JP5447352B2 - Fluorine-containing curable composition - Google Patents

Description

  The present invention is self-flowing at room temperature (25 ° C.), is easy to mold, has excellent heat resistance, chemical resistance, solvent resistance and mechanical strength, and particularly improves tear strength while maintaining hardness. The present invention relates to a fluorine-containing curable composition that gives a cured perfluoropolyether-based fluororubber cured product (elastic body).

  A linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, and at least two hydrogen atoms bonded to a silicon atom in one molecule It is possible to obtain a cured product excellent in heat resistance, chemical resistance, solvent resistance, releasability, water repellency, oil repellency, weather resistance, etc. from a composition comprising an organosilicon compound having a hydrosilylation reaction catalyst Japanese Patent No. 2990646 (Patent Document 1) and the like.

  This cured product has sufficient performance for most applications, but for use in applications where durability against bending stress and shear stress is required, further improvement in tear strength is required. It was sought after.

  The tear strength can be improved by reducing the crosslink density. However, the hardness is lowered and a bad feeling such as a feeling of sag occurs. In order to compensate for this, if the amount of filler such as filler is increased, a decrease in hardness and a feeling of sag can be suppressed, but a new problem that the viscosity when uncured significantly increases occurs.

Japanese Patent No. 2990646 Japanese Patent No. 3968944 JP 2005-200481 A JP 2006-36973 A

  The present invention has been made in view of the above circumstances, and is a perfluoropolyether type which is easy to mold with low viscosity, excellent in heat resistance, chemical resistance, solvent resistance and mechanical strength, and further improved in tear strength. It aims at providing the fluorine-containing curable composition which gives a fluororubber hardened | cured material (elastic body).

  In order to prevent the hardness of the cured product from being lowered, a method of blending a small amount of a compound having a plurality of alkenyl groups has been disclosed (Japanese Patent No. 396894, Japanese Patent Application Laid-Open No. 2005-200481, Japanese Patent Application Laid-Open No. 2006-36973). : Patent Documents 2 to 4). This method increases the hardness by increasing the crosslinking density. In order to achieve the above-mentioned object, the present inventors have taken this knowledge and intensively studied. As a result, the composition is blended into the composition in a balanced manner with a component that increases the crosslinking density and a component that decreases the crosslinking density. It has been found that the cured product can improve the tear strength while maintaining the same hardness as the cured product in which these components are not blended.

That is, (a) a perfluoropolyester having at least two alkenyl groups in one molecule and containing a repeating unit of -C _a F _2a O- (a is an integer of 1 to 6) in the main chain. A linear perfluoropolyether compound having an ether structure and a number average molecular weight of 5,000 to 100,000, (b) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule; c) Hydrosilylation reaction catalyst, (d) Silica-based filler having a BET specific surface area of 30 m ² / g or more, (e) Number having one alkenyl group in one molecule and having a perfluoropolyether structure A linear perfluoropolyether compound having an average molecular weight of 500 to 20,000, (f) having at least three alkenyl groups in one molecule and having a number average molecular weight of less than 5,000 It contains a polyfunctional alkenyl group-containing compound, and the molar ratio of the amount of alkenyl groups in the component (e) to the amount of alkenyl groups in the component (f) is (e) / (f) = 0.5 to 5 0.0, the fluorine-containing curable composition is self-flowing at room temperature (25 ° C.), is easy to mold, has excellent heat resistance, chemical resistance, solvent resistance and mechanical strength, and has a high tear strength. It has been found that an improved perfluoropolyether-based fluororubber cured product (elastic body) can be obtained, and the present invention has been made.

（式中、ａは１〜６の整数であり、ｑは２０〜６００の整数である。）
で表される構造を含むものであることを特徴とする請求項１記載の含フッ素硬化性組成物。
〔請求項３〕
（ａ）成分が、下記一般式（１）

［式中、Ｘは−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ¹−ＣＯ−〔但し、Ｙは−ＣＨ₂−、−Ｓｉ（ＣＨ₃）₂ＣＨ₂ＣＨ₂ＣＨ₂−又は下記構造式（Ｚ）

（ｏ，ｍ又はｐ位で示されるジメチルシリルフェニレン基）
で示される基であり、Ｒ¹は水素原子、メチル基、フェニル基又はアリル基である。〕である。Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−〔但し、Ｙ’は−ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）₂−又は下記構造式（Ｚ’）

（ｏ，ｍ又はｐ位で示されるジメチルシリルフェニレン基）
で示される基であり、Ｒ²は水素原子、メチル基、フェニル基又はアリル基である。〕である。ｐは独立に０又は１、ｒは２〜６の整数、ｍ，ｎはそれぞれ０〜６００の整数であり、更にｍとｎの和が３０〜６００である。］
で表されることを特徴とする請求項１又は２記載の含フッ素硬化性組成物。
〔請求項４〕
（ｅ）成分のパーフルオロポリエーテル構造が、

（式中、ａ’は１〜６の整数であり、ｑ’は２〜１５０の整数である。）
で表される構造を含むものであることを特徴とする請求項１〜３のいずれか１項記載の含フッ素硬化性組成物。
〔請求項５〕
（ｅ）成分が、下記一般式（２）

［式中、Ｘ”は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−、−ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）₂−又は−ＣＯ−ＮＲ³−Ｙ”−〔但し、Ｙ”は−ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）₂−又は下記構造式（Ｚ”）

（ｏ，ｍ又はｐ位で示されるジメチルシリルフェニレン基）
で示される基であり、Ｒ³は水素原子、メチル基、フェニル基又はアリル基である。〕である。ｐ’は０又は１、ｓは２〜１５０の整数である。］
で表されることを特徴とする請求項１〜４のいずれか１項記載の含フッ素硬化性組成物。
〔請求項６〕
（ｂ）成分が、１分子中に１個以上の１価のパーフルオロアルキル基、１価のパーフルオロオキシアルキル基、２価のパーフルオロアルキレン基及び２価のパーフルオロオキシアルキレン基から選ばれる含フッ素置換基を有し、かつケイ素原子に結合した水素原子を２個以上有する含フッ素有機ケイ素化合物であることを特徴とする請求項１〜５のいずれか１項記載の含フッ素硬化性組成物。
Accordingly, the present invention provides the following fluorine-containing curable composition.
[Claim 1]
(A) having at least two alkenyl groups in one molecule and —C _a F _2a O— in the main chain
(In the formula, a is an integer of 1 to 6.)
A linear perfluoropolyether compound having a perfluoropolyether structure containing a repeating unit of 5,000 to 100,000 and having a number average molecular weight of 5,000 to 100,000:
(B) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: the molar ratio of silicon atom-bonded hydrogen atoms in component (b) to alkenyl groups in component (a) is 0 An amount of 4 to 5.0,
(C) Transition metal or its compound as a hydrosilylation reaction catalyst: 0.1 to 1,000 ppm in terms of mass of transition metal with respect to the total of components (a) to (f) ,
(D) Silica-based filler having a BET specific surface area of 30 m ² / g or more: 1 to 100 parts by mass,
(E) a linear perfluoropolyether compound having one alkenyl group in one molecule and a number average molecular weight of 500 to 20,000 having a perfluoropolyether structure: 0.1 to 50 parts by mass;
(F) Polyfunctional alkenyl group-containing compound having at least three alkenyl groups in one molecule and having a number average molecular weight of less than 5,000: 0.02 to 20 parts by mass, The fluorine-containing curable composition, wherein the molar ratio of the amount of alkenyl groups in component e) and the amount of alkenyl groups in component (f) is (e) / (f) = 0.5 to 5.0 .
[Claim 2]
The perfluoropolyether structure of component (a) has the following general formula:

