JP2990646B2 - Curable composition - Google Patents
Curable compositionInfo
- Publication number
- JP2990646B2 JP2990646B2 JP7027296A JP2729695A JP2990646B2 JP 2990646 B2 JP2990646 B2 JP 2990646B2 JP 7027296 A JP7027296 A JP 7027296A JP 2729695 A JP2729695 A JP 2729695A JP 2990646 B2 JP2990646 B2 JP 2990646B2
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- group
- compound
- divalent
- formula
- fluorine
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、室温で放置しあるいは
加熱することによって容易に硬化し、耐溶剤性、耐薬品
性、耐熱性及び低温特性に優れるのみならず透湿性にも
優れる硬化物を与える硬化性組成物に関する。BACKGROUND OF THE INVENTION The present invention relates to a cured product which is easily cured by being left or heated at room temperature, and is excellent not only in solvent resistance, chemical resistance, heat resistance and low-temperature properties but also in moisture permeability. And a curable composition that gives
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、含フッ素有機化合物のポリマーと架橋剤を主成分と
する硬化性含フッ素エラストマー組成物は、各種分野で
使用されている。2. Description of the Related Art Curable fluorine-containing elastomer compositions containing a polymer of a fluorine-containing organic compound and a crosslinking agent as main components have been used in various fields.
【０００３】しかし、従来、上市されている含フッ素エ
ラストマー組成物より得られる硬化物には、ゴム材料と
しての耐溶剤性、耐薬品性、耐熱性、低温特性、低透湿
性をいずれも十分満足し得るものはなかった。例えば、
フッ素ゴムは低温特性に劣り、液状化は不可能であり、
シリコーンゴムは耐薬品性及び耐溶剤性に劣る材料であ
る。また、両者の性能を合わせ持つゴム材料として開発
されたフロロシリコーンゴムは耐薬品性及び極性溶剤に
対する耐溶剤性が不十分であった。However, conventionally, cured products obtained from commercially available fluoroelastomer compositions sufficiently satisfy solvent resistance, chemical resistance, heat resistance, low-temperature characteristics, and low moisture permeability as rubber materials. There was nothing to do. For example,
Fluoro rubber is inferior in low-temperature properties and cannot be liquefied,
Silicone rubber is a material having poor chemical resistance and solvent resistance. Fluorosilicone rubber, which has been developed as a rubber material having both properties, has insufficient chemical resistance and solvent resistance to polar solvents.
【０００４】本発明は上記事情に鑑みなされたもので、
耐溶剤性、耐薬品性、耐熱性及び低温特性に優れるのみ
ならず透湿性にも優れる硬化物を与える含フッ素アミド
化合物と含フッ素オルガノ水素シロキサンとを主成分と
する硬化性組成物を提供することを目的とする。[0004] The present invention has been made in view of the above circumstances,
Provided is a curable composition containing a fluorinated amide compound and a fluorinated organohydrogensiloxane as main components, which gives a cured product having not only excellent solvent resistance, chemical resistance, heat resistance and low-temperature properties but also excellent moisture permeability. The purpose is to:
【０００５】[0005]
【課題を解決するための手段及び作用】本発明者は、上
記目的を達成するため鋭意検討を重ねた結果、下記一般
式（１）で示される含フッ素アミド化合物に下記の含フ
ッ素オルガノシロキサンを架橋剤、鎖長延長剤として配
合し、白金族化合物を触媒として添加することにより、
耐溶剤性、耐薬品性、耐熱性及び低温特性に優れるのみ
ならず透湿性にも優れる硬化物を与える硬化性組成物が
得られることを知見し、本発明をなすに至った。The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the following fluorine-containing organosiloxane is added to the fluorine-containing amide compound represented by the following general formula (1). By compounding as a crosslinking agent and a chain extender, and adding a platinum group compound as a catalyst,
The present inventors have found that a curable composition which gives a cured product which is excellent not only in solvent resistance, chemical resistance, heat resistance and low-temperature properties but also in moisture permeability can be obtained, and has accomplished the present invention.
【０００６】従って、本発明は、（Ａ）下記一般式
（１）で示される含フッ素アミド化合物、（Ｂ）一分子
中に一個以上の一価のパーフルオロオキシアルキル基、
一価のパーフルオロアルキル基、二価のパーフルオロオ
キシアルキレン基又は二価のパーフロロアルキレン基を
有し、且つ二個以上のヒドロシリル基を有する含フッ素
オルガノ水素シロキサン、（Ｃ）触媒量の白金族化合物
を含有する組成物であって、上記（Ｂ）成分の量は該組
成物中の脂肪族不飽和基１モルに対し、ヒドロシリル
（Ｓｉ−Ｈ）基が０．５〜５モルとなる量であることを
特徴とする硬化性組成物を提供する。Accordingly, the present invention provides (A) a fluorine-containing amide compound represented by the following general formula (1), (B) one or more monovalent perfluorooxyalkyl groups in one molecule,
A fluorinated organohydrogensiloxane having a monovalent perfluoroalkyl group, a divalent perfluorooxyalkylene group or a divalent perfluoroalkylene group and having two or more hydrosilyl groups, and (C) a catalytic amount of platinum A composition containing an aromatic compound, wherein the amount of the component (B) is such that the hydrosilyl (Si-H) group is 0.5 to 5 mol per 1 mol of the aliphatic unsaturated group in the composition. Curable composition characterized in that the amount is curable.
【０００７】[0007]
【化４】 Embedded image
【０００８】以下、本発明につき更に詳述すると、本発
明の硬化性組成物は、主剤のベースポリマーとして上記
式（１）の含フッ素アミド化合物、その架橋剤乃至は鎖
長延長剤としての含フッ素オルガノ水素シロキサン及び
触媒としての白金族化合物を含有するものである。Hereinafter, the present invention will be described in more detail. The curable composition of the present invention contains a fluorine-containing amide compound represented by the above formula (1) as a base polymer as a base resin and a crosslinking agent or a chain extender thereof. It contains fluorine organohydrogensiloxane and a platinum group compound as a catalyst.
【０００９】本発明の第一必須成分［（Ａ）成分］は含
フッ素アミド化合物であり、この（Ａ）成分の含フッ素
アミド化合物は、下記一般式（１）で示されるものであ
る。The first essential component [component (A)] of the present invention is a fluorine-containing amide compound, and the fluorine-containing amide compound of the component (A) is represented by the following general formula (1).
【００１０】[0010]
【化５】 Embedded image
【００１１】ここで、上記式（１）中のＲ1としては、
炭素数１〜１０、特に１〜８の、好ましくは脂肪族不飽
和結合を除く、置換又は非置換の一価炭化水素基が好適
であり、例えばメチル基、エチル基、プロピル基、イソ
プロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチ
ル基、ペンチル基、ヘキシル基、オクチル基、デシル基
等のアルキル基、シクロペンチル基、シクロヘキシル
基、シクロヘプチル基等のシクロアルキル基、ビニル
基、アリル基、プロペニル基、イソプロペニル基、ブテ
ニル基、ヘキセニル基等のアルケニル基、フェニル基、
トリル基、キシリル基、ナフチル基等のアリール基、ベ
ンジル基、フェニルエチル基、フェニルプロピル基等の
アラルキル基、あるいはこれらの基の水素原子の一部又
は全部をハロゲン原子等で置換したクロロメチル基、ク
ロロプロピル基、ブロモエチル基、３，３，３−トリフ
ルオロプロピル基、６，６，６，５，５，４，４，３，
３−ノナフルオロヘキシル基等のフッ素置換アルキル基
などが挙げられる。Here, R 1 in the above formula (1) is:
A substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8, preferably excluding an aliphatic unsaturated bond, is suitable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl groups such as butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, vinyl group, allyl group, and propenyl group An alkenyl group such as an isopropenyl group, a butenyl group, a hexenyl group, a phenyl group,
Aryl groups such as tolyl group, xylyl group and naphthyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, or chloromethyl group in which part or all of the hydrogen atoms of these groups have been substituted with halogen atoms, etc. , Chloropropyl group, bromoethyl group, 3,3,3-trifluoropropyl group, 6,6,6,5,5,4,4,3
And a fluorine-substituted alkyl group such as a 3-nonafluorohexyl group.
