, and an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, octyl,
Methoxyethyl, ethoxyethyl, methoxypropyl,
An alkoxy group-substituted alkyl group such as methoxybutyl is exemplified. R 1 , R 2 and R 3 each have 1 to 3 carbon atoms
Is preferred, and more preferred is a methyl group. Y is an oxygen atom or a divalent hydrocarbon radical, divalent hydrocarbon radical -CH 2 CH 2 -, - CH 2 CH 2 CH
2 -, - CH 2 C ( CH 3) H- carbon atoms such as 1-8, is illustrated in particular 2-6 alkylene group, -CH 2 CH 2 - is preferred.
【０００９】（Ａ）成分の２５℃での粘度は２０〜１，
０００，０００センチポイズの範囲であり、これは２０
センチポイズ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
きないためであり、また、１，０００，０００センチポ
イズより大きいと組成物の粘度が高くなり、施工時の作
業性が著しく悪くなるためである。従って、より好まし
くは１００〜５００，０００センチポイズの範囲であ
る。The viscosity of component (A) at 25 ° C. is 20-1,
The range is, 000,000 centipoise, which is 20
This is because if it is less than centipoise, excellent physical properties, especially flexibility and high elongation cannot be imparted to the cured elastomer, and if it is more than 1,000,000 centipoise, the viscosity of the composition becomes high, and the application is difficult. This is because the workability at the time becomes extremely poor. Therefore, it is more preferably in the range of 100 to 500,000 centipoise.
【００１０】（Ａ）成分の酸素原子又は二価炭化水素基
を介してオルガノオキシシリル基、特にアルコキシシリ
ル基を末端に含有するオルガノポリシロキサンの製造方
法は、従来公知の方法で製造され得る。例えば、対応す
るアルケニル基末端オルガノポリシロキサンと下記一般
式（３）The organopolysiloxane containing an organooxysilyl group, especially an alkoxysilyl group at the terminal via the oxygen atom or divalent hydrocarbon group of the component (A) can be produced by a conventionally known method. For example, a corresponding alkenyl group-terminated organopolysiloxane and the following general formula (3)
【化４】
（式中、Ｒ1、Ｒ2及びｂは前記と同じである。）で示さ
れるアルコキシシランをＰｔ触媒存在下で付加反応させ
るか又は対応するＳｉＨ末端オルガノポリシロキサンと
下記一般式（４）[Chemical 4] (In the formula, R 1 , R 2 and b are the same as above.) The alkoxysilane represented by the formula (4) is reacted with the corresponding SiH-terminated organopolysiloxane by addition reaction in the presence of a Pt catalyst.
【化５】
（式中、Ｒ5はアルケニル基であり、Ｒ1、Ｒ2及びｂは
前記と同じである。）との付加反応などにより、（Ａ）
成分を製造することができる。[Chemical 5] (In the formula, R 5 is an alkenyl group, and R 1 , R 2 and b are the same as described above.)
The ingredients can be manufactured.
【００１１】本発明に使用される（Ｂ）成分であるカー
ボンブラックは、本発明の目的である耐油性、耐ＬＬＣ
性を付与するための必須成分で、最も重要な成分であ
る。The carbon black which is the component (B) used in the present invention is the oil resistance and LLC resistance which are the objects of the present invention.
It is an essential ingredient for imparting sex and is the most important ingredient.
【００１２】カーボンブラックとしては、アセチレンブ
ラック、ファーネスブラック、ケッチェンブラックなど
が挙げられる。中でも平均粒径が１５〜６５ｎｍ、特に
２０〜５５ｎｍのものが好ましく、ＤＢＰ吸油量は８０
〜３００ｍｌ／１００ｇ、特に１２０〜２５０ｍｌ／１
００ｇのものが好ましい。また、これらカーボンブラッ
クは処理されたものでもよく、その処理としては、シラ
ンによる表面処理、酸化処理、グラフト化、粒状化・ペ
レット処理、フッ化処理、黒鉛化処理、アモルファス化
等が挙げられる。この処理により、分散性、分散安定性
の向上や、機械的強度の向上、耐水性の向上等、種々の
特性改良が見られ、本組成物における耐油性、保存安定
性、適度な粘性、ゴム物性の向上に有効である。Examples of carbon black include acetylene black, furnace black and Ketjen black. Among them, those having an average particle size of 15 to 65 nm, particularly 20 to 55 nm are preferable, and the DBP oil absorption is 80.