(In the formula, a is an integer of 1 to 6, and q is an integer of 20 to 600.)
The fluorine-containing curable composition according to claim 1, comprising a structure represented by:
[Claim 3]
The component (a) is represented by the following general formula (1)

[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is _{-CH 2 -, - Si (CH} 3) 2 CH ₂ CH ₂ CH ₂ — or the following structural formula (Z)

(Dimethylsilylphenylene group shown at o, m or p position)
R ¹ is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ]. X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, where Y ′ is —CH ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ -or the following structural formula (Z ')

(Dimethylsilylphenylene group shown at o, m or p position)
R ² is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ]. p is independently 0 or 1, r is an integer of 2 to 6, m and n are each an integer of 0 to 600, and the sum of m and n is 30 to 600. ]
The fluorine-containing curable composition according to claim 1 or 2, wherein
[Claim 4]
The perfluoropolyether structure of component (e)

(In the formula, a ′ is an integer of 1 to 6, and q ′ is an integer of 2 to 150.)
The fluorine-containing curable composition according to any one of claims 1 to 3, wherein the fluorine-containing curable composition comprises a structure represented by:
[Claim 5]
(E) The component is represented by the following general formula (2)

[Wherein X ″ represents —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ Si (CH ₃ ) ₂ — or —CO—NR ³ —Y ″ — "the _{-CH 2 -, - CH 2 CH} 2 CH 2 Si (CH 3) 2 - or the following structural formula (Z ')

(Dimethylsilylphenylene group shown at o, m or p position)
R ³ is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ]. p ′ is 0 or 1, and s is an integer of 2 to 150. ]
The fluorine-containing curable composition according to any one of claims 1 to 4, which is represented by:
[Claim 6]
The component (b) is selected from one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups, and divalent perfluorooxyalkylene groups in one molecule. The fluorine-containing curable composition according to any one of claims 1 to 5, which is a fluorine-containing organosilicon compound having a fluorine-containing substituent and having two or more hydrogen atoms bonded to a silicon atom. object.

  According to the present invention, perfluorocarbon is self-flowing at room temperature (25 ° C.), easy to mold, excellent in heat resistance, chemical resistance, solvent resistance and mechanical strength, and in particular, can reduce fuel oil permeability. Since it is possible to provide a fluorinated curable composition that is liquid at room temperature (25 ° C.) that gives a polyether-based fluororubber cured product (elastic body), it is useful for use in rubber members such as automobiles, chemical equipment, and chemical plants. It is.

Hereinafter, the present invention will be described in more detail.
[(A) component]
Component (a) of the present invention is the main agent (base polymer) in the composition of the present invention, and is at least 2, preferably 2 to 20, more preferably 2 to 10, more preferably 2 per molecule. A linear perfluoropolyether compound having a number average molecular weight of 5,000 to 100,000 having -4, particularly preferably 2 alkenyl groups, and having a perfluoropolyether structure in the main chain .

（式中、ａは上記と同じであり、ｑは２０〜６００の整数、好ましくは３０〜４００の整数、より好ましくは３０〜２００の整数である。） Here, as the perfluoropolyether structure,
-C _a F _2a O-
(In the formula, a is an integer of 1 to 6.)
And a compound represented by the following general formula (3).

(In the formula, a is the same as described above, and q is an integer of 20 to 600, preferably an integer of 30 to 400, more preferably an integer of 30 to 200.)

Examples of the repeating unit represented by the above formula —C _a F _2a O— include the following units.
In addition, the said perfluoropolyether structure may be comprised by 1 type of these repeating units individually, and the combination of 2 or more types may be sufficient as it.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-
-C (CF _{3) 2} O-
Of these, the following units are particularly preferred.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-

As the alkenyl group in the linear perfluoropolyether compound of component (a), those having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms and having a CH ₂ ═CH— structure at the terminal are preferable. , Vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups and the like, groups having a CH ₂ ═CH— structure, particularly vinyl groups, allyl groups and the like are preferable.

（ｏ，ｍ又はｐ位で示されるジメチルシリルフェニレン基）
で示される基であり、Ｒ¹は水素原子、メチル基、フェニル基又はアリル基である。〕であり、Ｘ’は独立に−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−〔但し、Ｙ’は−ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）₂−又は下記構造式（Ｚ’）

（ｏ，ｍ又はｐ位で示されるジメチルシリルフェニレン基）
で示される基であり、Ｒ²は水素原子、メチル基、フェニル基又はアリル基である。〕である。Ｒｆ¹は２価のパーフルオロポリエーテル構造であり、上記式（３）、即ち−（Ｃ_aＦ_2aＯ）_q−で示される繰り返し単位を含むものが好ましい。Ｑは炭素数１〜１５の２価の炭化水素基であり、エーテル結合を含んでいてもよく、具体的にはアルキレン基、エーテル結合を含んでいてもよいアルキレン基である。ｐは独立に０又は１である。］ Examples of the component (a) include compounds represented by the following general formulas (4) and (5).
_{CH 2 = CH- (X) p} -Rf 1 - (X ') p -CH = CH 2 (4)
_{CH 2 = CH- (X) p} -Q-Rf 1 -Q- (X ') p -CH = CH 2 (5)
[-CH ₂ wherein, X is independently _{-, - CH 2 O -,} - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is _{-CH 2 -, - Si (CH} 3) ₂ CH ₂ CH ₂ CH ₂ — or the following structural formula (Z)

(Dimethylsilylphenylene group shown at o, m or p position)
R ¹ is a hydrogen atom, a methyl group, a phenyl group or an allyl group. X ′ is independently —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, where Y ′ is —CH ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ — or the following structural formula (Z ′)

(Dimethylsilylphenylene group shown at o, m or p position)
R ² is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ]. Rf ¹ is a divalent perfluoropolyether structure, and preferably contains a repeating unit represented by the above formula (3), that is, — (C _a F _2a O) _q —. Q is a divalent hydrocarbon group having 1 to 15 carbon atoms and may contain an ether bond, specifically an alkylene group or an alkylene group that may contain an ether bond. p is independently 0 or 1. ]

［式中、Ｘ，Ｘ’及びｐは前記と同じであり、ｒは２〜６の整数、好ましくは２〜４の整数、より好ましくは２、ｍ，ｎはそれぞれ０〜６００の整数、好ましくは１５〜３００の整数であり、更にｍとｎの和が３０〜６００、好ましくは３０〜３００である。］ As such a linear perfluoropolyether compound of component (a), those represented by the following general formula (1) are particularly suitable.