【００１２】次に、Ｒ2としては、水素原子又は前記Ｒ1
として例示したものと同様の炭素数１〜１０、特に１〜
８の、好ましくは脂肪族不飽和結合を除く、置換又は非
置換の一価炭化水素基が好適であり、一価炭化水素基と
しては、Ｒ1と同様の基を挙げることができ、例えばメ
チル基、エチル基、プロピル基、イソプロピル基等のア
ルキル基、シクロヘキシル基等のシクロアルキル基、ビ
ニル基、アリル基等のアルケニル基、フェニル基、トリ
ル基等のアリール基、あるいはこれらの基の水素原子の
一部をハロゲン原子等で置換したクロロメチル基、クロ
ロプロピル基、３，３，３−トリフルオロプロピル基、
６，６，６，５，５，４，４，３，３−ノナフルオロヘ
キシル基等のフッ素置換アルキル基などが挙げられる。Next, as R 2 , a hydrogen atom or the aforementioned R 1
Having the same carbon number as that exemplified as 1 to 10, particularly 1 to
8, preferably a substituted or unsubstituted monovalent hydrocarbon group excluding an aliphatic unsaturated bond, and examples of the monovalent hydrocarbon group include the same groups as R 1. Groups, alkyl groups such as ethyl group, propyl group and isopropyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group and allyl group, aryl groups such as phenyl group and tolyl group, or hydrogen atoms of these groups A chloromethyl group, a part of which is substituted with a halogen atom, a chloropropyl group, a 3,3,3-trifluoropropyl group,
And a fluorine-substituted alkyl group such as 6,6,6,5,5,4,4,3,3-nonafluorohexyl group.
【００１３】また、上記式（１）においてＱは下記一般
式（２）又は一般式（３）で示される基である。In the above formula (1), Q is a group represented by the following general formula (2) or (3).
【００１４】[0014]
【化６】 Embedded image
【００１５】上記式（２）中のＲ2は前記と同様であ
り、Ｒ3としては、置換又は非置換の二価炭化水素基で
あれば特に限定されないが、炭素数１〜２０、特に２〜
１０の二価炭化水素基が好適であり、具体的にはメチレ
ン基、エチレン基、プロピレン基、メチルエチレン基、
ブチレン基、ヘキサメチレン基等のアルキレン基、シク
ロヘキシレン基等のシクロアルキレン基、フェニレン
基、トリレン基、キシリレン基、ナフチレン基、ビフェ
ニレン基等のアリーレン基、あるいはこれらの基の水素
原子の一部をハロゲン原子等で置換した基、あるいはこ
れらの置換又は非置換のアルキレン基、アリーレン基の
組み合わせなどが例示される。R 2 in the above formula (2) is the same as described above, and R 3 is not particularly limited as long as it is a substituted or unsubstituted divalent hydrocarbon group. ~
10 divalent hydrocarbon groups are preferred, and specifically, a methylene group, an ethylene group, a propylene group, a methylethylene group,
Butylene group, alkylene group such as hexamethylene group, cycloalkylene group such as cyclohexylene group, arylene group such as phenylene group, tolylene group, xylylene group, naphthylene group, biphenylene group, or a part of hydrogen atom of these groups. Examples thereof include a group substituted with a halogen atom or the like, or a combination of these substituted or unsubstituted alkylene groups and arylene groups.
【００１６】また、Ｒ3は結合の途中に酸素原子、窒素
原子、ケイ素原子の１種又は２種以上を含んでも良い。
この場合、酸素原子は−Ｏ−、窒素原子は−ＮＲ’−
（Ｒ’は水素原子又は炭素数１〜８、特に１〜６のアル
キル基又はアリール基である）として介在することがで
き、またケイ素原子は、例えば下記の基のように直鎖状
又は環状のオルガノシロキサンを含有する基あるいはオ
ルガノシリレン基として介在することができる。R 3 may contain one or more of an oxygen atom, a nitrogen atom and a silicon atom in the middle of the bond.
In this case, the oxygen atom is -O-, and the nitrogen atom is -NR'-
(R ′ is a hydrogen atom or an alkyl group or an aryl group having 1 to 8, particularly 1 to 6 carbon atoms), and the silicon atom may be linear or cyclic, for example, Or a group containing an organosiloxane or an organosilylene group.
【００１７】[0017]
【化７】 （但し、Ｒ”は前記Ｒ1，Ｒ2として例示したものと同様
の炭素数１〜８のアルキル基又はアリール基、Ｒ'''は
前記Ｒ3として例示したものと同様の炭素数１〜６のア
ルキレン基又はアリーレン基であり、ｎ＝０〜１０、特
に０〜５の整数である。） このような基としては、下記の基を例示することができ
る。Embedded image (Provided that R ″ is the same alkyl group or aryl group having 1 to 8 carbon atoms as those exemplified as R 1 and R 2 , and R ′ ″ is 1 to 2 carbon atoms similar to those exemplified as R 3 . 6 is an alkylene group or an arylene group, and n is an integer of 0 to 10, particularly 0 to 5.) Examples of such a group include the following groups.
【００１８】[0018]
【化８】 （Ｍｅはメチル基を示す。）Embedded image (Me represents a methyl group.)
【００１９】更に、上記式（３）中のＲ4及びＲ5として
は、炭素数１〜１０、特に２〜６の置換又は非置換の二
価炭化水素基が好適であり、具体的にはメチレン基、エ
チレン基、プロピレン基、メチルエチレン基、ブチレン
基、ヘキサメチレン基等のアルキレン基、シクロヘキシ
レン基等のシクロアルキレン基、あるいはこれらの基の
水素原子の一部をハロゲン原子等で置換した基などが例
示される。Further, as R 4 and R 5 in the above formula (3), a substituted or unsubstituted divalent hydrocarbon group having 1 to 10, especially 2 to 6 carbon atoms is preferable. Methylene group, ethylene group, propylene group, methylethylene group, butylene group, alkylene group such as hexamethylene group, cycloalkylene group such as cyclohexylene group, or part of hydrogen atoms of these groups is substituted with halogen atom or the like. And the like.
【００２０】上記式（２）又は式（３）により示される
式（１）中のＱとして具体的には下記の基が例示され
る。なお、以下の化学式において、Ｍｅはメチル基、Ｐ
ｈはフェニル基を示す。The following groups are specifically exemplified as Q in the formula (1) represented by the above formula (2) or (3). In the following chemical formula, Me is a methyl group, P
h represents a phenyl group.
【００２１】[0021]
【化９】 Embedded image
【００２２】[0022]
【化１０】 Embedded image
【００２３】また、式（１）においてＲｆは二価パーフ
ルオロアルキレン基又は二価パーフルオロポリエーテル
基であり、特に二価パーフルオロアルキレン基としては −ＣmＦ2m− （但し、ｍ＝１〜１０、好ましくは２〜６である。）で
示されるものが好ましく、二価パーフルオロポリエーテ
ル基としては下記式で示されるものが好ましい。In the formula (1), Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and particularly, as a divalent perfluoroalkylene group, -C m F 2m- (where m = 1 To 10, and preferably 2 to 6.), and the divalent perfluoropolyether group is preferably a compound represented by the following formula.
