JP2010248280A - Fluorine-containing curable composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing curable composition which has low viscosity, is easily formed, is excellent in heat resistance, and specifically gives a cured material that can reduce fuel oil permeability; and to provide a method for producing the same. <P>SOLUTION: The fluorine-containing curable composition comprises: (a) 100 pts.mass of a straight-chain perfluoro polyether compound that has at least two alkenyl groups in one molecule and a number-average molecular weight of 3,000 to 100,000; (b) a fluorine-containing organosilicon compound that has at least two SiH groups in one molecule, in which the mole ratio of the SiH group in the (b) component to the alkenyl group in the (a) component is 0.4-5.0; (c) a catalytic amount of a hydrosilylation reaction catalyst; (d) 1-100 pts.mass of a silica-based filler; and (e) 1-100 pts.mass of a thermoplastic fluorinated resin with a melting point of 100-200°C, and, in the method for producing the composition, the (a) component or a mixture of the (a) component with the (d) component is added and mixed with the (e) component at a temperature of its melting point or higher, followed by adding and mixing the remaining components. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a fluorine-containing curable composition that is easy to mold with a low viscosity, is excellent in heat resistance, chemical resistance, solvent resistance and mechanical strength, and particularly provides a cured product that can reduce fuel oil permeability and its production. It is about the method.

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 Patent No. 2990646 is known.
Such a composition has sufficient performance in most applications, but in order to cope with recent environmental problems such as reduction of HC emissions, further reduction of fuel oil permeability is required. It has been.
However, in reality, there is no appropriate fluorine-containing curable composition that provides a cured product that can reduce the fuel oil permeability.

Japanese Patent No. 2990646

  The present invention has been made in view of the above circumstances, and provides a cured product that is easy to mold with low viscosity, excellent in heat resistance, chemical resistance, solvent resistance, and mechanical strength, and in particular, can reduce fuel oil permeability. It aims at providing a fluorine-containing curable composition and its manufacturing method.

As a result of studies conducted by the inventors to achieve the above-described object,
(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 number average molecular weight of 3,000 to 100,000 having a perfluoropolyether structure containing a repeating unit of:
(B) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: the molar ratio of SiH groups in component (b) to alkenyl groups in component (a) is 0.4 to An amount of 5.0,
(C) Hydrosilylation reaction catalyst: catalytic amount,
(D) Silica-based filler: 1 to 100 parts by mass,
(E) Thermoplastic fluorine-based resin having a melting point of 100 to 200 ° C .: According to the fluorine-containing curable composition characterized by containing 1 to 100 parts by mass, it is easy to mold with low viscosity, heat resistance In the production of the fluorine-containing curable composition, the component (e) is known to give a cured product that is excellent in heat resistance, chemical resistance, solvent resistance and mechanical strength, and in particular can reduce fuel oil permeability. Is added to and mixed with the component (a) or the mixture of the component (a) and the component (d) at a temperature equal to or higher than the melting point of the component (e), and then the remaining components are added and mixed. According to the method for producing a fluorinated curable composition, it has been found that a composition in which each component is uniform can be obtained, and the present invention has been made.

（式中、ｑは２０〜６００の整数である。）
で表され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−又は下記構造式（Ｚ）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−又は下記構造式（Ｚ’）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２０〜６００である。］