[Wherein, X, X ′ and p are the same as defined above, r is an integer of 2 to 6, preferably an integer of 2 to 4, more preferably 2, m and n are each an integer of 0 to 600, preferably Is an integer of 15 to 300, and the sum of m and n is 30 to 600, preferably 30 to 300. ]

  The linear perfluoropolyether compound of component (a) has a number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis (solvent: metaxylene hexafluoride) of 5,000 to 100,000. Preferably, it is 5,000 to 30,000. If the number average molecular weight is less than 5,000, the required chemical resistance cannot be satisfied, and if the number average molecular weight exceeds 100,000, there is a problem in compatibility with other components.

  Specific examples of the linear perfluoropolyether compound represented by the general formula (1) include those represented by the following formula.

（式中、ｍ，ｎはそれぞれ０〜６００、ｍ＋ｎ＝３０〜６００を満足する整数を示す。）

(In the formula, m and n are integers satisfying 0 to 600 and m + n = 30 to 600, respectively.)

Furthermore, in the present invention, in order to adjust the linear perfluoropolyether compound of the above formula (1) to a desired number average molecular weight according to the purpose, It is also possible to use, as component (a), a product obtained by subjecting an organosilicon compound containing two SiH groups to a hydrosilylation addition reaction in the usual conventional method and conditions to extend the chain length.
(A) The linear fluoropolyether compound of a component can be used individually by 1 type or in combination of 2 or more types.

[Component (b)]
The fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule of the component (b) acts as a crosslinking agent and / or a chain extender of the component (a) in the present composition. Is. In consideration of compatibility with component (a), dispersibility, and uniformity after curing, one or more, preferably 1 to 100, more preferably 1 to 30 monovalent perfluoro per molecule. Alkyl group, monovalent perfluorooxyalkyl group (ie, monovalent perfluoropolyether group), divalent perfluoroalkylene group, and divalent perfluorooxyalkylene group (ie, divalent perfluoropolyether) Group) and containing at least 2, preferably 3 or more, more preferably hydrogen atoms bonded to silicon atoms in one molecule (that is, hydrosilyl group represented by SiH). It is preferable to use 3 to 100 organosilicon compounds.

（式中、ｃは１〜２００の整数、好ましくは２〜１００の整数、ｄは１〜３の整数である。）
−Ｃ_bＦ_2b−
（式中、ｂは１〜２０の整数、好ましくは２〜１０の整数である。）

（式中、ｅ及びｆはそれぞれ１以上の整数、ｅ＋ｆの平均は２〜２００の整数、好ましくは２〜１００の整数である。）
−（ＣＦ₂Ｏ）_g−（ＣＦ₂ＣＦ₂Ｏ）_h−ＣＦ₂−
（式中、ｇ及びｈはそれぞれ１〜５０の整数、好ましくは１０〜５０の整数、ｇ＋ｈの平均は５〜１００の整数、好ましくは２０〜１００の整数である。） Examples of the monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, and divalent perfluorooxyalkylene group include groups represented by the following general formulas. Can do.
C _b F _{2b + 1} −
(In the formula, b is an integer of 1 to 20, preferably an integer of 2 to 10.)

(In the formula, c is an integer of 1 to 200, preferably an integer of 2 to 100, and d is an integer of 1 to 3.)
−C _b F _2b −
(In the formula, b is an integer of 1 to 20, preferably an integer of 2 to 10.)

(In the formula, e and f are each an integer of 1 or more, and the average of e + f is an integer of 2 to 200, preferably an integer of 2 to 100.)
_{- (CF 2 O) g -} (CF 2 CF 2 O) h -CF 2 -
(In the formula, g and h are each an integer of 1 to 50, preferably an integer of 10 to 50, and an average of g + h is an integer of 5 to 100, preferably an integer of 20 to 100.)

Further, these monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group or divalent perfluorooxyalkylene group may be directly bonded to the silicon atom. And may be bonded to a silicon atom via a divalent linking group. Here, the divalent linking group may be an alkylene group, an arylene group, or a combination thereof, or may further include an ether bond oxygen atom, an amide bond, a carbonyl bond, an ester bond, a silylene group, or the like. For example, a C2-C12 thing is preferable and the following bivalent coupling group etc. are mentioned.
- (CH _{2) t} -,
_{-CH 2 CH 2 CH 2 OCH 2} -,
_{-CH 2 CH 2 CH 2 -NH-} CO-,
_{-CH 2 CH 2 CH 2 -N (} Ph) -CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 2 CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -O-} CO-,
_{-Ph'-N (CH 3) -CO-} ,
_{-CH 2 CH 2 -Si (CH 3} ) 2 -CH 2 CH 2 CH 2 -N (Ph) -CO-,
_{-CH 2 CH 2 -Si (CH 3} ) 2 -Ph'-N (CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -Si (} CH 3) 2 -Ph'-N (CH 3) -CO-
(However, t is an integer of 1-8, Ph is a phenyl group, and Ph 'is a phenylene group.)

  In addition, the monovalent and divalent fluorine-containing substituents (monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group) in the fluorine-containing organosilicon compound of component (b) And monovalent substituents bonded to silicon atoms other than (a divalent perfluorooxyalkylene group) include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a decyl group. Alkyl groups such as phenyl groups, aryl groups such as tolyl groups and naphthyl groups; aralkyl groups such as benzyl groups and phenylethyl groups; or a part or all of hydrogen atoms of these groups are halogen atoms such as chlorine atoms, cyano Substituted with a group or the like, for example, a chloromethyl group, a chloropropyl group, a cyanoethyl group, etc., having 1 to 20 carbon atoms, preferably Such as unsubstituted or substituted monovalent hydrocarbon group of 12 can be mentioned.

  The fluorine-containing organosilicon compound as the component (b) may have any structure as long as it has an organosilicon compound structure composed of, for example, silane, siloxane, silalkylene, silarylene, and a combination thereof. Shape, branched chain shape, or ring shape, or a three-dimensional network shape. Further, the number of silicon atoms in the molecule in the fluorine-containing organosilicon compound is not particularly limited, but usually 2 to 60, particularly about 3 to 30 is preferable.