【００２４】[0024]
【化１１】 Ｒｆとして具体的には、下記のものが例示される。Embedded image The following are specifically exemplified as Rf.
【００２５】[0025]
【化１２】 Embedded image
【００２６】なお、上記式（１）においてａは０以上の
整数であり、従って、式（１）の含フッ素アミド化合物
は１分子中に二価パーフルオロアルキレン基又は二価パ
ーフルオロポリエーテル基を１個以上含むものである
が、ａは好ましくは０〜１０、特に１〜６の整数であ
る。In the above formula (1), a is an integer of 0 or more. Therefore, the fluorine-containing amide compound of the formula (1) has a divalent perfluoroalkylene group or a divalent perfluoropolyether group in one molecule. A is preferably an integer of 0 to 10, particularly 1 to 6.
【００２７】本発明においては、上記（Ａ）成分の含フ
ッ素アミド化合物として、粘度（２５℃、以下同様）が
数十ｃｓの低粘度ポリマーから固形の生ゴム状のポリマ
ーまで使用することができるが、取り扱いやすさの点か
らは、例えば熱加硫ゴム用としては生ゴム状のポリマー
が、また、液状ゴム用には粘度が１００〜１０００００
ｃｓ程度のポリマーが好適に使用される。低粘度すぎる
と得られる硬化物がエラストマーとしての伸びが小さく
なり、バランスのとれた物性が得られない場合が生じ
る。In the present invention, as the fluorine-containing amide compound as the component (A), a low viscosity polymer having a viscosity (25 ° C., hereinafter the same) of several tens cs to a solid raw rubber-like polymer can be used. From the viewpoint of ease of handling, for example, a raw rubber-like polymer is used for hot vulcanized rubber, and a viscosity of 100 to 100000 is used for liquid rubber.
Polymers of the order of cs are preferably used. If the viscosity is too low, the resulting cured product will have a low elongation as an elastomer, and may not have balanced physical properties.
【００２８】上記式（１）の含フッ素アミド化合物は、
下記の方法により得ることができる。即ち、上記式
（１）においてａが０である含フッ素アミド化合物は、
例えば下記一般式（４）で示される両末端に酸フロライ
ド基を有する化合物と下記一般式（５）で示される一級
あるいは二級アミン化合物とをトリメチルアミン等の受
酸剤の存在下で反応させることにより合成することがで
きる。The fluorine-containing amide compound of the above formula (1) is
It can be obtained by the following method. That is, the fluorine-containing amide compound in which a is 0 in the formula (1) is
For example, a compound having an acid fluoride group at both terminals represented by the following general formula (4) and a primary or secondary amine compound represented by the following general formula (5) are reacted in the presence of an acid acceptor such as trimethylamine. Can be synthesized by
【００２９】[0029]
【化１３】 （Ｒ1，Ｒ2，Ｒｆは上記と同様の意味を示す。）Embedded image (R 1 , R 2 , and Rf have the same meaning as described above.)
【００３０】更に、上記式（１）においてａが１以上の
整数となる含フッ素アミド化合物は、例えば上記式
（４）に示される両末端に酸フロライド基を有する化合
物と下記一般式（６） Ｈ−Ｑ−Ｈ …（６） （Ｑは上記と同様の意味を示す。）で示されるジアミン
化合物とを受酸剤の存在下で反応させ、更に上記式
（５）で示される一級あるいは二級アミン化合物を反応
させることにより合成することができる。Further, the fluorine-containing amide compound in which a is an integer of 1 or more in the above formula (1) is, for example, a compound having an acid fluoride group at both terminals represented by the above formula (4) and the following general formula (6) HQH (6) (wherein Q has the same meaning as described above) is reacted with a diamine compound in the presence of an acid acceptor, and further reacted with a primary or secondary compound represented by the above formula (5). It can be synthesized by reacting a secondary amine compound.
【００３１】この場合、式（４）の両末端に酸フロライ
ド基を有する化合物と式（５）の一級あるいは二級アミ
ン化合物との仕込量の比率は、特に限定されるものでは
ないが、モル換算で式（４）の化合物の仕込量（ａ）と
式（５）の化合物の仕込量（ｂ）との比率（ａ）／
（ｂ）を０．１〜１．２ｍｏｌ／ｍｏｌ、特に０．２〜
０．５ｍｏｌ／ｍｏｌとすると好適である。In this case, the ratio of the charged amount of the compound having an acid fluoride group at both terminals of the formula (4) to the primary or secondary amine compound of the formula (5) is not particularly limited, but is In conversion, the ratio (a) / (a) / the charged amount (a) of the compound of the formula (4) and the charged amount (b) of the compound of the formula (5)
(B) is 0.1 to 1.2 mol / mol, especially 0.2 to
It is preferable that the concentration be 0.5 mol / mol.
【００３２】また、上記式（４）の化合物の仕込量
（ａ）と式（６）の化合物の仕込量（ｃ）とは、モル換
算で（ａ）を（ｃ）より少なくしない限り、特に限定さ
れるものではない。式（１）中の繰り返し単位ａは、
（ａ）／（ｃ）を調整することにより目的に応じた適宜
な値にすることができ、（ａ）／（ｃ）を大きくすれば
比較的分子量の小さなポリマーを合成することができ、
（ａ）／（ｃ）の値を１に近づければ分子量の大きなポ
リマーを合成することができる。The charged amount (a) of the compound of the formula (4) and the charged amount (c) of the compound of the formula (6) are not particularly limited as long as (a) is not smaller than (c) in terms of mole. It is not limited. The repeating unit a in the formula (1) is
By adjusting (a) / (c), an appropriate value according to the purpose can be obtained. By increasing (a) / (c), a polymer having a relatively small molecular weight can be synthesized,
When the value of (a) / (c) approaches 1, a polymer having a large molecular weight can be synthesized.
【００３３】上記反応の条件は、特に制限されないが、
２０〜１００℃で１〜８時間、好ましくは２０〜５０℃
で２〜４時間反応させることが好ましい。The conditions for the above reaction are not particularly limited.
20 to 100 ° C for 1 to 8 hours, preferably 20 to 50 ° C
For 2 to 4 hours.
【００３４】なお、式（１）の含フッ素アミド化合物に
おいて、Ｑがケイ素原子を介在するものである含フッ素
アミド化合物は、例えばビニル基、アリル基等の脂肪族
不飽和基を有する一級あるいは二級アミン化合物として
例えば式（５）のアミン化合物を使用して上記反応によ
り例えば下記一般式（７）で示される両末端にビニル基
を有する化合物を合成し、これと例えば下記一般式
（８）で示される、分子中にヒドロシリル基を２個有す
るオルガノシロキサン化合物とを付加反応触媒の存在下
で反応させることにより合成することができる。In the fluorinated amide compound of the formula (1), Q is one in which a silicon atom is interposed, for example, a primary or secondary amide compound having an aliphatic unsaturated group such as a vinyl group or an allyl group. For example, a compound having a vinyl group at both terminals represented by the following general formula (7) represented by the following general formula (7) is synthesized by the above reaction using, for example, an amine compound of the general formula (5) as a primary amine compound. Can be synthesized by reacting with an organosiloxane compound having two hydrosilyl groups in the molecule represented by the following formula in the presence of an addition reaction catalyst.
【００３５】[0035]
【化１４】 （但し、式中Ｒ1，Ｒ2，Ｒｆは前記と同様の意味を示
す。）Embedded image (However, in the formula, R 1 , R 2 , and Rf have the same meanings as described above.)