（ｏ，ｍ又はｐ位で示されるジメチルフェニルシリレン基）

（ｏ，ｍ又はｐ位で示されるジメチルフェニルシリレン基）
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：
（ｂ）成分が、１分子中に１個以上の一価のパーフルオロ基、一価のパーフルオロオキシ基、二価のパーフルオロ基又は二価のパーフルオロオキシ基を有し、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：
（ｄ）成分が、ＢＥＴ比表面積３０ｍ²／ｇ以上で表面が疎水化処理されたシリカ系充填材である請求項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：
（ｅ）成分の熱可塑性フッ素系樹脂が、下記一般式（２）で示される
ＣＦ₂＝ＣＸＲ¹ （２）
（式中、Ｘは水素原子又はハロゲン原子であり、Ｒ¹はハロゲン原子又は１〜１０個の炭素原子を有するアルキル基、環状アルキル基、若しくはアリール基であり、これらの基はヘテロ原子を１個以上含んでいてもよく、また部分的に若しくは完全にハロゲン化されていてもよい。）
なる構造を有する少なくとも１種のモノマーから誘導される共重合単位を含む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。
請求項７：
請求項１〜６のいずれか１項に記載の含フッ素硬化性組成物の製造に際し、（ｅ）成分を、該（ｅ）成分の溶融点以上の温度で、（ａ）成分、又は（ａ）成分と（ｄ）成分の混合物に添加混合した後、残りの成分を添加混合することを特徴とする含フッ素硬化性組成物の製造方法。 Therefore, this invention provides the following fluorine-containing curable composition and its manufacturing method.
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 number average molecular weight of 3,000 to 100,000 having a perfluoropolyether structure containing a repeating unit of:
(B) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: the molar ratio of SiH groups in component (b) to alkenyl groups in component (a) is 0.4 to An amount of 5.0,
(C) Hydrosilylation reaction catalyst: catalytic amount,
(D) Silica-based filler: 1 to 100 parts by mass,
(E) Thermoplastic fluorine-based resin having a melting point of 100 to 200 ° C .: 1 to 100 parts by mass A fluorine-containing curable composition characterized by comprising:
Claim 2:
The perfluoropolyether structure of component (a)

(In the formula, q is an integer of 20 to 600.)
The fluorine-containing curable composition according to claim 1, wherein
Claim 3:
(A) Component is 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 - represented by or the following structural formula (Z) And 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 represented by —CH ₂ — or the following structural formula (Z ′)). And 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 20 to 600. ]

(Dimethylphenylsilylene group shown at o, m or p position)

(Dimethylphenylsilylene group shown at o, m or p position)
The fluorine-containing curable composition according to claim 1 or 2, wherein
Claim 4:
The component (b) has one or more monovalent perfluoro group, monovalent perfluorooxy group, divalent perfluoro group or divalent perfluorooxy group in one molecule, and a silicon atom The fluorine-containing curable composition according to any one of claims 1 to 3, wherein the fluorine-containing curable composition has two or more hydrogen atoms bonded to each other.
Claim 5:
The fluorine-containing curable composition according to any one of claims 1 to 4, wherein the component (d) is a silica-based filler having a BET specific surface area of 30 m ² / g or more and having a hydrophobized surface.
Claim 6:
The thermoplastic fluororesin as component (e) is represented by the following general formula (2): CF ₂ = CXR ¹ (2)
(In the formula, X is a hydrogen atom or a halogen atom, R ¹ is a halogen atom or an alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, or an aryl group. Or may be partially or completely halogenated.)
The fluorine-containing curable composition according to any one of claims 1 to 5, which comprises a copolymer unit derived from at least one monomer having a structure.
Claim 7:
In the production of the fluorinated curable composition according to any one of claims 1 to 6, the component (e) is added at a temperature equal to or higher than the melting point of the component (e), the component (a), or (a A method for producing a fluorine-containing curable composition, wherein the remaining component is added and mixed after being added to and mixed with a mixture of the component)) and the component (d).

  According to the present invention, a fluorine-containing curable composition that provides a cured product that has low viscosity, is easy to mold, is excellent in heat resistance, chemical resistance, solvent resistance, and mechanical strength, and can reduce fuel oil permeability. Since the manufacturing method can be provided, it is useful for the use of rubber members such as automobiles, chemical equipment, and chemical plants.

Hereinafter, the present invention will be described in more detail.
[(A) component]
The component (a) of the present invention is a linear chain having a number average molecular weight of 3,000 to 100,000 having at least two alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain. It is a perfluoropolyether compound.

（式中、ｑは２０〜６００、好ましくは３０〜４００、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 (2).

(In the formula, q is an integer of 20 to 600, preferably 30 to 400, more preferably 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 and having a CH ₂ ═CH— structure at the terminal are preferable. A group having a CH ₂ ═CH— structure at the end, such as a vinyl group or an allyl group, such as a group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group or a hexenyl group is preferred.