  Examples of such organosilicon compounds include the following compounds, and these compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group, and Ph represents a phenyl group.

This (b) component may be used individually by 1 type, and may use 2 or more types together.
The amount of component (b) is such that the hydrosilyl group in component (b), i.e., the SiH group, per mole of alkenyl groups such as vinyl, allyl, and cycloalkenyl groups contained in component (a). The total amount of is 0.4 to 5.0 mol, preferably 0.8 to 3.0 mol. If the blending amount of the component (b) is too small, the degree of crosslinking is insufficient and the strength of the cured product is insufficient, and if it is too large, the strength of the cured product is similarly insufficient.
Furthermore, in the present invention, the SiH group of the component (b) is 0.4 to 5.0 mol with respect to 1 mol of the total alkenyl group of the component (a) and the components (e) and (f) described later. The component (b) is preferably used in an amount of 0.6 to 4.0 mol, particularly 0.8 to 3.5 mol.

[Component (c)]
As the hydrosilylation reaction catalyst of component (c), transition metals, for example, simple substances such as platinum group metals such as Pt, Rh and Pd, and compounds of transition metals such as platinum group metals are preferably used. In the present invention, since these compounds are generally precious metal compounds and are expensive, platinum compounds that are relatively easily available are preferably used. Specific examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinylsiloxane, platinum / silica, alumina, or carbon. It is not limited.

The platinum group metal compounds other than the platinum compounds include rhodium, ruthenium, and iridium or palladium compounds such as are known, for _{example, RhCl (PPh 3) 3,} RhCl (CO) (PPh 3) 2, RhC1 (C 2 H ₄ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) _{4 and the} like (Ph represents a phenyl group).

  The amount of these catalysts to be used is not particularly limited, and a desired curing rate can be obtained with the amount of catalyst. However, in order to obtain an economical viewpoint or a good cured product, the total amount of the composition is used. 0.1 to 1,000 ppm (platinum (for example, with respect to the sum of the components (a) to (f), particularly the sum of the components (a), (b), (c), (e), (f)) In terms of mass of transition metals such as group metals), more preferably in the range of about 0.5 to 500 ppm (same as above).

[Component (d)]
The component (d) of the present invention is a silica-based filler (or silica filler). Silica-based fillers include pulverized silica obtained by pulverizing quartz or glass, fused silica that is once melted and then formed into a spherical shape, wet silica (precipitated silica) produced by adding mineral acid to sodium silicate, silane compound Examples include finely divided silica such as dry silica (fumed silica) produced by combusting silica, but from the viewpoint of improving mechanical strength, the BET specific surface area is 30 m ² / g or more, usually 30 to 400 m ² / g, preferably 50 to 400 m ² / g, more preferably about 100 to 350 m ² / g. Wet silica (precipitated silica), dry silica (fumed silica), and the like correspond to this, but dry silica (fumed silica) with less adsorbed moisture is more preferable. If the BET specific surface area is less than 30 m ² / g, sufficient mechanical strength cannot be obtained.

  Furthermore, in consideration of wettability with the polymer components (components (a), (b), (e), (f)), the surface of the silica filler is composed of organosilicon compounds such as organosilane, organosiloxane, organosilazane, etc. A hydrophobic silica-based filler that has been hydrophobized is preferred. If the silica filler surface is not hydrophobized, sufficient mechanical strength is not obtained, and the viscosity of the composition may be abnormally high.

  (D) The compounding quantity of a component is 1-100 mass parts with respect to 100 mass parts of (a) component, Preferably it is 5-50 mass parts. When the amount is less than 1 part by mass, the reinforcing effect of the filler cannot be sufficiently obtained, and when the amount exceeds 100 parts by mass, the viscosity of the composition increases and workability is impaired.

[(E) component]
The component (e) of the present invention has a number average molecular weight of 500 to 20,000 having one alkenyl group per molecule, preferably at one end of the molecular chain, and having a perfluoropolyether structure. It is a chain perfluoropolyether compound. The component (e) reacts with the crosslinking agent of the component (b) when the composition is heat-cured, but since it has only one alkenyl group in the molecule, the component (e) and the component (b) In the reaction, a three-dimensional network structure for forming a so-called rubber-like material is not formed. Accordingly, as a result, it plays a role of lowering the crosslinking density of the entire cured product and mainly improving the tear strength.

  The component (e) has a number average molecular weight in terms of polystyrene in a gel permeation chromatography (GPC) analysis (solvent: metaxylene hexafluoride) of 500 to 20,000, preferably 500 to 10,000. . When the number average molecular weight is less than 500, the compatibility with the component (a) is poor, and when the number average molecular weight exceeds 20,000, the mechanical strength of the rubber after curing is lowered.

As the alkenyl group in the linear perfluoropolyether compound of component (e), those having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and having a CH ₂ ═CH— structure at the terminal are preferable. , Vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups and the like, groups having a CH ₂ ═CH— structure, particularly vinyl groups, allyl groups and the like are preferable.

As the perfluoropolyether structure in the linear perfluoropolyether compound of component (e), one having one end blocked with a fluorine atom (F) or a CF ₃ group (ie, monovalent perfluoro) An oxyalkyl group), and the main chain portion of the perfluoropolyether structure is preferably the same as the perfluoropolyether structure of the component (a). Here, as the perfluoropolyether structure,
-C _{a '} F _2a' O-
(In the formula, a ′ is an integer of 1 to 6.)
And a compound represented by the following general formula (6).

（式中、ａ’は上記と同じであり、ｑ’は２〜１５０の整数である。）

(In the formula, a ′ is the same as above, and q ′ is an integer of 2 to 150.)

Examples of the repeating unit represented by the above formula -C _{a ′} F _{2a ′} O— include the following units. In addition, the said perfluoropolyether structure may be comprised by 1 type of these repeating units individually, and the combination of 2 or more types may be sufficient as it.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-
-C (CF _{3) 2} O-
Of these, the following units are particularly preferred.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-

The linear perfluoropolyether compound (e) is a monovalent perfluorooxyalkyl group in which one end of the molecular chain is an alkenyl group and the other end of the molecular chain has a perfluoropolyether structure. It is preferable that In this case, the perfluoropolyether structure may be directly bonded to the alkenyl group, but may be bonded to the alkenyl group (for example, vinyl group) via a divalent group. Here, as the divalent linking group, an alkylene group, an arylene group or a combination thereof, or an ether bond oxygen atom, an amide bond, a silylene group or the like interposed therebetween, for example, having 1 to 16 carbon atoms, The thing of C2-C12 is preferable and the following bivalent group etc. are mentioned.
-CH ₂ -,
-OCH ₂ -,
-CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ -,
-CH ₂ OCH ₂ -,
_{-CH 2 CH 2 CH 2 OCH 2} -,
-CH ₂ -NH-CO-,
-CH ₂ -N (Ph) -CO-,
_{-CH 2 CH 2 CH 2 -NH-} CO-,
_{-CH 2 CH 2 CH 2 -N (} Ph) -CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-,
_{-Si (CH 3) 2 -CH 2} CH 2 CH 2 -N (Ph) -CO-,
_{-Si (CH 3) 2 -Ph'-} N (CH 3) -CO-,
_{-Si (CH 3) 2 -CH 2} CH 2 -,
_{-Si (CH 3) 2 -CH 2} CH 2 CH 2 OCH 2 -,
(However, Ph is a phenyl group, and Ph ′ is a phenylene group.)