【００３６】 Ｈ−Ｐ−Ｈ …（８） 但し、式中Ｐはシロキサン結合を有する二価の有機基で
あり、具体的には下記の基が例示される。H—P—H (8) wherein P is a divalent organic group having a siloxane bond, and specific examples include the following groups.
【００３７】[0037]
【化１５】 Embedded image
【００３８】この反応で上記式（７）で示される両末端
にビニル基を有する化合物と式（８）の化合物との仕込
量との比率は、モル換算で式（７）の化合物の仕込量
（ｄ）を式（８）の化合物の仕込量（ｅ）より多くしな
くてはならないが、その比率（ｄ）／（ｅ）は最大で２
である。即ち、１＜（ｄ）／（ｅ）≦２である。In this reaction, the ratio of the charged amount of the compound having a vinyl group at both terminals represented by the above formula (7) to the compound of the formula (8) is calculated in terms of moles. (D) must be greater than the charge (e) of the compound of formula (8), but the ratio (d) / (e) is at most 2
It is. That is, 1 <(d) / (e) ≦ 2.
【００３９】なお、（ｄ）／（ｅ）を大きくすれば比較
的分子量の小さなポリマーを合成することができ、
（ｄ）／（ｅ）の値を１に近づければ分子量の大きなポ
リマーを合成することができる。By increasing (d) / (e), a polymer having a relatively small molecular weight can be synthesized.
When the value of (d) / (e) approaches 1, a polymer having a large molecular weight can be synthesized.
【００４０】この場合、上記触媒としては周期表第ＶＩ
ＩＩ族元素又はその化合物、例えば塩化白金酸、アルコ
ール変性塩化白金酸（米国特許第３２２０９７２号参
照）、塩化白金酸とオレフィンとの錯体（米国特許第３
１５９６０１号、同第３１５９６６２号、同第３７７５
４５２号参照）、白金黒又はパラジウム等をアルミナ、
シリカ、カーボン等の担体に担持させたもの、ロジウム
−オレフィン錯体、クロロトリス（トリフェニルホスフ
ィン）ロジウム（ウィルキンソン触媒）等を使用し得、
その添加量は触媒量とすることができる。上記の錯体は
アルコール系、ケトン系、エーテル系、炭化水素系の溶
剤に溶解して使用することが好ましい。[0040] In this case, the catalyst may be the VI in the periodic table.
Group II elements or compounds thereof, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972), complexes of chloroplatinic acid with olefins (U.S. Pat.
No. 159601, No. 3159662, No. 3775
No. 452), platinum black or palladium is alumina,
Silica, carbon-supported carrier, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson's catalyst), etc.
The addition amount can be a catalyst amount. The above complex is preferably used after being dissolved in an alcohol, ketone, ether or hydrocarbon solvent.
【００４１】また、上記反応の条件は、５０〜１５０
℃、好ましくは８０〜１２０℃で２〜４時間反応させる
ことが好ましい。The conditions for the above reaction are 50 to 150.
C., preferably at 80 to 120.degree. C. for 2 to 4 hours.
【００４２】次に、本発明の第二必須成分［（Ｂ）成
分］は含フッ素オルガノ水素シロキサンであり、上記含
フッ素アミド化合物の架橋剤、鎖長延長剤として働くも
のである。この（Ｂ）成分の含フッ素オルガノ水素シロ
キサンは、一分子中に一個以上の一価のパーフルオロオ
キシアルキル基、一価のパーフルオロアルキル基、二価
のパーフルオロオキシアルキレン基又は二価のパーフロ
ロアルキレン基を有し、且つ二個以上、好ましくは３個
以上のヒドロシリル基、即ちＳｉ−Ｈ基を有するもので
あれば良い。このパーフルオロオキシアルキル基、パー
フルオロアルキル基、パーフルオロオキシアルキレン
基、パーフロロアルキレン基としては、特に下記一般式
で示されるものを挙げることができる。The second essential component (component (B)) of the present invention is a fluorine-containing organohydrogensiloxane, which functions as a crosslinking agent and a chain extender for the above-mentioned fluorine-containing amide compound. The fluorine-containing organohydrogensiloxane of the component (B) has one or more monovalent perfluorooxyalkyl group, monovalent perfluoroalkyl group, divalent perfluorooxyalkylene group or divalent perfluorooxyalkyl group in one molecule. Any material having a fluoroalkylene group and having two or more, preferably three or more hydrosilyl groups, that is, Si—H groups may be used. Examples of the perfluorooxyalkyl group, perfluoroalkyl group, perfluorooxyalkylene group, and perfluoroalkylene group include those represented by the following general formula.
【００４３】[0043]
【化１６】 Embedded image
【００４４】この含フッ素オルガノ水素シロキサンとし
ては、環状でも鎖状でもよく、更に三次元網状でもよ
く、特にケイ素原子に結合した一価の置換基として下記
一般式で示されるパーフルオロアルキル基、パーフルオ
ロアルキルエーテル基あるいはパーフロロアルキレン基
を含有する一価の有機基を分子中に少なくとも１個有す
るものを挙げることができる。The fluorinated organohydrogensiloxane may be cyclic or chain, and may be three-dimensional network. Particularly, as a monovalent substituent bonded to a silicon atom, a perfluoroalkyl group or a perfluoroalkyl group represented by the following general formula: Examples include those having at least one monovalent organic group containing a fluoroalkyl ether group or a perfluoroalkylene group in a molecule.
【００４５】[0045]
【化１７】 Embedded image
【００４６】ここで、Ｒ6はメチレン基、エチレン基、
プロピレン基、メチルエチレン基、テトラメチレン基、
ヘキサメチレン基等のアルキレン基、フェニレン基等の
アリーレン基などの好ましくは炭素数１〜１０、特に２
〜６の二価炭化水素基、Ｒ7は水素原子あるいは前記し
たＲ2と同様の好ましくは炭素数１〜８、特に１〜６の
一価炭化水素基、Ｒｆ1 は前記一般式で挙げた一価のパ
ーフルオロアルキル基、一価のパーフルオロオキシアル
キル基、二価のパーフルオロオキシアルキレン基又は二
価のパーフロロアルキレン基である。Where R6Is a methylene group, an ethylene group,
Propylene group, methylethylene group, tetramethylene group,
Alkylene group such as hexamethylene group, phenylene group
Preferably, it has 1 to 10 carbon atoms, particularly 2
To 6 divalent hydrocarbon groups, R7Is a hydrogen atom or
RTwoAs described above, preferably having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms
Monovalent hydrocarbon group, Rf1 Is the monovalent compound listed in the above general formula.
-Fluoroalkyl group, monovalent perfluorooxyal
A kill group, a divalent perfluorooxyalkylene group or
Is a monovalent perfluoroalkylene group.
【００４７】また、この（Ｂ）成分の含フッ素オルガノ
水素シロキサンにおける一価又は二価の含フッ素置換
基、即ちパーフルオロアルキル基、パーフルオロオキシ
アルキル基、パーフルオロオキシアルキレン基あるいは
パーフロロアルキレン基を含有する一価の有機基以外の
ケイ素原子に結合した一価の置換基としては、前記した
Ｒ2と同様の好ましくは脂肪族不飽和結合を含まない炭
素数１〜１０、特に１〜８の一価炭化水素基が挙げられ
る。Further, a monovalent or divalent fluorine-containing substituent in the fluorine-containing organohydrogensiloxane of the component (B), that is, a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluorooxyalkylene group or a perfluoroalkylene group As the monovalent substituent bonded to a silicon atom other than the monovalent organic group containing the same, preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms not containing an aliphatic unsaturated bond, as described above for R 2. A monovalent hydrocarbon group.