~ 300ml / 100g, especially 120-250ml / 1
It is preferably 00 g. Further, these carbon blacks may be treated, and examples of the treatment include surface treatment with silane, oxidation treatment, grafting, granulation / pellet treatment, fluorination treatment, graphitization treatment, amorphization and the like. By this treatment, various properties such as improvement of dispersibility and dispersion stability, improvement of mechanical strength, improvement of water resistance, etc. are observed, and oil resistance, storage stability, moderate viscosity, rubber in the present composition are observed. Effective for improving physical properties.
【００１３】（Ｂ）成分は、予め処理されたカーボンを
使用してもよく、また本組成物の製造時にシラン処理し
てもよい。この場合、本組成物の特性を維持するために
は、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も重要である。As the component (B), carbon which has been previously treated may be used, or silane treatment may be carried out when the composition is produced. In this case, in order to maintain the characteristics of the present composition, it is important that substantially no by-products and catalysts during the treatment remain in the present composition.
【００１４】（Ｂ）成分の添加量は、（Ａ）成分１００
重量部に対して通常０．５〜５０重量部であるが、好ま
しくは５〜４０重量部である。多すぎると組成物の粘度
が上がりすぎて混合及び施工時の作業性が悪くなり、ま
た、少なすぎると硬化後のゴム物性が悪くなる。The amount of component (B) added is 100 parts of component (A).
The amount is usually 0.5 to 50 parts by weight, preferably 5 to 40 parts by weight, based on parts by weight. If it is too large, the viscosity of the composition will be too high and the workability during mixing and construction will be poor, and if it is too small, the physical properties of the rubber after curing will be poor.
【００１５】本発明に使用される（Ｃ）成分は、本組成
物の架橋剤として作用し、組成物が硬化してゴム弾性体
となるための成分である。これには下記一般式（２）
Ｒ1 aＳｉ（ＯＲ2）4-a （２）
（式中、Ｒ1は一価炭化水素基、Ｒ2は一価炭化水素基又
はアルコキシ基置換一価炭化水素基、ａは０又は１であ
る。一価炭化水素基及びアルコキシ基置換一価炭化水素
基は、（Ａ）成分の説明で挙げたものと同様のものが例
示される。）で示されるオルガノオキシシラン、特にア
ルコキシシラン又はその部分加水分解縮合物が使用され
る。The component (C) used in the present invention acts as a cross-linking agent of the present composition and is a component for curing the composition to give a rubber elastic body. This includes the following general formula (2) R 1 a Si (OR 2 ) 4-a (2) (wherein R 1 is a monovalent hydrocarbon group, R 2 is a monovalent hydrocarbon group or an alkoxy group-substituted monovalent group). The hydrocarbon group, a is 0 or 1. The monovalent hydrocarbon group and the alkoxy group-substituted monovalent hydrocarbon group are exemplified by the same as those mentioned in the description of the component (A). Organooxysilanes, especially alkoxysilanes or their partial hydrolyzed condensates are used.
【００１６】（Ｃ）成分の具体例としては、テトラメト
キシシラン、テトラエトキシシラン、メチルセロソルブ
オルソシリケートなどの４官能アルコキシシラン類、メ
チルトリメトキシシラン、メチルトリエトキシシラン、
エチルトリメトキシシラン、ビニルトリメトキシシラ
ン、フェニルトリメトキシシラン、メチルトリメトキシ
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。これらは単独
で用いてもよく、また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、ジメチルジメトキ
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 (C) include tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, methylcellosolvoorthosilicate, methyltrimethoxysilane, methyltriethoxysilane, and the like.
Examples thereof include trifunctional alkoxysilanes such as ethyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and methyltrimethoxyethoxysilane, and partially hydrolyzed condensates thereof. These may be used alone or in combination of two or more. Further, in order to impart a low modulus property to the rubber elastic body after curing, bifunctional alkoxysilanes such as diphenyldimethoxysilane and dimethyldimethoxysilane may be additionally added.