（ｏ，ｍ又はｐ位で示されるジメチルシリルフェニレン基）
で示される基であり、Ｒ³は水素原子、メチル基、フェニル基又はアリル基である。〕である。ｐ’は０又は１である。］ Examples of such component (e) include those represented by the following general formula (7).
_{^{Rf 2 - (X ") p}} '-CH = CH 2 (7)
[Wherein Rf ² represents the following general formula (i) or (ii)
_{F- [C 3 F 6 O]} i -C j F 2j - (i)
_{CF 3 - [OCF (Y)} CF 2] k - (OCF 2) l - (ii)
(Wherein i is an integer of 1 to 100, preferably 2 to 50, j is an integer of 1 to 4, k is an integer of 1 to 50, preferably 10 to 50, and l is 1 to 50. An integer, preferably an integer of 10-50.)
Y is F (fluorine atom) or CF ₃ group, X ″ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ Si (CH ₃ ) ₂₋ , —CH ₂ OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ — or —CO—NR ³ —Y ″ — [where Y ″ represents —CH ₂ —, —CH ₂ CH ₂ CH ₂ Si ( CH ₃ ) ₂ — or the following structural formula (Z ″)

(Dimethylsilylphenylene group shown at o, m or p position)
R ³ is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ]. p ′ is 0 or 1. ]

［式中、Ｘ”、ｐ’は上記と同じ。ｓは２〜１５０の整数、好ましくは５〜５０の整数である。］ Among them, those represented by the following general formula (2) are preferable.

[Wherein, X ″ and p ′ are the same as described above. S is an integer of 2 to 150, preferably an integer of 5 to 50.]

(E) As a linear perfluoropolyether compound of a component, the following compounds are mentioned.

This (e) component may be used individually by 1 type, and may use 2 or more types together.
(E) The compounding quantity of a component is 0.1-50 mass parts with respect to 100 mass parts of (a) component, Preferably it is 0.5-30 mass parts, More preferably, it is 0.5-20 masses. Part. If the blending amount of the component (e) is too small, the effect of improving the tear strength cannot be obtained, and if it is too large, the curability is deteriorated and the rubber strength of the cured product is lowered, resulting in a very rubber.

[Component (f)]
The component (f) of the present invention has at least 3, usually 3 to 30, preferably 3 to 20, alkenyl groups in one molecule and has a number average molecular weight of less than 5,000 (usually 4,900 or less), a relatively low molecular weight and multifunctional alkenyl group-containing compound, which may or may not contain a fluorine atom in the molecule, Among those containing, those corresponding to component (a) are not included. This compound has a function of increasing the crosslinking density when the composition of the present invention is cured, and can maintain the hardness of the cured rubber. Therefore, the component (f) desirably has a high alkenyl group concentration. For example, the alkenyl group content per unit mass is 0.6 mmol / g or more, preferably 0.6 to 30 mmol / g, more preferably It is desirable to be about 1 to 20 mmol / g, more preferably about 2 to 20 mmol / g.

As the alkenyl group in the polyfunctional alkenyl compound of component (f), those having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms and having a CH ₂ ═CH— structure at the terminal are preferable. , An allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, or the like, a group having a CH ₂ ═CH— structure at the end, particularly a vinyl group or an allyl group is preferable.

  Component (f) has a number average molecular weight in terms of polystyrene of less than 5,000 (usually 4,900 or less) in gel permeation chromatography (GPC) analysis (solvent: metaxylene hexafluoride or tetrahydrofuran (THF)). Preferably, it is 200-4,000. If the number average molecular weight is too large, the blending amount (mass) increases, resulting in a decrease in rubber physical properties and difficulty in maintaining rubber hardness. On the other hand, if it is less than 200, the alkenyl group is too localized, and the effect of increasing the crosslinking density may not be obtained.

Specific examples of such a polyfunctional alkenyl group-containing compound having a high alkenyl group concentration include the following compounds. In the following formulae, Me represents a methyl group.

（式中、ｗは１以上の整数であり、かつ数平均分子量５，０００未満を満足する整数である。）

(In the formula, w is an integer of 1 or more and an integer satisfying a number average molecular weight of less than 5,000.)

This (f) component may be used individually by 1 type, and may use 2 or more types together.
(F) The compounding quantity of a component is 0.02-20 mass parts with respect to 100 mass parts of (a) component, Preferably it is 0.02-15 mass parts, More preferably, it is 0.05-10 mass. Part. When the blending amount of the component (f) is too small, it is difficult to maintain the rubber hardness of the cured product, and when it is too large, the elongation characteristics of the cured product are deteriorated and the rubber becomes brittle.

  In the present invention, the ratio of the amount of alkenyl groups in component (e) to the amount of alkenyl groups in component (f), that is, the moles of alkenyl groups in component (e) relative to alkenyl groups in component (f). The ratio is (e) / (f) = 0.5-5.0, preferably 0.5-3.0, more preferably 0.8-2.5. If (e) / (f) is less than 0.5, the desired tear strength cannot be obtained. When (e) / (f) exceeds 5.0, the hardness of the rubber after curing decreases, and the same hardness as when the (e) and (f) components are not blended cannot be maintained.

Other components In addition to the components (a) to (f), conventionally known various additives can be blended in the composition of the present invention within a range not impairing the effects of the present invention. Specific examples of such components include 1-ethyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl- Control agents for hydrosilylation reaction catalysts such as acetylene alcohols such as 1-pentyn-3-ol and phenylbutynol, 3-methyl-3-penten-1-in and 3,5-dimethyl-3-hexen-1-in And pigments such as iron oxide, cerium oxide, and carbon black, colorants, dyes, antioxidants, oil-like compounds partially or entirely modified with fluorine, and the like. In addition, the addition amount of these arbitrary components can be made into a normal amount in the range which does not inhibit the effect of this invention.