【００４８】この含フッ素オルガノ水素シロキサンにお
ける分子中のケイ素原子数はこれに限られるものではな
いが、通常２〜６０、好ましくは４〜３０程度のものが
挙げられる。The number of silicon atoms in the molecule in the fluorinated organohydrogensiloxane is not limited to this, but usually 2 to 60, preferably about 4 to 30.
【００４９】このような含フッ素オルガノ水素シロキサ
ンとしては、例えば下記の化合物が挙げられ、Ｍｅはメ
チル基、Ｐｈはフェニル基を示す。なお、これらの化合
物は、単独で使用しても良く、併用しても良い。Examples of such a fluorine-containing organohydrogensiloxane include the following compounds. Me represents a methyl group and Ph represents a phenyl group. These compounds may be used alone or in combination.
【００５０】[0050]
【化１８】 Embedded image
【００５１】[0051]
【化１９】 Embedded image
【００５２】なお、本発明の硬化性組成物は、第二必須
成分の含フッ素オルガノ水素シロキサンとして第一必須
成分の含フッ素アミド化合物と相溶するものを使用する
ことにより、均一な硬化物を得ることができる。The curable composition of the present invention can be used to obtain a uniform cured product by using a fluorine-containing organohydrogensiloxane as the second essential component that is compatible with the fluorinated amide compound as the first essential component. Obtainable.
【００５３】上記（Ｂ）成分の配合量は組成物全系、特
に（Ａ）成分中に含まれるビニル基、アリル基、シクロ
アルケニル基等の脂肪族不飽和基１モルに対し（Ｂ）成
分中のヒドロシリル基、即ちＳｉ−Ｈ基を、好ましくは
０．５〜５モル、より好ましくは１〜２モル供給する量
である。０．５モル未満では架橋度合いが不充分にな
り、５モル以上では鎖長延長が優先し硬化が不充分とな
ったり、発泡したり、耐熱性、圧縮永久歪特性等を悪化
させる場合がある。なお、この（Ｂ）成分の（Ａ）成分
に対する配合量は、通常、（Ａ）成分１００重量部に対
して０．１〜５０重量部の範囲とすることもできる。The amount of the component (B) is based on 1 mole of the aliphatic unsaturated group such as vinyl group, allyl group and cycloalkenyl group contained in the component (A). The amount of the hydrosilyl group, i.e., Si-H group, is preferably 0.5 to 5 mol, more preferably 1 to 2 mol. If the amount is less than 0.5 mol, the degree of crosslinking is insufficient, and if the amount is 5 mol or more, the chain length is prioritized and curing is insufficient, foaming, heat resistance, compression set properties and the like may be deteriorated. . The amount of the component (B) to be added to the component (A) can be usually in the range of 0.1 to 50 parts by weight based on 100 parts by weight of the component (A).
【００５４】更に、本発明の第三必須成分［（Ｃ）成
分］である白金族化合物は、上記含フッ素アミド化合物
と上記含フッ素オルガノ水素シロキサンとの付加反応
（ヒドロシリル化）用触媒であり、硬化促進剤として作
用する。この白金族化合物は一般に貴金属の化合物であ
り、高価格であることから、比較的入手しやすい白金化
合物がよく用いられる。The platinum group compound, which is the third essential component [component (C)] of the present invention, is a catalyst for an addition reaction (hydrosilylation) between the above-mentioned fluorinated amide compound and the above-mentioned fluorinated organohydrogensiloxane, Acts as a hardening accelerator. This platinum group compound is generally a compound of a noble metal and is expensive, so a platinum compound which is relatively easily available is often used.
【００５５】白金化合物としては、例えば塩化白金酸又
は塩化白金酸とエチレン等のオレフィンとの錯体、アル
コールやビニルシロキサンとの錯体、白金／シリカ又は
アルミナ又はカーボン等を例示することができるが、こ
れらに限定されるものではない。白金化合物以外の白金
族化合物としては、ロジウム、ルテニウム、イリジウ
ム、パラジウム系化合物も知られており、例えばＲｈＣ
ｌ（ＰＰｈ3）3，ＲｈＣｌ（ＣＯ）（ＰＰｈ3）2，Ｒｈ
Ｃｌ（Ｃ2Ｈ4）2，Ｒｕ3（ＣＯ）12，ＩｒＣｌ（ＣＯ）
（ＰＰｈ3）2，Ｐｄ（ＰＰｈ3）4等を例示することがで
きる。Examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid with an olefin such as ethylene, a complex of alcohol or vinyl siloxane, platinum / silica, alumina or carbon. However, the present invention is not limited to this. As platinum group compounds other than platinum compounds, rhodium, ruthenium, iridium and palladium compounds are also known.
1 (PPh 3 ) 3 , RhCl (CO) (PPh 3 ) 2 , Rh
Cl (C 2 H 4 ) 2 , Ru 3 (CO) 12 , IrCl (CO)
(PPh 3 ) 2 , Pd (PPh 3 ) 4 and the like.
【００５６】これらの触媒の使用にあたっては、それが
固体触媒であるときには固体状で使用することも可能で
あるが、より均一な硬化物を得るために塩化白金酸や錯
体を適切な溶剤に溶解したものを第一成分の含フッ素ア
ミド化合物に相溶させて使用することが好ましい。In the use of these catalysts, when they are solid catalysts, they can be used in solid form. However, in order to obtain a more uniform cured product, chloroplatinic acid or a complex is dissolved in an appropriate solvent. It is preferable to use the compound obtained by compatibilizing the fluorinated amide compound as the first component.
【００５７】これらの触媒の使用量は、特に制限するも
のではなく、触媒量で所望とする硬化速度を得ることが
できるが、経済的見地又は良好な硬化物を得るために
は、硬化性組成物全量に対して１〜１０００ｐｐｍ（白
金族換算）、より好ましくは１０〜５００ｐｐｍ（同
上）程度の範囲とするのが良い。The amount of the catalyst used is not particularly limited, and a desired curing rate can be obtained with the amount of the catalyst. However, in order to obtain an economical viewpoint or a good cured product, the curable composition must be used. The amount is preferably in the range of about 1 to 1000 ppm (in terms of platinum group), more preferably about 10 to 500 ppm (as described above), based on the total amount of the substance.
【００５８】なお、本発明の硬化性組成物には、その実
用性を高めるために種々の添加剤を必要に応じて添加す
ることができる。具体的には、硬化性組成物の硬化速度
を制御する目的で加えるＣＨ2＝ＣＨ（Ｒ）ＳｉＯ単位
（式中、Ｒは水素原子又は置換又は非置換の一価炭化水
素基である。）を含むポリシロキサン（特公昭４８−１
０９４７号公報参照）及びアセチレン化合物（米国特許
第３４４５４２０号及び特公昭５４−３７７４号公報参
照）、さらに重金属のイオン性化合物（米国特許第３５
３２６４９号参照）等を例示することができる。Various additives can be added to the curable composition of the present invention, if necessary, in order to enhance its practicality. Specifically, CH 2 ＣＨCH (R) SiO units added for the purpose of controlling the curing rate of the curable composition (where R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group). -Containing polysiloxane (Japanese Patent Publication No. 48-1)
No. 0947) and acetylene compounds (see U.S. Pat. No. 3,445,420 and Japanese Patent Publication No. 54-3774), and ionic compounds of heavy metals (U.S. Pat.
No. 32649) and the like.