【００１７】（Ｃ）成分の添加量は、（Ａ）成分１００
重量部に対して通常０．５〜１５重量部の範囲であり、
好ましくは１〜１０重量部の範囲である。添加量が少な
すぎると組成物が十分に硬化しなかったり、カートリッ
ジ内に保存中に増粘・ゲル化し易くなる。また、多すぎ
ると硬化が遅くなったり、十分なゴム物性がでなかった
り、経済的に不利益となる。The amount of component (C) added is 100 parts of component (A).
It is usually in the range of 0.5 to 15 parts by weight,
It is preferably in the range of 1 to 10 parts by weight. If the amount added is too small, the composition may not be sufficiently cured, or the composition may easily thicken or gel during storage in the cartridge. On the other hand, if the amount is too large, the curing may be delayed, the rubber may not have sufficient physical properties, and it may be economically disadvantageous.
【００１８】本発明に使用される（Ｄ）成分は、本組成
物の架橋密度向上剤として作用し、（Ｂ）成分と共に耐
油性向上に重要な成分である。これは、Ｒ4 3ＳｉＯ1/2
単位（式中、Ｒ4はアルキル基、ハロゲン置換アルキル
基、アルケニル基、フェニル基等の炭素数１〜６の非置
換又は置換の一価炭化水素基を表す。）及びＳｉＯ4/ 2
単位から本質的になり、ＳｉＯ4/2単位に対するＲ4 3Ｓ
ｉＯ1/2単位のモル比が０．６〜１．２であって、ヒド
ロキシシリル基含有量が０．７重量％未満であるオルガ
ノシロキサンが使用される。The component (D) used in the present invention acts as a crosslinking density improver for the composition and is an important component for improving the oil resistance together with the component (B). This is R 4 3 SiO 1/2
Units (in the formula, R 4 represents an alkyl group, a halogen-substituted alkyl group, an alkenyl group, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms such as a phenyl group.), And SiO 4/2
Consisting essentially of units, R 4 3 S to SiO 4/2 units
Organosiloxanes with a molar ratio of iO 1/2 units of 0.6 to 1.2 and a hydroxysilyl group content of less than 0.7% by weight are used.
【００１９】（Ｄ）成分の添加量は、（Ａ）成分１００
重量部に対して通常１〜５０重量部の範囲であり、好ま
しくは２〜４０重量部の範囲である。添加量が少なすぎ
ると耐油後の機械的強度が低い組成物となる。また、多
すぎると硬化が遅くなったり、十分なゴム物性がでなか
ったりする。The amount of component (D) added is 100 parts of component (A).
It is usually in the range of 1 to 50 parts by weight, and preferably in the range of 2 to 40 parts by weight, based on parts by weight. If the amount added is too small, the composition has low mechanical strength after oil resistance. On the other hand, if the amount is too large, the curing may be delayed, or the rubber may not have sufficient physical properties.
【００２０】本発明に使用される（Ｅ）成分は、本組成
物を硬化せしめるための触媒であり、本組成物の改善さ
れた保存安定性を得るためにはチタンキレート触媒であ
ることが必要である。チタンキレート触媒としては、下
記一般式（５）、（６）、（７）から選ばれた少なくと
も１種のチタンキレート触媒であることが好ましい。The component (E) used in the present invention is a catalyst for curing the composition, and a titanium chelate catalyst is necessary for obtaining the improved storage stability of the composition. Is. The titanium chelate catalyst is preferably at least one titanium chelate catalyst selected from the following general formulas (5), (6) and (7).