（ｏ，ｍ又はｐ−ジメチルシリルフェニレン基）

（ｏ，ｍ又はｐ−ジメチルシリルフェニレン基）
で表される基である。Ｒｆ¹は二価のパーフルオロポリエーテル構造であり、上記式（２）、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の二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 formula.
_{CH 2 = CH- (X) p} -Rf 1 - (X ') p -CH = CH 2 (3)
_{CH 2 = CH- (X) p} -Q-Rf 1 -Q- (X ') p -CH = CH 2 (4)
[-CH ₂ wherein, X is independently _{-, - CH 2 O -,} - CH 2 OCH 2 - or -Y-NR ¹ -CO- (where, Y is -CH ₂ - or the following structural formula (Z) And R ¹ is a hydrogen atom, a methyl group, a phenyl group or an allyl group.) And X ′ is independently —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′— (where Y ′ is —CH ₂ — or a group represented by the following structural formula (Z ′), and R ² is a hydrogen atom, a methyl group, a phenyl group, or an allyl group. .)

(O, m or p-dimethylsilylphenylene group)

(O, m or p-dimethylsilylphenylene group)
It is group represented by these. Rf ¹ is a divalent perfluoropolyether structure, and preferably contains a repeating unit represented by the above formula (2), that is, — (C _a F _2a O) _q —. Q is a C1-C15 divalent hydrocarbon group which may contain an ether bond, specifically an alkylene group or an alkylene group which 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、ｍ、ｎはそれぞれ０〜６００の整数であり、更にｍとｎの和が２０〜６００である。］ As such a linear perfluoropolyether compound (A), those represented by the following general formula (1) are particularly suitable.

[Wherein, X, X ′ and p are the same as above, 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 20 to 600] . ]

  The linear perfluoropolyether compound of the above formula (1) preferably has a number average molecular weight of 3,000 to 100,000, particularly 3,000 to 30,000, as determined by gel permeation chromatography (GPC). . If the number average molecular weight is less than 3,000, the required chemical resistance may not be satisfied, which is not preferable. If the number average molecular weight exceeds 100,000, there is a problem in compatibility with other components. Since it may occur, it is not preferable.

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

（式中、ｍ及びｎはそれぞれ０〜６００、ｍ＋ｎ＝２０〜６００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 = 20 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 a component (a), a product obtained by subjecting an organosilicon compound containing two SiH groups to a hydrosilylation reaction in the usual manner and conditions and extending the chain length.
These linear fluoropolyether compounds can be used singly or in combination of two or more.

[Component (b)]
The fluorine-containing organosilicon compound as component (b) acts as a crosslinking agent and chain extender as component (a). In consideration of compatibility with component (a), dispersibility, and uniformity after curing, one or more monovalent perfluoro group, monovalent perfluorooxy group, divalent perfluoro in one molecule There is no particular limitation as long as it is an organosilicon compound having a group or a divalent perfluorooxy group and having at least 2, preferably 3 or more hydrogen atoms bonded to a silicon atom in one molecule. .

（式中、ｆは２〜２００、好ましくは２〜１００、ｈは１〜３の整数である。）

（式中、ｉ及びｊは１以上の整数、ｉ＋ｊの平均は２〜２００、好ましくは２〜１００である。）
−（ＣＦ₂Ｏ）_c−（ＣＦ₂ＣＦ₂Ｏ）_d−ＣＦ₂−
（但し、ｃ及びｄはそれぞれ１〜５０の整数である。） Examples of the monovalent or divalent perfluoro group and perfluorooxy group include groups represented by the following general formula.
C _g F _{2g + 1} −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)
−C _g F _2g −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)

(In the formula, f is 2 to 200, preferably 2 to 100, and h is an integer of 1 to 3.)

(In the formula, i and j are integers of 1 or more, and the average of i + j is 2 to 200, preferably 2 to 100.)
_{- (CF 2 O) c -} (CF 2 CF 2 O) d -CF 2 -
(However, c and d are each an integer of 1 to 50.)