【００５９】これらの添加剤を添加した場合において、
含フッ素オルガノ水素シロキサンの配合量は、（Ａ）成
分に加えてこれら添加剤の配合量をも考慮して決定さ
れ、上述したように、全組成物中のビニル基、アリル
基、シクロアルケニル基等の脂肪族不飽和基１モルに対
してＳｉ−Ｈ基を０．５〜５モル存在させる必要があ
る。When these additives are added,
The blending amount of the fluorine-containing organohydrogensiloxane is determined in consideration of the blending amounts of these additives in addition to the component (A), and as described above, the vinyl group, allyl group, cycloalkenyl group in the total composition. It is necessary that 0.5 to 5 mol of Si—H groups be present per 1 mol of the aliphatic unsaturated group such as described above.
【００６０】更に、本発明の硬化性組成物には、硬化時
における熱収縮の減少、硬化して得られる弾性体の熱膨
張率の低下、熱安定性、耐候性、耐薬品性、難燃性ある
いは機械的強度を向上させたり、ガス透過率を下げる目
的で充填剤を添加しても良く、例えばヒュームドシリ
カ、石英粉末、ガラス繊維、カーボン、酸化鉄、酸化チ
タン及び酸化セリウム等の金属酸化物、炭酸カルシウ
ム、炭酸マグネシウム等の金属炭酸塩を挙げることがで
き、更に必要に応じて適当な顔料、染料あるいは酸化防
止剤を添加することも可能である。Further, the curable composition of the present invention has a reduced heat shrinkage during curing, a reduced coefficient of thermal expansion of an elastic material obtained by curing, heat stability, weather resistance, chemical resistance, and flame retardancy. A filler may be added for the purpose of improving the properties or mechanical strength or lowering the gas permeability, such as fumed silica, quartz powder, glass fiber, carbon, iron oxide, titanium oxide, and cerium oxide. Oxides, metal carbonates such as calcium carbonate, magnesium carbonate and the like can be mentioned, and if necessary, suitable pigments, dyes or antioxidants can be added.
【００６１】本発明の硬化性組成物の製造方法は特に制
限されず、上記成分を練り合わせることにより製造する
ことができる。製造された硬化性組成物は、第一必須成
分の含フッ素アミド化合物の官能基、第三必須成分の触
媒の種類により室温硬化も可能であるが、１００〜１５
０℃にて数分から数時間程度の時間で硬化させることが
好ましい。The method for producing the curable composition of the present invention is not particularly limited, and it can be produced by kneading the above components. The produced curable composition can be cured at room temperature depending on the functional group of the fluorine-containing amide compound as the first essential component and the type of the catalyst as the third essential component.
It is preferable to cure at 0 ° C. for several minutes to several hours.
【００６２】なお、本発明の硬化性組成物を使用するに
当たり、その用途、目的に応じて該組成物を適当なフッ
素系溶剤、例えばメタキシレンヘキサフロライド、フロ
リナート等に所望の濃度に溶解して使用しても良い。In using the curable composition of the present invention, the composition is dissolved in a suitable fluorine-based solvent, for example, meta-xylene hexafluoride, florinate, or the like, to a desired concentration depending on the use and purpose. May be used.
【００６３】[0063]
【発明の効果】本発明の硬化性組成物は、種々の用途に
利用することができる。即ち、本発明の硬化性組成物に
より得られる硬化物は、フッ素含有率が高いため、耐溶
剤性、耐薬品性に優れ、また、透湿性も低く、しかも低
表面エネルギーを有するため離型性、撥水性に優れてお
り、耐油性を要求される自動車用ゴム材料、テント膜材
料、シーラント、成形部品、押出部品、被覆材料、複写
機ロール材料、電気用防湿コーティング材料等として有
効に使用することができる。The curable composition of the present invention can be used for various uses. That is, the cured product obtained from the curable composition of the present invention has a high fluorine content, so that it has excellent solvent resistance and chemical resistance, has low moisture permeability, and has a low surface energy. Effectively used as automotive rubber materials, tent film materials, sealants, molded parts, extruded parts, coating materials, copier roll materials, electric moisture-proof coating materials, etc., which have excellent water repellency and oil resistance. be able to.
【００６４】[0064]
【実施例】以下、実施例を示して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、以下においてＭｅはメチル基を示す。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the following, Me indicates a methyl group.
【００６５】［実施例１］下記式（９）で示されるポリ
マー（粘度９５００ｃｓ、平均分子量５７２０、ビニル
基量０．０３５モル／１００ｇ）１００重量部にトリメ
チルシロキシ基で処理された比表面積２００ｍ2／ｇの
煙霧質シリカ１０重量部を加え、混合、熱処理した後、
三本ロールミル上にて混合し、更に、下記式（１０）で
示される含フッ素環状水素シロキサン４５．０重量部、
塩化白金酸をＣＨ2＝ＣＨＳｉＭｅ2ＯＳｉＭｅ2ＣＨ＝
ＣＨ2で変性した触媒のトルエン溶液（白金濃度１．０
重量％）０．２重量部を加え、混合した。[Example 1] A polymer represented by the following formula (9) (viscosity: 9500 cs, average molecular weight: 5720, vinyl group content: 0.035 mol / 100 g) was treated with a trimethylsiloxy group on 100 parts by weight, and the specific surface area was 200 m 2. / G of fumed silica / g, and after mixing and heat treatment,
The mixture was mixed on a three-roll mill, and further 45.0 parts by weight of a fluorinated cyclic hydrogen siloxane represented by the following formula (10):
Chloroplatinic acid is converted to CH 2 ＣＨCHSiMe 2 OSiMe 2 CH =
A toluene solution of a catalyst modified with CH 2 (platinum concentration 1.0
0.2% by weight) and mixed.
【００６６】[0066]
【化２０】 Embedded image
【００６７】これを減圧下で脱泡し、２ｍｍ厚の長方形
の枠に置き、再び空気抜きをし、１２０ｋｇ／ｃｍ2、
１５０℃で１０分間プレス硬化した。試験片を硬化した
試料から切り取り、ＪＩＳ Ｋ６３０１に準じて物性を
測定したところ、以下に示す結果を得た。This was defoamed under reduced pressure, placed in a rectangular frame having a thickness of 2 mm, evacuated again, and dried at 120 kg / cm 2 ,
Press hardening was performed at 150 ° C. for 10 minutes. The test piece was cut out from the cured sample, and the physical properties were measured in accordance with JIS K6301, and the following results were obtained.
【００６８】 硬さ（ＪＩＳ−Ａ） ４６ 伸び（％） ２４０ 引っ張り強さ（ｋｇｆ／ｃｍ2） ５９ （ＪＩＳ−Ａ：ＪＩＳ Ｋ６３０１に規定のＡ型スプリ
ング式硬さ試験機を使用して測定）Hardness (JIS-A) 46 Elongation (%) 240 Tensile strength (kgf / cm 2 ) 59 (JIS-A: Measured using an A-type spring hardness tester specified in JIS K6301)
【００６９】次に、上記試験片を用いて、耐熱性、耐薬
品性、溶剤膨潤性、低温特性及び透湿性を測定した。そ
れらの結果を表１、表２、表３、表４及び表５に示す。Next, heat resistance, chemical resistance, solvent swellability, low-temperature characteristics and moisture permeability were measured using the test pieces. The results are shown in Table 1, Table 2, Table 3, Table 4, and Table 5.
【００７０】[0070]
【表１】 [Table 1]
【００７１】[0071]
【表２】 [Table 2]
【００７２】[0072]
【表３】 [Table 3]
【００７３】[0073]
【表４】 [Table 4]
【００７４】[0074]
【表５】 [Table 5]
【００７５】［実施例２］実施例１のポリマーの代わり
に下記式（１１）で示されるポリマー（粘度２１０００
ｃｓ、平均分子量１６０００、ビニル基量０．０１３モ
ル／１００ｇ）を使用し、実施例１の含フッ素環状水素
シロキサン１６．３重量部を使用した以外は実施例１と
同様に組成物を調製し、硬化シートを作成した。Example 2 Instead of the polymer of Example 1, a polymer represented by the following formula (11) (having a viscosity of 21000)
cs, average molecular weight of 16000, vinyl group content of 0.013 mol / 100 g), and a composition was prepared in the same manner as in Example 1 except that 16.3 parts by weight of the fluorinated cyclic hydrogen siloxane of Example 1 was used. , To prepare a cured sheet.