【００２１】[0021]
【化６】
（式中、ＸはＲ1、炭素数１〜６のアルコキシ基、アミ
ノ基、アセチル基から選ばれる基を表し、Ｒは水素原子
又はＲ1を表し、Ｒ1、Ｒ2、Ｒ3は前記と同じである。ｍ
は１〜８の整数である。なおこの場合、Ｒ1とＲ3とは互
いに結合して、これらが結合するＣ＝Ｃと共に合計炭素
数５〜８の環を形成してもよい。）[Chemical 6] (In the formula, X represents a group selected from R 1 , an alkoxy group having 1 to 6 carbon atoms, an amino group, and an acetyl group, R represents a hydrogen atom or R 1 , and R 1 , R 2 , and R 3 are the above. Same as m
Is an integer of 1 to 8. In this case, R 1 and R 3 may be bonded to each other to form a ring having 5 to 8 carbon atoms in total together with C═C to which they are bonded. )
【００２２】[0022]
【化７】
（式中、Ｒ2はメチル基又はエチル基、Ｒ3はメチル基、
エチル基、フェニル基又はビニル基を表し、ｘは５〜３
０、ｙは１〜１０である。）[Chemical 7] (In the formula, R 2 is a methyl group or an ethyl group, R 3 is a methyl group,
Represents an ethyl group, a phenyl group or a vinyl group, and x is 5 to 3
0 and y are 1-10. )
【００２３】（Ｅ）成分の具体例は、ジイソプロポキシ
ビス（アセト酢酸エチル）チタン、ジイソプロポキシビ
ス（アセチルアセトン）チタン、ジブトキシビス（アセ
ト酢酸メチル）チタンや下記に示すものなどが例示され
る。Specific examples of the component (E) include diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetone) titanium, dibutoxybis (methylacetoacetate) titanium and those shown below.
【００２４】[0024]
【化８】 [Chemical 8]
【００２５】[0025]
【化９】 [Chemical 9]
【００２６】（Ｅ）成分の添加量は、（Ａ）成分１００
重量部に対して０．１〜１０重量部の範囲であり、好ま
しくは０．２〜７重量部の範囲である。添加量が少なす
ぎると本組成物の硬化が遅くなり、多すぎると硬化が早
すぎたり、保存安定性が悪くなる。The amount of component (E) added is 100 parts of component (A).
It is in the range of 0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight, based on parts by weight. If the amount added is too small, the curing of the composition will be delayed, while if it is too large, the curing will be too fast or the storage stability will be poor.
【００２７】本発明の組成物は、前記した（Ａ）〜
（Ｅ）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、炭酸
カルシウム、煙霧質二酸化チタン、けいそう土、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。The composition of the present invention comprises the above (A) to
In addition to the component (E), a fine powdery inorganic filler is further added, if necessary, in order to improve the flow characteristics before curing and impart necessary mechanical properties to the rubber-like elastic body after curing. It can also be added. As the inorganic filler, fine quartz powder, calcium carbonate, fumed titanium dioxide, diatomaceous earth, aluminum hydroxide, particulate alumina, magnesia, zinc oxide, zinc carbonate and silanes, silazanes, low-polymerization degree siloxanes of these , Those surface-treated with organic compounds and the like.
【００２８】更に、本発明の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。Further, an organic solvent, an antifungal agent, a flame retardant, a heat-resistant agent, a plasticizer, a thixotropic agent, an adhesion promoter, a curing accelerator, a pigment and the like can be added to the composition of the present invention.
【００２９】本発明の組成物は、（Ａ）〜（Ｅ）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さらすこ
とによりゴム状弾性体に硬化する、いわゆる１液型室温
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 composition of the present invention can be obtained by mixing the components (A) to (E) and, if necessary, various additives in a state where moisture is blocked. The obtained composition can be used as a so-called one-pack type room temperature curable organopolysiloxane composition which 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 at the time of use.
【００３０】本発明の組成物は自動車用シーリング材の
他、建築用シーリング材、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
剤としての用途にも適用することができる。The composition of the present invention is used as a sealing material for automobiles, as a sealing material for construction, a sealing material for electric / electronic parts, an adhesive or a moisture-proof coating agent, as a textile product, a glass product,
It can also be applied to applications such as coating agents and adhesives for metal products and plastic products.
【００３１】[0031]
【実施例】以下、実施例及び比較例を示し、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いずれも重
量部を示し、粘度は２５℃における値である。EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, all parts are parts by weight, and the viscosity is the value at 25 ° C.