These mono- or divalent perfluoroalkyl groups and perfluorooxy groups may be directly bonded to the silicon atom, but may be bonded to the 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 an ether bond oxygen atom, an amide bond, a carbonyl bond, or the like interposed therebetween. The thing of number 2-12 is preferable and the following group etc. are mentioned.
—CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
_{-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— (where Ph is a phenyl group)
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-
—CH ₂ CH ₂ CH ₂ —O—CO—

  Examples of the monovalent substituent bonded to the silicon atom other than the monovalent or divalent fluorine-containing substituent in the organosilicon compound of component (b) include, for example, a methyl group, an ethyl group, a propyl group, and a butyl group. Alkyl groups such as hexyl group, cyclohexyl group, octyl group and decyl group; aryl groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as benzyl group and phenylethyl group: or one of hydrogen atoms of these groups Examples thereof include an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms such as a chloromethyl group, a chloropropyl group, and a cyanoethyl group in which a part is substituted with a chlorine atom, a cyano group, or the like.

  The fluorine-containing organosilicon compound as component (b) may be cyclic or chain-like, and may be a three-dimensional network. 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.

（ｎ＝１〜５０，ｍ＝１〜５０，ｎ＋ｍ＝２〜５０）

(N = 1-50, m = 1-50, n + m = 2-50)

  The blending amount of component (b) is usually that of hydrosilyl group in component (b), that is, SiH group, relative to 1 mol of alkenyl group such as vinyl group, allyl group, cycloalkenyl group and the like contained in component (a). The total amount is preferably 0.4 to 5.0 mol, more preferably 0.8 to 3.0 mol. If the amount of component (b) is too small, the degree of crosslinking may be insufficient and the strength of the cured product may be insufficient, and if too large, the strength of the cured product may be insufficient. Moreover, this (b) component may be used individually by 1 type, and may use 2 or more types together.

[Component (c)]
As the hydrosilylation reaction catalyst of component (c), transition metals, for example, platinum group metals such as Pt, Rh, and Pd, and compounds of these transition 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 olefin such as ethylene, a complex of alcohol or pinylsiloxane, platinum / silica, alumina or carbon. It is not limited to.

As platinum group metal compounds other than platinum compounds, rhodium, ruthenium, iridium, palladium compounds and the like 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 (Ph represents a phenyl group). The amount of these catalysts 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. It is good to set it as the range of about 0.1-1,000 ppm (platinum group metal conversion), More preferably about 0.1-500 ppm (same as the above).

[Component (d)]
The component (d) of the present invention is a silica-based filler. Silica-based fillers include pulverized silica obtained by pulverizing quartz and glass, fused silica that is once melted and then formed into spherical particles, wet silica produced by adding a mineral acid to sodium silicate, and silane compounds. Examples include dry silica produced, but from the viewpoint of improving mechanical strength, a silica-based filler having a BET specific surface area of 30 m ² / g or more is good, and wet silica and dry silica fall under this category. Dry silica with low moisture is preferred. Furthermore, when the wettability with the polymer component is taken into consideration, it is preferable that the silica filler surface be subjected to a hydrophobic treatment. If the surface of the silica filler is not hydrophobized, it is liable to cause adverse effects such as insufficient mechanical strength and abnormally high viscosity of the composition.
(D) The compounding quantity of a component is 1-100 mass parts with respect to 100 mass parts of (a) component. If the amount is less than 1 part by mass, the reinforcing effect of the filler may not be sufficiently obtained. If the amount exceeds 100 parts by mass, the viscosity of the composition increases, and workability may be impaired.

[(E) component]
The component (e) of the present invention is a thermoplastic fluororesin having a melting point of 100 to 200 ° C. Such a compound is represented by the following general formula (2): CF ₂ = CXR ¹ (2)
(Wherein, X is a hydrogen atom or a halogen atom, R ¹ is a halogen atom or 1 to 10 preferably an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group, or aryl group, these The group may contain one or more heteroatoms such as oxygen or nitrogen, and may be partially or fully halogenated.)
And a copolymer unit derived from at least one monomer having the following structure.

Examples of such monomers include tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, 2-chloropentafluoropropene, dichlorodifluoroethylene, perfluoroalkyl vinyl ethers such as CF ₃ OCF═CF ₂ or CF ₃ CF ₂ CF ₂ OCF═CF ₂ , and mixtures thereof.