【００７６】[0076]
【化２１】 Embedded image
【００７７】得られた硬化シートの試験片を切り取り、
上記と同様に物性を測定したところ、以下に示す結果を
得た。A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.
【００７８】 硬さ（ＪＩＳ−Ａ） ３３ 伸び（％） ４１０ 引っ張り強さ（ｋｇｆ／ｃｍ2） ３２Hardness (JIS-A) 33 Elongation (%) 410 Tensile strength (kgf / cm 2 ) 32
【００７９】［実施例３］実施例１のポリマーの代わり
に下記式（１２）で示されるポリマー（粘度１２８６０
０ｃｓ、平均分子量２３０００、ビニル基量０．００９
モル／１００ｇ）１００重量部を使用し、実施例１の含
フッ素環状水素シロキサン１１．６重量部を使用した以
外は実施例１と同様にして組成物を調製し、硬化シート
を作成した。Example 3 Instead of the polymer of Example 1, a polymer represented by the following formula (12) (having a viscosity of 12860)
0cs, average molecular weight 23000, vinyl group content 0.009
A composition was prepared in the same manner as in Example 1 except that 100 parts by weight (mol / 100 g) was used and 11.6 parts by weight of the fluorinated cyclic hydrogen siloxane of Example 1 was used to prepare a cured sheet.
【００８０】[0080]
【化２２】 Embedded image
【００８１】得られた硬化シートの試験片を切り取り、
上記と同様に物性を測定したところ、以下に示す結果を
得た。A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.
【００８２】 硬さ（ＪＩＳ−Ａ） ３１ 伸び（％） ３９０ 引っ張り強さ（ｋｇｆ／ｃｍ2） ４０Hardness (JIS-A) 31 Elongation (%) 390 Tensile strength (kgf / cm 2 ) 40
【００８３】［実施例４］実施例１のポリマーの代わり
に下記式（１３）で示されるポリマー（粘度６５１００
ｃｓ、平均分子量２７６４０、ビニル基量０．００７モ
ル／１００ｇ）１００重量部を使用し、実施例１の含フ
ッ素環状水素シロキサン９．０重量部を使用した以外は
実施例１と同様にして組成物を調製し、硬化シートを作
成した。Example 4 Instead of the polymer of Example 1, a polymer represented by the following formula (13) (having a viscosity of 65100
cs, average molecular weight 27640, vinyl group content 0.007 mol / 100 g) 100 parts by weight, and the same composition as in Example 1 except that 9.0 parts by weight of the fluorinated cyclic hydrogen siloxane of Example 1 was used. An article was prepared and a cured sheet was prepared.
【００８４】[0084]
【化２３】 Embedded image
【００８５】得られた硬化シートの試験片を切り取り、
上記と同様に物性を測定したところ、以下に示す結果を
得た。A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.
【００８６】 硬さ（ＪＩＳ−Ａ） ３５ 伸び（％） ４５０ 引っ張り強さ（ｋｇｆ／ｃｍ2） ４９Hardness (JIS-A) 35 Elongation (%) 450 Tensile strength (kgf / cm 2 ) 49
【００８７】[0087]
【００８８】[0088]
【００８９】[0089]
【００９０】[0090]
【００９１】[0091]
【００９２】[0092]
【００９３】［参考例１］下記式（１６）で示される両
末端に酸フロライド基を有する化合物１０００ｇを撹拌
棒、温度計、ジムロート、滴下ロートを付した１リット
ルの四つ口フラスコ内に仕込み、撹拌しながら滴下ロー
トより下記式（１７）で示されるビニルシリルアニリン
７２．０ｇとトリエチルアミン４４．８ｇとの混合物を
２０℃にて滴下した。Reference Example 1 1000 g of a compound having an acid fluoride group at both terminals represented by the following formula (16) was charged into a 1-liter four-necked flask equipped with a stir bar, a thermometer, a Dim funnel, and a dropping funnel. While stirring, a mixture of 72.0 g of vinylsilylaniline represented by the following formula (17) and 44.8 g of triethylamine was added dropwise at 20 ° C. from the dropping funnel.
【００９４】[0094]
【化２５】 Embedded image
【００９５】滴下後に６０℃にて反応を２時間行い、反
応混合物を加圧濾過して得られた濾液を１２０℃／３ｍ
ｍＨｇで減圧ストリップしたところ、淡黄色透明な液状
化合物９８９．５ｇが得られた。After the dropwise addition, the reaction was carried out at 60 ° C. for 2 hours, and the reaction mixture was filtered under pressure to obtain a filtrate obtained at 120 ° C./3 m
Stripping under reduced pressure at mHg yielded 989.5 g of a pale yellow transparent liquid compound.
【００９６】得られた化合物は、粘度９５００ｃｓ（２
５℃）、比重１．８２９（２５℃）、屈折率１．３２５
８（２５℃）であった。この化合物をＩＲ測定した結
果、以下に示す吸収が認められた。The obtained compound had a viscosity of 9500 cs (2
5 ° C.), specific gravity 1.829 (25 ° C.), refractive index 1.325
8 (25 ° C.). As a result of IR measurement of this compound, the following absorptions were recognized.
【００９７】[0097]
【化２６】 Embedded image
【００９８】また、この化合物のビニル基量を定量した
ところ、０．０３５モル／１００ｇであり、得られた化
合物は、下記構造式（１８）で示される有機フッ素化合
物のポリマーであることが確認された。The amount of vinyl groups of this compound was determined to be 0.035 mol / 100 g. It was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (18). Was done.
【００９９】[0099]
【化２７】 Embedded image
【０１００】［参考例２］下記式（１９）で示される両
末端に酸フロライド基を有する化合物５００ｇを撹拌
棒、温度計、ジムロート、滴下ロートを付した５００ｍ
ｌの四つ口フラスコ内に仕込み、撹拌しながら滴下ロー
トより上記式（１７）で示されるビニルシリルアニリン
１２．４ｇとトリエチルアミン７．７ｇとの混合物を２
０℃にて滴下した。Reference Example 2 500 g of a compound represented by the following formula (19) having an acid fluoride group at both terminals was attached to a stirring bar, a thermometer, a Dim funnel, and a dropping funnel.
of a vinylsilylaniline represented by the above formula (17) and 7.7 g of triethylamine from a dropping funnel while stirring.
It was added dropwise at 0 ° C.
【０１０１】[0101]
【化２８】 Embedded image
【０１０２】滴下後に６０℃にて反応を２時間行い、反
応混合物を加圧濾過して得られた濾液を１２０℃／３ｍ
ｍＨｇで減圧ストリップしたところ、淡黄色透明な液状
化合物４６９．４ｇが得られた。After the dropwise addition, the reaction was carried out at 60 ° C. for 2 hours, and the reaction mixture was subjected to pressure filtration to obtain a filtrate obtained at 120 ° C./3 m
After stripping under reduced pressure at mHg, 469.4 g of a pale yellow transparent liquid compound was obtained.
【０１０３】得られた化合物は、粘度２１０００ｃｓ
（２５℃）、比重１．８８４（２５℃）、屈折率１．３
１３６（２５℃）であった。この化合物をＩＲ測定した
結果、以下に示す吸収が認められた。The obtained compound had a viscosity of 21,000 cs.