Method of Use The composition of the present invention is a liquid that is self-flowing at room temperature (25 ° C.), and handles all the essential components (a) to (f) as one composition depending on the application. May be configured as a so-called one-component type, or, for example, the components (a), (c), (d), (e) and (f) are one composition, and (a), (b) , (D), (e) and (f) may be configured as a so-called two-component type having the other composition and mixed in use.

It is also possible to use the composition after dissolving and diluting it. As such a solvent, those capable of dissolving the component (a) are preferable. For example, C ₄ F ₁₀ , C ₈ F ₁₈ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , 2-n- Examples include fluorinated solvents such as nonafluorobutyl-tetrafluorofuran, tris (n-nonafluorobutyl) amine, metaxylene hexafluoride, paraxylene hexafluoride, benzotrifluoride and the like.

  The fluorine-containing curable composition of the present invention can be easily cured by allowing it to stand at room temperature or heating, but usually room temperature (for example, 5-35 ° C.) to 200 ° C., 1 minute to 24 hours. It is preferable to thermally cure in the range described above. By such curing, a perfluoropolyether-based fluororubber cured product (rubber elastic body) having excellent characteristics can be obtained.

  The perfluoropolyether fluororubber cured product (rubber elastic body) obtained by curing the composition of the present invention can be used for various applications. That is, since the fluorine content is high, it has excellent solvent resistance and chemical resistance, and also has low moisture permeability and low surface energy, so it has excellent releasability and water repellency, and requires oil resistance. Rubber parts for automobiles, specifically diaphragms for fuel regulators, diaphragms for pulsation dampers, diaphragms for oil pressure switches, diaphragms for EGR, valves for canisters, valves for power control, quick connectors O-rings such as O-rings for injectors and O-rings for injectors, or sealing materials such as oil seals and gaskets for cylinder heads, rubber parts for chemical plants, specifically diaphragms for valves, valves, O- Rings, hoses, packings, oil seals, gas Sealing materials such as inkjets, rubber parts for inkjet printers, rubber parts for semiconductor production lines, specifically sealing materials such as diaphragms, valves, O-rings, packings, and gaskets for equipment that comes into contact with chemicals, low friction resistance Valves that require wear, analysis, rubber parts for physics and chemistry equipment, specifically diaphragms for pumps, valves, seal parts (O-rings, packing, etc.), rubber parts for medical equipment, specifically pumps, Useful for valves, joints, tent film materials, sealants, molded parts, extruded parts, coating materials, copier roll materials, electrical moisture-proof coating materials, sensor potting materials, fuel cell sealing materials, laminated rubber cloths, etc. is there.

  Hereinafter, although a reference example, an example, and a comparative example are shown and the present invention is explained concretely, the present invention is not restricted to the following example. In addition, a viscosity is a value in 25 degreeC and Me represents a methyl group by the following formula. Moreover, the number average molecular weight of each component shows the number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis (solvent: metaxylene hexafluoride).

で表されるポリマー（粘度５，５００ｍｍ²／ｓ、数平均分子量１５，７００、ビニル基量０．０１２モル／１００ｇ）１００質量部、（ｄ）成分として、Ｒ９７２（日本アエロジル社製乾式シリカ、ＢＥＴ比表面積１１０ｍ²／ｇ）４０質量部をニーダー中で１７５℃／２時間混合した。その後、プラネタリーミキサーでＲ９７２の配合量が（ａ）成分１００質量部に対して２０質量部になるように、上記式（８）のポリマー１００質量部を添加して調製し、３本ロールミル処理を施して混合物Ａを調製した。
混合物Ａ １２０質量部に、（ｂ）成分として、下記式（９）

で表される含フッ素有機ケイ素化合物３．４質量部（（ａ）成分中のビニル基に対する（ｂ）成分中のＳｉＨ基のモル比＝１．１０）、（ｃ）成分として、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０．５質量％）０．２質量部及びエチニルシクロヘキサノールの５０質量％トルエン溶液０．３質量部を加え、プラネタリーミキサーで混合し、硬化性組成物を調製した。この組成物を１５０℃、１０分間のプレス架橋（一次架橋）及び２００℃、２時間のオーブン架橋（二次架橋）を行って硬化シート（１７０ｍｍ×１３０ｍｍ×２ｍｍ）を得た。得られた硬化シートの物性は、ＪＩＳ Ｋ６２５３、ＪＩＳ Ｋ６２５１、ＪＩＳ Ｋ６２５２に準拠して測定した。これらの結果を表１に示す。 [Reference Example 1]
As component (a), the following formula (8)

100 parts by mass of a polymer represented by the formula (viscosity 5,500 mm ² / s, number average molecular weight 15,700, vinyl group content 0.012 mol / 100 g), (d) as component, R972 (Nippon Aerosil Co., Ltd. dry silica, BET specific surface area 110 m ² / g) 40 parts by mass were mixed in a kneader at 175 ° C./2 hours. Thereafter, the mixture is prepared by adding 100 parts by mass of the polymer of the above formula (8) so that the blending amount of R972 is 20 parts by mass with respect to 100 parts by mass of the component (a) using a planetary mixer, To prepare a mixture A.
In 120 parts by mass of the mixture A, as the component (b), the following formula (9)

3.4 parts by mass of a fluorine-containing organosilicon compound represented by the formula (Molar ratio of SiH group in component (b) to 1.10) relative to the vinyl group in component (a) = 1, and (c) chloroplatinic acid as component the _{CH 2 = CHSiMe 2 OSiMe 2 CH} = modified with CH ₂ toluene solution of the catalyst (platinum concentration 0.5 wt%) to 50 wt% toluene solution 0.3 parts by weight of 0.2 part by weight and ethinyl cyclohexanol added The mixture was mixed with a planetary mixer to prepare a curable composition. This composition was subjected to press crosslinking (primary crosslinking) at 150 ° C. for 10 minutes and oven crosslinking (secondary crosslinking) at 200 ° C. for 2 hours to obtain a cured sheet (170 mm × 130 mm × 2 mm). The physical properties of the obtained cured sheet were measured according to JIS K6253, JIS K6251 and JIS K6252. These results are shown in Table 1.