Further, as a substantially non-fluorinated olefin-based monomer copolymerized with the above-mentioned plural types of fluorinated monomers, CH ₂ = CXR ² (3) represented by the following general formula (3)
(In the formula, X is a hydrogen atom or a halogen atom, R ² is a hydrogen atom, a halogen atom, 1-10, preferably 1-6, provided that R ² and X are not both fluorine atoms. Alkyl groups having 1 carbon atom, cyclic alkyl groups, or aryl groups, these groups may contain one or more heteroatoms such as oxygen or nitrogen, and may be partially or fully halogenated May be.)
If necessary, it may contain copolymerized units derived from at least one monomer having the structure:

  Examples of such monomers include ethylene, propylene, 1-butene, isobutene and the like.

  Examples of copolymers derived from these monomer units include copolymers of vinylidene fluoride and hexafluoropropylene, copolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. Examples thereof include a copolymer of fluoropropylene and ethylene or propylene, a copolymer of tetrafluoroethylene and propylene, a copolymer of tetrafluoroethylene, vinylidene fluoride, and propylene.

The component (e) includes the above-described copolymer unit, and a thermoplastic fluorine-based resin having a melting point of 100 to 200 ° C. and a flexural modulus (test method: ASTM D790) of 50 to 300 MPa, preferably 70 to 250 MPa is desirable.
Specific examples of such thermoplastic fluororesins include those obtained by copolymerizing tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. In order to obtain the above characteristics, a copolymer of 30 to 70% by mass of tetrafluoroethylene, 10 to 30% by mass of hexafluoropropylene, and 5 to 50% by mass of vinylidene fluoride is exemplified.

  Such thermoplastic fluororesins are commercially available, for example, Dyneon THV series, Solvay KYNER, Central Glass Cefral Soft, Daikin Daiel Thermoplastic, Examples include AFLAS from Asahi Glass.

The blending of the component (e) must be performed at a temperature equal to or higher than the melting point of the component (e). If it is less than the melting point, the component (e) maintains a solid state, and thus cannot be uniformly dispersed in the composition. By mixing at or above the melting point of the component (e), it is possible to apply a shear stress in the molten state and uniformly disperse it.
(E) The compounding quantity of a component is 1-100 mass parts with respect to 100 mass parts of (a) component. Preferably, it is 3-50 mass parts. If the amount is too small, a sufficient effect of reducing fuel permeation may not be obtained. If the amount is too large, the rubber properties of the cured product may be impaired.

Other components In addition to the components (a) to (e), various conventionally known additives can be blended in the composition of the present invention as long as the effects of the present invention are not impaired. Specific examples of such components include 1-ethyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl-1. -Control agents for hydrosilylation reaction catalysts such as acetylene alcohols such as pentyn-3-ol and phenylbutynol, 3-methyl-3-penten-1-in, and 3,5-dimethyl-3-hexen-1-in, Examples thereof include pigments such as iron oxide, cerium oxide, and carbon black, colorants, dyes, antioxidants, oil-like compounds partially or entirely modified with fluorine. 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 for Producing Composition In producing the fluorine-containing curable composition of the present invention, component (e) is mixed with component (a) or component (a) and (d) at a temperature equal to or higher than the melting point of component (e). ) After adding and mixing to the mixture of components, the remaining components are added and mixed.
The meaning of adding and mixing the component (e) at a temperature equal to or higher than the melting point is as described above. In addition, after the component (e) is added to the component (a) or the mixture of the component (a) and the component (d), the remaining component is added and mixed to prevent the composition from being easily scorched. It is to do.

Method of Use The composition of the present invention may be configured as a so-called one-component type in which all the essential components (a) to (e) are handled as one composition depending on the application, or, for example, ( A so-called two-component type in which the components a), (c), (d) and (e) are one composition and the components (a), (b), (d) and (e) are the other composition And may be mixed for use.
Also in this case, in the production of the composition, as described above, the component (e) is converted into the component (a) or the mixture of the component (a) and the component (d) at a temperature equal to or higher than the melting point of the component (e). After the addition and mixing, the remaining components are preferably added and mixed to produce one-component type composition or one-component type composition and the other composition.

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 it is 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, and rubber having excellent characteristics can be obtained by such curing.

  The composition of this invention can be utilized for various uses. 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, Sealing materials such as skets, rubber parts for inkjet printers, rubber parts for semiconductor production lines, specifically diaphragms for devices that come in contact with chemicals, valves, O-rings, packing, gaskets, low friction and abrasion 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

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, a viscosity is a value in 25 degreeC and Me represents a methyl group by the following formula.