(25 ° C.), specific gravity 1.884 (25 ° C.), refractive index 1.3
136 (25 ° C.). As a result of IR measurement of this compound, the following absorptions were recognized.
【０１０４】[0104]
【化２９】 Embedded image
【０１０５】また、この化合物のビニル基量を定量した
ところ、０．０１３モル／１００ｇであり、得られた化
合物は、下記構造式（２０）で示される有機フッ素化合
物のポリマーであることが確認された。The amount of vinyl groups in this compound was determined to be 0.013 mol / 100 g. The obtained compound was confirmed to be a polymer of an organic fluorine compound represented by the following structural formula (20). Was done.
【０１０６】[0106]
【化３０】 Embedded image
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松田 高至 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 (72)発明者 山本 靖 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 (56)参考文献 特開 平８−104862（ＪＰ，Ａ) 特開 平６−271765（ＪＰ，Ａ) 特開 平６−234923（ＪＰ，Ａ) 特開 平６−256500（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 71/00 - 71/02 C08L 83/00 - 83/16 C08G 65/32 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koji Matsuda 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Yasushi Yasushi, Gunma Prefecture No. 1 Hitomi, Matsuida-machi, Shin-Etsu Chemical Co., Ltd. Inside Silicone Electronic Materials Technology Research Laboratory (56) References JP-A-8-100462 (JP, A) JP-A-6-271765 (JP, A) 6-234923 (JP, A) JP-A-6-256500 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C08L 71/00-71/02 C08L 83/00-83 / 16 C08G 65/32
Claims (2)
ッ素アミド化合物、 【化１】 ［但し、式中Ｒ1は置換又は非置換の一価炭化水素基、
Ｒ2は水素原子又は置換又は非置換の一価炭化水素基、
Ｑは下記一般式（２）又は下記一般式（３）で示される
基 【化２】 （但し、式中Ｒ3は結合途中に酸素原子、窒素原子及び
ケイ素原子の１種又は２種以上を介在させてもよい置換
又は非置換の二価炭化水素基を示す。） 【化３】 （但し、式中Ｒ4及びＲ5はそれぞれ置換又は非置換の二
価炭化水素基を示す。）、Ｒｆは二価のパーフルオロア
ルキレン基又は二価のパーフルオロポリエーテル基であ
り、ａは０以上の整数である。］ （Ｂ）一分子中に一個以上の一価のパーフルオロオキシ
アルキル基、一価のパーフルオロアルキル基、二価のパ
ーフルオロオキシアルキレン基又は二価のパーフロロア
ルキレン基を有し、且つ二個以上のヒドロシリル基を有
する含フッ素オルガノ水素シロキサン、 （Ｃ）触媒量の白金族化合物を含有する組成物であっ
て、上記（Ｂ）成分の量は該組成物中の脂肪族不飽和基
１モルに対し、ヒドロシリル（Ｓｉ−Ｈ）基が０．５〜
５モルとなる量であることを特徴とする硬化性組成物。(A) a fluorine-containing amide compound represented by the following general formula (1): Wherein R 1 is a substituted or unsubstituted monovalent hydrocarbon group,
R 2 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group,
Q is a group represented by the following general formula (2) or the following general formula (3): (However, in the formula, R 3 represents a substituted or unsubstituted divalent hydrocarbon group in which one or more of an oxygen atom, a nitrogen atom and a silicon atom may be interposed in the bond.) (Wherein R 4 and R 5 each represent a substituted or unsubstituted divalent hydrocarbon group), Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and a is It is an integer of 0 or more. (B) one molecule has one or more monovalent perfluorooxyalkyl group, monovalent perfluoroalkyl group, divalent perfluorooxyalkylene group or divalent perfluoroalkylene group; (C) a composition containing a catalytic amount of a platinum group compound, wherein the amount of the component (B) is one or more of the number of aliphatic unsaturated groups in the composition. Hydrosilyl (Si-H) group is 0.5 to
A curable composition having an amount of 5 mol.
キサンが、下記式（ｉ）〜（ｉｖ）で示されるいずれか
の有機基を分子中に少なくとも１個有するものである請
求項１記載の硬化性組成物。 （式中、Ｒ6は、炭素数１〜１０の二価炭化水素基、Ｒ7
は水素原子又は炭素数１〜８の一価炭化水素基、Ｒｆ1
は、式（ｉ），（ｉｉ）の場合、 ＣmＦ2m+1−（ｍは１〜２０の整数）又は であり、式（ｉｉｉ），（ｉｖ）の場合、−ＣmＦ2m−
（ｍは１〜２０の整数）又は である。）2. The composition according to claim 1, wherein the fluorine-containing organohydrogensiloxane of the component (B) has at least one organic group represented by any of the following formulas (i) to (iv) in the molecule. Curable composition. (Wherein, R 6 is a divalent hydrocarbon group having 1 to 10 carbon atoms, R 7
Is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, Rf 1
Is C m F 2m + 1 − (m is an integer of 1 to 20) in the case of formulas (i) and (ii), or In the case of the formulas (iii) and (iv), −C m F 2m −
(M is an integer of 1 to 20) or It is. )
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7027296A JP2990646B2 (en) | 1995-01-23 | 1995-01-23 | Curable composition |
| DE69610445T DE69610445T2 (en) | 1995-01-23 | 1996-01-23 | Fluorinated amide silicone compounds and crosslinkable siloxane compositions |
| US08/590,318 US5665846A (en) | 1995-01-23 | 1996-01-23 | Fluorinated amide compounds and curable compositions |
| EP96300438A EP0725113B1 (en) | 1995-01-23 | 1996-01-23 | Fluorinated amide silicone compounds and curable siloxane compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7027296A JP2990646B2 (en) | 1995-01-23 | 1995-01-23 | Curable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08199070A JPH08199070A (en) | 1996-08-06 |
| JP2990646B2 true JP2990646B2 (en) | 1999-12-13 |
Family
ID=12217133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7027296A Expired - Fee Related JP2990646B2 (en) | 1995-01-23 | 1995-01-23 | Curable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2990646B2 (en) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6528562B2 (en) | 2000-07-10 | 2003-03-04 | Shin-Etsu Chemical Co., Ltd. | Curable fluoropolyether rubber compositions |
| US6552152B2 (en) | 2000-06-29 | 2003-04-22 | Shin-Etsu Chemical Co., Ltd. | Curable fluoropolyether rubber compositions |
| EP1605018A1 (en) | 2004-06-11 | 2005-12-14 | Shin-Etsu Chemical Co., Ltd. | Curable perfluoropolyether compositions and rubber or gel articles comprising the same |
| US6979710B2 (en) | 2002-11-19 | 2005-12-27 | Shin-Etsu Chemical Co., Ltd. | Curable fluoropolyether rubber compositions and rubber articles |
| EP1616895A1 (en) | 2004-07-12 | 2006-01-18 | Shinetsu Chemical Co., Ltd. | Primer composition for a fluorinated elastomer or a fluorinated gel |
| WO2006068099A1 (en) * | 2004-12-20 | 2006-06-29 | Nippon Valqua Industries, Ltd. | Rubber composition and sealing material for plasma treatment device |
| US7081508B2 (en) | 2004-06-25 | 2006-07-25 | Shin-Etsu Chemical Co., Ltd. | Primer composition |
| US7091279B2 (en) | 2002-08-15 | 2006-08-15 | Shin-Etsu Chemical Co., Ltd. | Curable fluoropolyether rubber compositions and rubber articles |
| US7332538B2 (en) | 2003-03-06 | 2008-02-19 | Shin-Etsu Chemical Co., Ltd. | Heat-curable fluoropolyether rubber compositions and rubber articles |
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