【００３２】［合成例１］粘度が３０，０００センチポ
イズのα，ω−ジメチルビニル−ジメチルポリシロキサ
ン１００部と、トリメトキシシラン７部及び触媒として
塩化白金酸の１％イソプロパノール溶液１部を添加し、
Ｎ2気流下、８０℃で８時間混合した。その後１０ｍｍ
Ｈｇの減圧下で５０℃に加熱して、余剰のトリメトキシ
シランを留去した。[Synthesis Example 1] 100 parts of α, ω-dimethylvinyl-dimethylpolysiloxane having a viscosity of 30,000 centipoise, 7 parts of trimethoxysilane and 1 part of a 1% isopropanol solution of chloroplatinic acid as a catalyst were added. ,
Mixing was performed at 80 ° C. for 8 hours under N 2 flow. Then 10 mm
The mixture was heated to 50 ° C. under reduced pressure of Hg, and excess trimethoxysilane was distilled off.
【００３３】得られたポリマーは粘度が３０，５００セ
ンチポイズであり、テトラブチルチタネートと１００：
１の比率で混合したところ、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
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。The polymer obtained has a viscosity of 30,500 centipoise and is 100: 100 with tetrabutyl titanate.
When mixed at a ratio of 1, the viscosity did not increase immediately and it was cured after 1 day. From this, it can be confirmed that trimethoxysilane was added to the vinyl group at the terminal of the polymer. This polymer is referred to as polymer A.
【００３４】［合成例２］粘度が２０，０００センチポ
イズのα，ω−ジヒドロキシ−ジメチルポリシロキサン
１００部と、テトラメトキシシラン１０部及び触媒とし
てイソプロピルアミン０．１部を添加し、Ｎ2気流下で
１００℃で６時間混合した。その後１０ｍｍＨｇの減圧
下で５０℃に加熱して、余剰のテトラメトキシシランを
留去した。[Synthesis Example 2] 100 parts of α, ω-dihydroxy-dimethylpolysiloxane having a viscosity of 20,000 centipoise, 10 parts of tetramethoxysilane and 0.1 part of isopropylamine as a catalyst were added, and the mixture was added under a stream of N 2. At 100 ° C. for 6 hours. After that, it was heated to 50 ° C. under a reduced pressure of 10 mmHg to distill off excess tetramethoxysilane.
【００３５】得られたポリマーは粘度が２１，０００セ
ンチポイズであり、テトラブチルチタネートと１００：
１の比率で混合したところ、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がトリメトキ
シシリル基で置換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。The polymer obtained has a viscosity of 21,000 centipoise and is 100: 100 with tetrabutyl titanate.
When mixed at a ratio of 1, the viscosity did not increase immediately and it was cured after 1 day. From this, it can be confirmed that the polymer terminal was substituted with a trimethoxysilyl group. This polymer is referred to as polymer B.
【００３６】［実施例１］ポリマーＡ１００部と、デン
カブラックＨＳ−１００［平均粒径４８ｎｍ、ＤＢＰ吸
油量１４０ｍｌ／１００ｇ（電気化学工業社製）］２０
部を均一に混合し、これにビニルトリメトキシシラン６
部とジイソプロポキシ−ビス（アセト酢酸エチル）チタ
ン２部を減圧下で均一になるまで混合して組成物を調製
した。これをポリカートリッジに入れて密封した。Example 1 100 parts of Polymer A and Denka Black HS-100 [average particle size 48 nm, DBP oil absorption 140 ml / 100 g (manufactured by Denki Kagaku Kogyo KK)] 20
Parts are mixed evenly and mixed with vinyltrimethoxysilane 6
Parts and diisopropoxy-bis (ethyl acetoacetate) titanium 2 parts were mixed under reduced pressure until uniform to prepare a composition. This was placed in a poly cartridge and sealed.