で表されるポリマー（粘度６７０ｍｍ²／ｓ、数平均分子量４，３００、ビニル基量０．０２３モル／１００ｇ）１００質量部、（ｄ）成分として、Ｒ９７２（日本アエロジル社製乾式シリカ、ＢＥＴ比表面積１１０ｍ²／ｇ）５０質量部をニーダー中で１７５℃／２時間混合した。その後、プラネタリーミキサーでＲ９７２の配合量が（ｅ）成分１００質量部に対して２０質量部になるように、上記式（１０）のポリマー１５０質量部を添加して調製し、３本ロールミル処理を施して混合物Ｂを調製した。
参考例１で調製した混合物Ａ １０８質量部、上記混合物Ｂ １２質量部に、（ｂ）成分として、上記式（９）で表される含フッ素有機ケイ素化合物４．３質量部（（ａ）成分中のビニル基に対する（ｂ）成分中のＳｉＨ基のモル比＝１．５４）、（ｆ）成分として、下記式（１１）

で表される多官能性ビニル化合物（分子量約６７８、ビニル基量０．００４４モル／ｇ）０．４質量部、（ｃ）成分として、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０．５質量％）０．２質量部及びエチニルシクロヘキサノールの５０質量％トルエン溶液０．３質量部を加え、プラネタリーミキサーで混合し、硬化性組成物を調製した。この組成物を１５０℃、１０分間のプレス架橋（一次架橋）及び２００℃、２時間のオーブン架橋（二次架橋）を行って硬化シート（１７０ｍｍ×１３０ｍｍ×２ｍｍ）を得た。得られた硬化シートの物性は、ＪＩＳ Ｋ６２５３、ＪＩＳ Ｋ６２５１、ＪＩＳ Ｋ６２５２に準拠して測定した。これらの結果を表１に示す。
なお、この組成物中の（ｅ）成分と（ｆ）成分のアルケニル基の比率（モル比）は、（ｅ）／（ｆ）＝１．３であった。 [Example 1]
As the component (e), the following formula (10)

100 parts by mass of a polymer represented by the formula (viscosity 670 mm ² / s, number average molecular weight 4,300, vinyl group amount 0.023 mol / 100 g), (d) as component, R972 (Nippon Aerosil Co., Ltd. dry silica, BET ratio) 50 parts by mass of a surface area of 110 m ² / g) were mixed in a kneader at 175 ° C./2 hours. Thereafter, 150 parts by mass of the polymer of the above formula (10) is added and prepared with a planetary mixer so that the blending amount of R972 is 20 parts by mass with respect to 100 parts by mass of the component (e). To prepare a mixture B.
108 parts by mass of the mixture A prepared in Reference Example 1 and 12 parts by mass of the above mixture B were used as the component (b), and 4.3 parts by mass of the fluorine-containing organosilicon compound represented by the above formula (9) (component (a) The molar ratio of the SiH group in the component (b) to the vinyl group in the component = 1.54), and as the component (f), the following formula (11)

0.4 parts by mass of a polyfunctional vinyl compound (molecular weight: about 678, vinyl group amount: 0.0044 mol / g), and chloroplatinic acid as CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH Add 0.2 parts by weight of the toluene solution of the catalyst modified in ₂ (platinum concentration: 0.5% by weight) and 0.3 parts by weight of 50% by weight toluene solution of ethynylcyclohexanol and mix them with a planetary mixer. A product was prepared. This composition was subjected to press crosslinking (primary crosslinking) at 150 ° C. for 10 minutes and oven crosslinking (secondary crosslinking) at 200 ° C. for 2 hours to obtain a cured sheet (170 mm × 130 mm × 2 mm). The physical properties of the obtained cured sheet were measured according to JIS K6253, JIS K6251 and JIS K6252. These results are shown in Table 1.
In addition, the ratio (molar ratio) of the alkenyl groups of the component (e) and the component (f) in this composition was (e) / (f) = 1.3.

[Comparative Example 1]
In Example 1, the compounding amount of the compound represented by the formula (9) is 3.9 parts by mass, and the compounding amount of the compound represented by the formula (11) is 0.1 part by mass. A curable composition was prepared according to the formulation, and a cured sheet was produced. The physical properties of the obtained cured sheet were measured according to JIS K6253, JIS K6251 and JIS K6252. These results are shown in Table 1.
In addition, the ratio (molar ratio) of the alkenyl groups of the component (e) and the component (f) in this composition was e) / (f) = 5.2.

[Comparative Example 2]
In Example 1, the compounding amount of the compound represented by the formula (9) is 5.3 parts by mass, and the compounding amount of the compound represented by the formula (11) is 1.2 parts by mass. A curable composition was prepared according to the formulation, and a cured sheet was produced. The physical properties of the obtained cured sheet were measured according to JIS K6253, JIS K6251 and JIS K6252. These results are shown in Table 1.
In addition, the ratio (molar ratio) of the alkenyl groups of the component (e) and the component (f) in this composition was (e) / (f) = 0.44.

で表される含フッ素有機ケイ素化合物２．６質量部（（ａ）成分中のビニル基に対する（ｂ）成分中のＳｉＨ基のモル比＝１．０８）、（ｃ）成分として、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０．５質量％）０．２質量部及びエチニルシクロヘキサノールの５０質量％トルエン溶液０．３質量部を加え、プラネタリーミキサーで混合し、硬化性組成物を調製した。この組成物を１５０℃、１０分間のプレス架橋（一次架橋）及び２００℃、２時間のオーブン架橋（二次架橋）を行って硬化シート（１７０ｍｍ×１３０ｍｍ×２ｍｍ）を得た。得られた硬化シートの物性は、ＪＩＳ Ｋ６２５３、ＪＩＳ Ｋ６２５１、ＪＩＳ Ｋ６２５２に準拠して測定した。これらの結果を表１に示す。 [Reference Example 2]
As the component (a), 100 parts by mass of the polymer represented by the above formula (8) (viscosity 5,500 mm ² / s, number average molecular weight 15,700, vinyl group amount 0.012 mol / 100 g), component (d) As described above, 50 parts by mass of a filler obtained by treating the surface of a dry silica filler having a BET specific surface area of 300 m ² / g with hexamethyldisilazane was mixed in a kneader at 175 ° C./2 hours. Thereafter, 100 parts by mass of the polymer of the above formula (8) is added and prepared by a planetary mixer so that the compounding amount of the silica filler is 25 parts by mass with respect to 100 parts by mass of the component (a). Treatment was performed to prepare mixture C.
In 125 parts by mass of the mixture C, as the component (b), the following formula (12)

2.6 parts by mass of a fluorine-containing organosilicon compound represented by the formula (molar ratio of SiH group in component (b) to vinyl group in component (a) = 1.08), (c) chloroplatinic acid as component the _{CH 2 = CHSiMe 2 OSiMe 2 CH} = modified with CH ₂ toluene solution of the catalyst (platinum concentration 0.5 wt%) to 50 wt% toluene solution 0.3 parts by weight of 0.2 part by weight and ethinyl cyclohexanol added The mixture was mixed with a planetary mixer to prepare a curable composition. This composition was subjected to press crosslinking (primary crosslinking) at 150 ° C. for 10 minutes and oven crosslinking (secondary crosslinking) at 200 ° C. for 2 hours to obtain a cured sheet (170 mm × 130 mm × 2 mm). The physical properties of the obtained cured sheet were measured according to JIS K6253, JIS K6251 and JIS K6252. These results are shown in Table 1.

