JP2005330434A - Curable perfluoropolyether rubber composition and rubber product - Google Patents

Abstract

[Ｒｆ¹は１価のパーフルオロアルキル基又はパーフルオロオキシアルキル基。Ｒ¹は水素原子又は１価炭化水素基。]
【選択図】 なしPROBLEM TO BE SOLVED: To provide a cured film having excellent heat resistance, chemical resistance, solvent resistance, releasability, water repellency, oil repellency, low temperature characteristics, etc., and a cured film having a smooth surface and a uniform film thickness. A perfluoropolyether rubber composition is provided.
SOLUTION: (A) A linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure, and (B) a hydrogen atom directly bonded to a silicon atom in one molecule. A curable perfluoropolyether rubber composition containing two or more fluorine-containing organohydrogensiloxanes, (C) a platinum group compound, and (D) a fluorine-containing amide compound represented by the following general formula (1).
[Chemical 1]

[Rf ¹ is a monovalent perfluoroalkyl group or a perfluorooxyalkyl group. R ¹ is a hydrogen atom or a monovalent hydrocarbon group. ]
[Selection figure] None

Description

  The present invention relates to a curable perfluoropolyether rubber composition that gives a cured product having good heat resistance, chemical resistance, solvent resistance, mold release, water repellency, oil repellency, low temperature characteristics, and the like. In particular, the present invention relates to a curable perfluoropolyether rubber composition capable of providing a cured film having a smooth and uniform film thickness, and a rubber product obtained by curing the same.

  A linear fluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, and having two or more hydrogen atoms directly bonded to silicon atoms in one molecule From a composition comprising a fluorine-containing organohydrogensiloxane and a platinum group compound, a cured product having excellent balance of properties such as heat resistance, chemical resistance, solvent resistance, mold release, water repellency, oil repellency, and low temperature characteristics is obtained. This is proposed in Patent Document 1: Japanese Patent No. 2990646.

Various additives can be added to the composition as necessary in order to enhance its practicality. For example, in order to suppress curing at room temperature from the viewpoint of storage stability, a method of adding an acetylene compound is known as a typical example (Patent Documents 2 and 3: US Pat. No. 3,445,420 and JP-B-54). -3774).
However, when an acetylene compound is used, depending on the curing method, when the thickness of the cured film increases, the surface of the cured product may not be smooth and the surface characteristics may not be uniform.

Japanese Patent No. 2990646 U.S. Pat. No. 3,445,420 Japanese Patent Publication No.54-3774

  The present invention has been made in view of the above circumstances, and is excellent in heat resistance, chemical resistance, solvent resistance, releasability, water repellency, oil repellency, low temperature characteristics, etc., and has a smooth and uniform film thickness. An object of the present invention is to provide a curable perfluoropolyether rubber composition and a rubber product that give a cured film.

[式中、Ｒｆ¹は１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基である。また、Ｒ¹は水素原子、又は置換もしくは非置換の１価炭化水素基である。]
を添加した組成物が、上記目的を達成できることを知見し、本発明をなすに至ったものである。 As a result of diligent studies to achieve the above object, the present inventor has (A) a linear polyfluoro having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain. (D) a compound, (B) a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to a silicon atom in one molecule, and (C) an addition reaction type thermosetting composition comprising a platinum group compound. Fluorine-containing amide compound represented by the following general formula (1)

[Wherein, Rf ¹ represents a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group. R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. ]
It has been found that a composition to which is added can achieve the above object, and has led to the present invention.

  Accordingly, the present invention provides a curable perfluoropolyether rubber composition comprising the above components (A) to (D) and a rubber product obtained by curing it.

  According to the present invention, a cured film having excellent heat resistance, chemical resistance, solvent resistance, releasability, water repellency, oil repellency, low temperature characteristics, etc., and a smooth surface and a uniform film thickness can be provided. it can.

で表されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基、Ｒ²は水素原子、置換もしくは非置換の１価炭化水素基、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（４）

で表されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基であり、Ｒ²は上記と同じ基である。Ｒｆ²は２価のパーフルオロポリエーテル基であり、ａは独立に０又は１である。］ [(A) component]
(A) component of this invention is a linear polyfluoro compound which has a 2 or more alkenyl group in 1 molecule, and what is represented by following General formula (2) is preferable.
_{CH 2 = CH- (X) a} -Rf 2 - (X ') a -CH = CH 2 (2)
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ² -CO- (Y is -CH ₂ - or the following structural formula (3)

O, m or p-dimethylsilylphenylene group represented by the formula: R ² is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —. , —CH ₂ OCH ₂ — or —CO—NR ² —Y′— (Y ′ is —CH ₂ — or the following structural formula (4)

O, m or p-dimethylsilylphenylene group represented by the formula (I), R ² is the same group as described above. Rf ² is a divalent perfluoropolyether group, and a is independently 0 or 1. ]

Here, as R ² , in the case of other than a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms is preferable. Alkyl groups such as hexyl, cyclohexyl and octyl groups; aryl groups such as phenyl and tolyl groups; aralkyl groups such as benzyl and phenylethyl groups; and some or all of the hydrogen atoms of these groups are fluorine, etc. And a substituted monovalent hydrocarbon group substituted with a halogen atom.

Further, Rf ² in formula (2) is a divalent perfluoropolyether structure, compounds represented by the following general formula (5) or (6) are preferred.

（式中、ｐ及びｑはそれぞれ１〜１５０の整数であって、かつｐとｑの和の平均は、２〜２００である。また、ｒは０〜６の整数、ｔは２又は３である。）

（式中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは上記と同じである。）

(Wherein p and q are each an integer of 1 to 150, and the average of the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3. is there.)