【００３７】［実施例２］ポリマーＡ１００部と、トリ
メチルシロキシ単位（（ＣＨ3）3ＳｉＯ1/2単位）及び
ＳｉＯ4/2単位からなり、（ＣＨ3）3ＳｉＯ1/2／ＳｉＯ
4/2モル比が０．７４で、シラノール基含有量が０．０
６ｍｏｌ／１００ｇであり、固形分が５０重量％となる
ようにトルエンに溶解された樹脂状シロキサンコポリマ
ー１０部、デンカブラックＨＳ−１００（電気化学工業
社製）２０部を均一に混合し、これにビニルトリメトキ
シシラン６部とジイソプロポキシ−ビス（アセト酢酸エ
チル）チタン２部を減圧下で均一になるまで混合して組
成物を調製した。これをポリカートリッジに入れて密封
した。Example 2 100 parts of polymer A, trimethylsiloxy units ((CH 3 ) 3 SiO 1/2 units) and SiO 4/2 units were used, and (CH 3 ) 3 SiO 1/2 / SiO
4/2 molar ratio is 0.74, silanol group content is 0.0
6 mol / 100 g, 10 parts of a resinous siloxane copolymer dissolved in toluene so that the solid content is 50% by weight, and 20 parts of Denka Black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.) were uniformly mixed, and mixed with this. A composition was prepared by mixing 6 parts of vinyltrimethoxysilane and 2 parts of diisopropoxy-bis (ethylacetoacetate) titanium under reduced pressure until uniform. This was placed in a poly cartridge and sealed.
【００３８】［実施例３］ポリマーＢ１００部と、トリ
メチルシロキシ単位（（ＣＨ3）3ＳｉＯ1/2単位）及び
ＳｉＯ4/2単位からなり、（ＣＨ3）3ＳｉＯ1/2／ＳｉＯ
4/2モル比が０．７４で、シラノール基含有量が０．０
６ｍｏｌ／１００ｇであり、固形分が５０重量％となる
ようにトルエンに溶解された樹脂状シロキサンコポリマ
ー１０部、デンカブラックＨＳ−１００（電気化学工業
社製）２０部を均一に混合し、これにビニルトリメトキ
シシラン６部とジイソプロポキシ−ビス（アセト酢酸エ
チル）チタン２部を減圧下で均一になるまで混合して組
成物を調製した。これをポリカートリッジに入れて密封
した。Example 3 100 parts of Polymer B, trimethylsiloxy units ((CH 3 ) 3 SiO 1/2 units) and SiO 4/2 units were used, and (CH 3 ) 3 SiO 1/2 / SiO
4/2 molar ratio is 0.74, silanol group content is 0.0
6 mol / 100 g, 10 parts of a resinous siloxane copolymer dissolved in toluene so that the solid content is 50% by weight, and 20 parts of Denka Black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.) were uniformly mixed, and mixed with this. A composition was prepared by mixing 6 parts of vinyltrimethoxysilane and 2 parts of diisopropoxy-bis (ethylacetoacetate) titanium under reduced pressure until uniform. This was placed in a poly cartridge and sealed.
【００３９】上記で得られた組成物で厚さ２ｍｍのシー
トを作製し、２３℃，５０％ＲＨの雰囲気下で７日間硬
化させ、ＪＩＳ−Ｋ６２４９に準じてゴム物性（硬さ、
引張強さ、切断時伸び）を測定した。更に、以下の条件
で保存後、及び、耐油後、耐ＬＬＣ後のゴム物性（硬
さ、引張強さ、切断時伸び）を測定した。結果を表１に
示す。
保存条件：乾燥機にて７０℃加熱で７日間保存した。
耐油評価条件：トヨタエンジンオイル ネオＳＪ２０を
使用し、１２０℃で２４０時間の条件で評価した。
耐ＬＬＣ評価条件：トヨタＬＬＣ５０％水溶液を使用
し、１２０℃で２４０時間の条件で評価した。A sheet having a thickness of 2 mm was prepared from the composition obtained above and cured in an atmosphere of 23 ° C. and 50% RH for 7 days. According to JIS-K6249, the physical properties of rubber (hardness, hardness,
Tensile strength and elongation at break) were measured. Furthermore, the rubber properties (hardness, tensile strength, elongation at break) after storage under the following conditions, and after oil resistance and after LLC resistance were measured. The results are shown in Table 1. Storage condition: It was stored in a dryer at 70 ° C. for 7 days. Oil resistance evaluation conditions: Toyota engine oil Neo SJ20 was used and evaluated at 120 ° C. for 240 hours. LLC-resistant evaluation condition: Toyota LLC 50% aqueous solution was used, and it evaluated on condition of 240 degreeC at 120 degreeC.