で表される多官能性ビニル化合物（分子量約２４９、ビニル基量０．０１２モル／ｇ）０．１５質量部、（ｃ）成分として、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０．５質量％）０．２質量部及びエチニルシクロヘキサノールの５０質量％トルエン溶液０．３質量部を加え、プラネタリーミキサーで混合し、硬化性組成物を調製した。この組成物を１５０℃、１０分間のプレス架橋（一次架橋）及び２００℃、２時間のオーブン架橋（二次架橋）を行って硬化シート（１７０ｍｍ×１３０ｍｍ×２ｍｍ）を得た。得られた硬化シートの物性は、ＪＩＳ Ｋ６２５３、ＪＩＳ Ｋ６２５１、ＪＩＳ Ｋ６２５２に準拠して測定した。これらの結果を表１に示す。
なお、この組成物中の（ｅ）成分と（ｆ）成分のアルケニル基の比率（モル比）は、（ｅ）／（ｆ）＝１．３であった。 [Example 2]
100 parts by mass of the polymer represented by the above formula (10) as the component (e), and 50 parts by mass of the dry silica filler having a BET specific surface area of 300 m ² / g treated with hexamethyldisilazane as the component (d). The parts were mixed in a kneader at 175 ° C./2 hours. Thereafter, a planetary mixer is used to add 100 parts by mass of the polymer of the above formula (10) so that the compounding amount of the silica filler is 25 parts by mass with respect to 100 parts by mass of the component (e). Treatment was performed to prepare mixture D.
112.5 parts by mass of the mixture C prepared in Reference Example 2, 12.5 parts by mass of the mixture D, and 3.3 parts by mass of the fluorine-containing organosilicon compound represented by the above formula (12) as the component (b) (( (a) molar ratio of SiH groups in component (b) to vinyl groups in component = 1.53), (f) as component (13)

0.15 parts by mass of a polyfunctional vinyl compound (molecular weight: about 249, vinyl group content: 0.012 mol / g), and chloroplatinic acid as CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH as component (c) Add 0.2 parts by weight of the toluene solution of the catalyst modified in ₂ (platinum concentration: 0.5% by weight) and 0.3 parts by weight of 50% by weight toluene solution of ethynylcyclohexanol and mix them with a planetary mixer. A product was prepared. This composition was subjected to press crosslinking (primary crosslinking) at 150 ° C. for 10 minutes and oven crosslinking (secondary crosslinking) at 200 ° C. for 2 hours to obtain a cured sheet (170 mm × 130 mm × 2 mm). The physical properties of the obtained cured sheet were measured according to JIS K6253, JIS K6251 and JIS K6252. These results are shown in Table 1.
In addition, the ratio (molar ratio) of the alkenyl groups of the component (e) and the component (f) in this composition was (e) / (f) = 1.3.

Example 1 is a case where (e) component and (f) component are blended with Reference Example 1 in a balanced manner. Example 2 is a case where the component (e) and the component (f) are blended with the reference example 2 in a well-balanced manner. In both cases, the tear strength is remarkably improved and the other properties are not substantially affected.
Comparative Example 1 and Comparative Example 2 are cases where the ratio of the component (e) and the component (f) departs from the scope of the present invention. In this case, the hardness is not changed with respect to the original characteristics (Reference Example 1), and the tear strength is not improved.

Claims (6)

(A) having at least two alkenyl groups in one molecule and —C _a F _2a O— in the main chain
(In the formula, a is an integer of 1 to 6.)
A linear perfluoropolyether compound having a perfluoropolyether structure containing a repeating unit of 5,000 to 100,000 and having a number average molecular weight of 5,000 to 100,000:
(B) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: the molar ratio of silicon atom-bonded hydrogen atoms in component (b) to alkenyl groups in component (a) is 0 An amount of 4 to 5.0,
(C) Transition metal or its compound as a hydrosilylation reaction catalyst: 0.1 to 1,000 ppm in terms of mass of transition metal with respect to the total of components (a) to (f) ,
(D) Silica-based filler having a BET specific surface area of 30 m ² / g or more: 1 to 100 parts by mass,
(E) a linear perfluoropolyether compound having one alkenyl group in one molecule and a number average molecular weight of 500 to 20,000 having a perfluoropolyether structure: 0.1 to 50 parts by mass;
(F) Polyfunctional alkenyl group-containing compound having at least three alkenyl groups in one molecule and having a number average molecular weight of less than 5,000: 0.02 to 20 parts by mass, The fluorine-containing curable composition, wherein the molar ratio of the amount of alkenyl groups in component e) and the amount of alkenyl groups in component (f) is (e) / (f) = 0.5 to 5.0 . The perfluoropolyether structure of component (a) has the following general formula:

(In the formula, a is an integer of 1 to 6, and q is an integer of 20 to 600.)
The fluorine-containing curable composition according to claim 1, comprising a structure represented by: The component (a) is represented by the following general formula (1)

[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is _{-CH 2 -, - Si (CH} 3) 2 CH ₂ CH ₂ CH ₂ — or the following structural formula (Z)

(Dimethylsilylphenylene group shown at o, m or p position)
R ¹ is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ]. X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, where Y ′ is —CH ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ -or the following structural formula (Z ')

(Dimethylsilylphenylene group shown at o, m or p position)
R ² is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ]. p is independently 0 or 1, r is an integer of 2 to 6, m and n are each an integer of 0 to 600, and the sum of m and n is 30 to 600. ]
The fluorine-containing curable composition according to claim 1 or 2, wherein The perfluoropolyether structure of component (e)

(In the formula, a ′ is an integer of 1 to 6, and q ′ is an integer of 2 to 150.)
The fluorine-containing curable composition according to any one of claims 1 to 3, wherein the fluorine-containing curable composition comprises a structure represented by: (E) The component is represented by the following general formula (2)

[Wherein X ″ represents —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ Si (CH ₃ ) ₂ — or —CO—NR ³ —Y ″ — "the _{-CH 2 -, - CH 2 CH} 2 CH 2 Si (CH 3) 2 - or the following structural formula (Z ')

(Dimethylsilylphenylene group shown at o, m or p position)
R ³ is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ]. p ′ is 0 or 1, and s is an integer of 2 to 150. ]
The fluorine-containing curable composition according to any one of claims 1 to 4, which is represented by:   The component (b) is selected from one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups, and divalent perfluorooxyalkylene groups in one molecule. The fluorine-containing curable composition according to any one of claims 1 to 5, which is a fluorine-containing organosilicon compound having a fluorine-containing substituent and having two or more hydrogen atoms bonded to a silicon atom. object.