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、Ｒ９７２（日本アエロジル社製乾式シリカ）４０質量部、ＴＨＶ５５０Ｇ（ダイニオン社製熱可塑性フッ素樹脂；融点１６０〜１７５℃）２０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２０質量部になるように、式（６）のポリマー１００質量部添加して調製し、３本ロールミル処理を施した。以上調製した組成物１３０質量部に、次に下記式（８）で表される含フッ素有機ケイ素化合物３．４質量部、

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％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た。この混合物を１５０℃、１０分のプレス架橋（一次架橋）及び１８０℃、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、及び１３０ｍｍ×１３０ｍｍ×１ｍｍ）を得た。得られた硬化シートの物性はＪＩＳ Ｋ６２５３、ＪＩＳ Ｋ６２５１に準拠して測定した。また、燃料油透過性の測定は、ＪＩＳ Ｚ０２０８のカップ法を応用して測定した。カップの中にＦｕｅｌ Ｃ［トルエン／イソオクタン＝５０／５０（体積比）］を２ｇ仕込み、を直径７０ｍｍの円形状に切り取った上記硬化シート（厚さ１ｍｍ）で密封して、２３℃の恒温室に静置し、単位時間当たりの質量変化を測定した。結果を表１に示す。 [Example 1]
Following formula (6)

Polymer (viscosity 5,500 mm ² / s, number average molecular weight 15,700, vinyl group content 0.012 mol / 100 g) 100 parts by mass, R972 (Nippon Aerosil Co., Ltd. dry silica) 40 parts by mass, THV550G ( 20 parts by mass of Dyneon's thermoplastic fluororesin; melting point 160-175 ° C.) were mixed in a kneader at 175 ° C./2 hours. Thereafter, 100 parts by mass of the polymer of the formula (6) was added and prepared with a planetary mixer so that the blending amount of R972 was 20 parts by mass, and a three-roll mill treatment was performed. Next, 130 parts by mass of the composition prepared above, 3.4 parts by mass of a fluorine-containing organosilicon compound represented by the following formula (8),

0.2 parts by mass of a toluene solution (platinum concentration: 0.5% by mass) of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ and 0.3 parts by mass of a 50% toluene solution of ethynylcyclohexanol And mixed with a planetary mixer. This mixture was subjected to press crosslinking (primary crosslinking) at 150 ° C. for 10 minutes and oven crosslinking (secondary crosslinking) at 180 ° C. for 2 hours to obtain cured sheets (170 mm × 130 mm × 2 mm and 130 mm × 130 mm × 1 mm). It was. The physical properties of the obtained cured sheet were measured according to JIS K6253 and JIS K6251. The fuel oil permeability was measured by applying the cup method of JIS Z0208. 2 g of Fuel C [toluene / isooctane = 50/50 (volume ratio)] was charged into the cup and sealed with the cured sheet (thickness 1 mm) cut into a circular shape with a diameter of 70 mm, and the temperature-controlled room at 23 ° C. The mass change per unit time was measured. The results are shown in Table 1.

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、比表面積３００m²/gの乾式シリカフィラーの表面をヘキサメチルジシラザンで処理したフィラー５０質量部、ＴＨＶ５５０Ｇ（ダイニオン社製熱可塑性フッ素樹脂；融点１６０〜１７５℃）２０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シリカフィラーの配合量が２５質量部になるように、式（６）のポリマー１００質量部添加して調製し、３本ロールミル処理を施した。以上調製した組成物１３５質量部に、次に下記式（９）で表される含フッ素有機ケイ素化合物２．９質量部、

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％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た。この混合物を１５０℃、１０分のプレス架橋（一次架橋）および１８０℃、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、及び１３０ｍｍ×１３０ｍｍ×１ｍｍ）を得た。得られた硬化シートの物性はＪＩＳ Ｋ６２５３、ＪＩＳ Ｋ６２５１に準拠して測定した。また、燃料油透過性の測定は、実施例１と同じ方法で測定した。結果を表１に示す。 [Example 2]
Following formula (6)