【００４０】［比較例１］実施例１において、デンカブ
ラックＨＳ−１００（電気化学工業社製）の代わりにジ
メチルジクロロシランで表面処理された乾式シリカ２０
部を使用した以外は実施例１と同様の手法で組成物を調
製した。この組成物を使用して実施例１と同様の試験を
行った結果を表１に示す。Comparative Example 1 Dry silica 20 surface-treated with dimethyldichlorosilane instead of Denka Black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.) in Example 1
A composition was prepared in the same manner as in Example 1 except that parts were used. The results of the same tests as in Example 1 using this composition are shown in Table 1.
【００４１】［比較例２］実施例２において、デンカブ
ラックＨＳ−１００（電気化学工業社製）の代わりにジ
メチルジクロロシランで表面処理された乾式シリカ２０
部を使用した以外は実施例２と同様の手法で組成物を調
製した。この組成物を使用して実施例２と同様の試験を
行った結果を表１に示す。Comparative Example 2 Dry silica 20 surface-treated with dimethyldichlorosilane instead of Denka Black HS-100 (manufactured by Denki Kagaku Kogyo) in Example 2
A composition was prepared in the same manner as in Example 2 except that parts were used. The results of the same test as in Example 2 using this composition are shown in Table 1.
【００４２】［比較例３］実施例２において、ポリマー
Ａの代わりに粘度が２０，０００センチポイズのα，ω
−ジヒドロキシ−ジメチルポリシロキサン１００部、デ
ンカブラックＨＳ−１００（電気化学工業社製）の代わ
りにジメチルジクロロシランで表面処理された乾式シリ
カ２０部を使用した以外は実施例２と同様の手法で組成
物を調製した。この組成物を使用して実施例２と同様の
試験を行った結果を表１に示す。COMPARATIVE EXAMPLE 3 In Example 2, instead of the polymer A, α, ω having a viscosity of 20,000 centipoise.
Composition in the same manner as in Example 2 except that 100 parts of dihydroxy-dimethylpolysiloxane and 20 parts of dry silica surface-treated with dimethyldichlorosilane were used instead of Denka Black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.). The thing was prepared. The results of the same test as in Example 2 using this composition are shown in Table 1.
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【発明の効果】本発明の組成物は、従来の１液型脱アル
コールタイプの室温硬化性オルガノポリシロキサン組成
物に比べ、密封条件下での保存安定性にも優れ、自動車
エンジン周りという過酷な条件下でも殆ど物性値の変化
の少ないエラストマー状硬化物を与える室温硬化性オル
ガノポリシロキサン組成物である。INDUSTRIAL APPLICABILITY The composition of the present invention has excellent storage stability under sealed conditions and is more harsh around the automobile engine than the conventional one-pack dealcohol type room temperature curable organopolysiloxane composition. A room-temperature-curable organopolysiloxane composition that gives an elastomer-like cured product with little change in physical properties even under conditions.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） (Ｃ０８Ｌ 83/06 Ｃ０８Ｌ 83:04 83:04） (72)発明者 木村 恒雄 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子材料 技術研究所内 Ｆターム(参考） 4H017 AA04 AA29 AB15 AC03 AD06 AE05 4J002 CP032 CP051 CP081 CP091 CP131 CP141 DA036 EE048 EH038 EX037 GH00 GJ01 GJ02 GN00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI theme code (reference) (C08L 83/06 C08L 83:04 83:04) (72) Inventor Tsuneo Kimura Matsuida Town, Usui District, Gunma Prefecture Hitomi No. 1 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory F-term (reference) 4H017 AA04 AA29 AB15 AC03 AD06 AE05 4J002 CP032 CP051 CP081 CP091 CP131 CP141 DA036 EE048 EH038 EX037 GH00 GJ01 GJ02 GN00
Claims (4)
はアルコキシ基置換一価炭化水素基、Ｒ3は非置換又は
置換の一価炭化水素基、Ｙは酸素原子又は二価炭化水素
基、ｂは１〜３の整数、ｎは２５℃における粘度が２０
〜１，０００，０００センチポイズとなるような整数で
ある。） で表されるオルガノオキシシリル基を末端に有する直鎖
状オルガノポリシロキサ ン１００重量部 （Ｂ）カーボンブラック０．５〜５０重量部 （Ｃ）下記一般式（２） Ｒ1 aＳｉ（ＯＲ2）4-a （２） （式中、Ｒ1は一価炭化水素基、Ｒ2は一価炭化水素基又
はアルコキシ基置換一価炭化水素基、ａは０又は１であ
る。）で表されるオルガノオキシシラン又はその部分加
水分解縮合物０．５〜１５重量部を必須成分としてなる
室温硬化性オルガノポリシロキサン組成物。1. (A) The following general formula (1): (In the formula, R 1 is a monovalent hydrocarbon group, R 2 is a monovalent hydrocarbon group or an alkoxy group-substituted monovalent hydrocarbon group, R 3 is an unsubstituted or substituted monovalent hydrocarbon group, Y is an oxygen atom or Divalent hydrocarbon group, b is an integer of 1 to 3, n is 25 at a viscosity of 20
It is an integer such that it is about 1,000,000 centipoise. ) 100 parts by weight of a linear organopolysiloxane having an organooxysilyl group at the end (B) 0.5 to 50 parts by weight of carbon black (C) the following general formula (2) R 1 a Si (OR 2 ) 4-a (2) (in the formula, R 1 is a monovalent hydrocarbon group, R 2 is a monovalent hydrocarbon group or an alkoxy group-substituted monovalent hydrocarbon group, and a is 0 or 1). A room temperature curable organopolysiloxane composition comprising 0.5 to 15 parts by weight of an organooxysilane or a partially hydrolyzed condensate thereof as an essential component.
中、Ｒ4は炭素数１〜６の非置換又は置換の一価炭化水
素基を表す。）及びＳｉＯ4/2単位から本質的になり、
ＳｉＯ4/2単位に対するＲ4 3ＳｉＯ1/2単位のモル比が
０．６〜１．２であって、ヒドロキシシリル基の含有量
が０．７重量％未満であるオルガノシロキサン１〜５０
重量部を含有する請求項１記載の室温硬化性オルガノポ
リシロキサン組成物。2. (D) R 4 3 SiO 1/2 unit (wherein R 4 represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) and SiO 4/2. Becomes essential from the unit,
The molar ratio of R 4 3 SiO 1/2 units to SiO 4/2 units is a 0.6-1.2 organosiloxane 1-50 content of hydroxysilyl groups is less than 0.7 wt%
The room temperature-curable organopolysiloxane composition according to claim 1, which comprises parts by weight.
〜１０重量部を含有する請求項１又は２記載の室温硬化
性オルガノポリシロキサン組成物。3. (E) titanium chelate catalyst 0.1
The room temperature curable organopolysiloxane composition according to claim 1 or 2, containing 10 to 10 parts by weight.
５ｎｍであり、ＤＢＰ吸油量が８０〜３００ｍｌ／１０
０ｇである請求項１乃至３のいずれか１項記載の室温硬
化性オルガノポリシロキサン組成物。4. The average particle size of carbon black is 15 to 6.
5 nm, DBP oil absorption is 80-300 ml / 10
The room temperature curable organopolysiloxane composition according to claim 1, which has an amount of 0 g.
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| JP2003327829A (en) * | 2002-05-09 | 2003-11-19 | Shin Etsu Chem Co Ltd | Room temperature-curable organopolysiloxane composition |
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| JP2006316190A (en) * | 2005-05-13 | 2006-11-24 | Shin Etsu Chem Co Ltd | Room temperature-curable organopolysiloxane composition |
| JP2007169356A (en) * | 2005-12-20 | 2007-07-05 | Momentive Performance Materials Japan Kk | Polyorganosiloxane composition curable at room temperature |
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| US7674348B2 (en) | 2003-04-25 | 2010-03-09 | Shin-Etsu Chemical Co., Ltd. | Air bag sealer silicone rubber composition |
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| JP2009197188A (en) * | 2008-02-25 | 2009-09-03 | Three Bond Co Ltd | Oily face-adhesive room temperature curable organopolysiloxane composition and cured product using the same |
| JP2021134259A (en) * | 2020-02-26 | 2021-09-13 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition, and article |
| JP7392514B2 (en) | 2020-02-26 | 2023-12-06 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane compositions and articles |
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