The surface of a dry silica filler having a viscosity of 5,500 mm ² / s, a number average molecular weight of 15,700, and a vinyl group content of 0.012 mol / 100 g and a specific surface area of 300 m ² / g is represented by hexamethyl. 50 parts by mass of a filler treated with disilazane and 20 parts by mass of THV550G (a thermoplastic fluororesin manufactured by Dinion Co., Ltd .; melting point: 160 to 175 ° C.) were mixed in a kneader at 175 ° C./2 hours. Then, 100 mass parts of polymers of Formula (6) were added and prepared so that the compounding quantity of a silica filler might be 25 mass parts with a planetary mixer, and the 3 roll mill process was performed. To 135 parts by mass of the composition prepared above, 2.9 parts by mass of a fluorine-containing organosilicon compound represented by the following formula (9),

0.2 parts by mass of a toluene solution (platinum concentration: 0.5% by mass) of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ and 0.3 parts by mass of a 50% toluene solution of ethynylcyclohexanol And mixed with a planetary mixer. This mixture was subjected to press crosslinking (primary crosslinking) at 150 ° C. for 10 minutes and oven crosslinking (secondary crosslinking) at 180 ° C. for 2 hours to obtain cured sheets (170 mm × 130 mm × 2 mm and 130 mm × 130 mm × 1 mm). It was. The physical properties of the obtained cured sheet were measured according to JIS K6253 and JIS K6251. The fuel oil permeability was measured by the same method as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, a composition was prepared with the same formulation except that THV550G was not blended to obtain a cured sheet. The physical properties of the obtained cured sheet were measured according to JIS K6253 and JIS K6251. The fuel oil permeability was measured by the same method as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
In Example 2, a composition was prepared with the same formulation except that THV550G was not blended to obtain a cured sheet. The physical properties of the obtained sheet were measured according to JIS K6253 and JIS K6251. The fuel oil permeability was measured by the same method as in Example 1. The results are shown in Table 1.

  When Example 1 and Comparative Example 1 are compared with Example 2 and Comparative Example 2, respectively, it can be seen that Examples 1 and 2 containing THV550G have lower fuel permeability.

Claims (7)

(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 number average molecular weight of 3,000 to 100,000 having a perfluoropolyether structure containing a repeating unit of:
(B) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: the molar ratio of SiH groups in component (b) to alkenyl groups in component (a) is 0.4 to An amount of 5.0,
(C) Hydrosilylation reaction catalyst: catalytic amount,
(D) Silica-based filler: 1 to 100 parts by mass,
(E) Thermoplastic fluorine-based resin having a melting point of 100 to 200 ° C .: 1 to 100 parts by mass A fluorine-containing curable composition characterized by comprising: The perfluoropolyether structure of component (a)

(In the formula, q is an integer of 20 to 600.)
The fluorine-containing curable composition according to claim 1, wherein (A) Component is 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 - represented by or the following structural formula (Z) And 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 represented by —CH ₂ — or the following structural formula (Z ′)). And 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 20 to 600. ]

(Dimethylphenylsilylene group shown at o, m or p position)

(Dimethylphenylsilylene group shown at o, m or p position)
The fluorine-containing curable composition according to claim 1 or 2, wherein   The component (b) has one or more monovalent perfluoro group, monovalent perfluorooxy group, divalent perfluoro group or divalent perfluorooxy group in one molecule, and a silicon atom The fluorine-containing curable composition according to any one of claims 1 to 3, wherein the fluorine-containing curable composition has two or more hydrogen atoms bonded to each other. The fluorine-containing curable composition according to any one of claims 1 to 4, wherein the component (d) is a silica-based filler having a BET specific surface area of 30 m ² / g or more and having a hydrophobized surface. The thermoplastic fluororesin as component (e) is represented by the following general formula (2): CF ₂ = CXR ¹ (2)
(In the formula, X is a hydrogen atom or a halogen atom, R ¹ is a halogen atom or an alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, or an aryl group. Or may be partially or completely halogenated.)
The fluorine-containing curable composition according to any one of claims 1 to 5, which comprises a copolymer unit derived from at least one monomer having a structure.   In the production of the fluorinated curable composition according to any one of claims 1 to 6, the component (e) is added at a temperature equal to or higher than the melting point of the component (e), the component (a), or (a A method for producing a fluorine-containing curable composition, wherein the remaining components are added and mixed after being added to and mixed with a mixture of the component)) and the component (d).