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)

（式中、ｍ及びｎは１以上の整数、ｍ＋ｎ（平均）＝２〜２００である。）

（式中、ｍ及びｎは１以上の整数、ｍ＋ｎ（平均）＝２〜２００である。）

（式中、ｍは１〜２００の整数、ｎは１〜５０の整数である。） Preferable examples of the Rf ² group include those represented by the following formulas (a) to (c). More preferably, it is a divalent group having the structure of the formula (a).

(In the formula, m and n are integers of 1 or more, and m + n (average) = 2 to 200).

(In the formula, m and n are integers of 1 or more, and m + n (average) = 2 to 200).

(In the formula, m is an integer of 1 to 200, and n is an integer of 1 to 50.)

［式中、Ｘは−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ²−ＣＯ−（Ｙは−ＣＨ₂−又は下記構造式（３）

で表されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基、Ｒ²は水素原子、メチル基、フェニル基又はアリル基、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（４）

で表されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基であり、Ｒ²は上記と同じ基である。ａは独立に０又は１、Ｌは２〜６の整数、ｂ及びｃはそれぞれ０〜２００の整数である。］ (A) As a preferable example of a component, the compound represented by following General formula (7) is mentioned.

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

O, m or p-dimethylsilylphenylene group represented by the formula: R ² is a hydrogen atom, methyl group, phenyl group or allyl group, X ′ is —CH ₂ —, —OCH ₂ —, — CH ₂ OCH ₂ — or —CO—NR ² —Y′— (Y ′ is —CH ₂ — or the following structural formula (4)

O, m or p-dimethylsilylphenylene group represented by the formula (I), R ² is the same group as described above. a is independently 0 or 1, L is an integer of 2 to 6, and b and c are integers of 0 to 200, respectively. ]

  Specific examples of the linear polyfluoro compound represented by the general formula (7) include those represented by the following formula.

（式中、ｍ及びｎはそれぞれ０〜２００、ｍ＋ｎ＝６〜２００を満足する整数を示す。）

(In the formula, m and n are integers satisfying 0 to 200 and m + n = 6 to 200, respectively.)

  In addition, the viscosity (23 degreeC) of the linear polyfluoro compound of the said General formula (7) is 100-100,000 mPa * s by the viscosity measurement based on JISK6249, More preferably, it is 500-50,000 mPa * s, More preferably, it is within the range of 1,000 to 20,000 mPa · s, and when the composition is used for sealing, potting, coating, impregnation, etc., it has appropriate physical characteristics even in a cured product. This is desirable. Within the viscosity range, the most appropriate viscosity can be selected according to the application.

  These linear polyfluoro compounds can be used singly or in combination of two or more.

[Component (B)]
Component (B) is a fluorine-containing organohydrogensiloxane having 2 or more, preferably 3 or more hydrogen atoms directly bonded to silicon atoms in one molecule. The component (B) of the present invention functions as a crosslinking agent or chain extender for the component (A), and is compatible with the component (A), dispersibility, uniformity after curing, etc. From the viewpoint, fluorine-containing groups such as one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups, or divalent perfluorooxyalkylene groups are contained in one molecule. What has is preferable.

（式中、ｆは２〜２００、好ましくは２〜１００、ｈは１〜３の整数である。）
２価のパーフルオロオキシアルキレン基：

（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）_r−（ＣＦ₂ＣＦ₂Ｏ）_s−ＣＦ₂−
（但し、ｒ及びｓはそれぞれ１〜５０の整数である。） Examples of the fluorine-containing group include those represented by the following general formula.
Monovalent perfluoroalkyl group:
C _g F _{2g + 1} −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)
Divalent perfluoroalkylene group:
−C _g F _2g −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)
Monovalent perfluorooxyalkyl group:

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

(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) r -} (CF 2 CF 2 O) s -CF 2 -
(However, r and s are each an integer of 1 to 50.)

In addition, as the divalent linking group that connects the perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group or perfluorooxyalkylene group and the silicon atom, an alkylene group, an arylene group, a combination thereof, or these In this group, an ether bond oxygen atom, an amide bond, a carbonyl bond, etc. may be interposed.
—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—
And those having 2 to 12 carbon atoms.

  Examples of the component (B) having such a fluorine-containing group include the following compounds. 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.

  The blending amount of the component (B) is an effective amount for curing the component (A), and is usually (1 mol of an alkenyl group such as vinyl group, allyl group, cycloalkenyl group, etc. contained in the component (A) ( The amount of the hydrosilyl group of component B), that is, the Si—H group, is preferably 0.5 to 3.0 mol, more preferably 0.8 to 2.0 mol. If the amount of hydrosilyl groups (≡Si—H) is too small, the degree of cross-linking may be insufficient. As a result, a cured product may not be obtained, and if too large, foaming may occur during curing.

[Component (C)]
The platinum group compound which is the component (C) of the present invention is a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst is a catalyst that promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B). Since this hydrosilylation reaction catalyst is generally a noble metal compound and is expensive, platinum or a platinum group compound that is relatively easily available is often used.

Examples of the platinum group compound include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinylsiloxane, metal platinum supported on silica, alumina, carbon or the like. Rhodium, ruthenium, iridium, and palladium-based compounds are also known as platinum group metal catalysts other than platinum group compounds. For example, RhCl (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) _{4 and the} like. In the above formula, Ph is a phenyl group.

  When these catalysts are used, they can be used in solid form when they are solid catalysts, but in order to obtain a more uniform cured product, chloroplatinic acid or a complex dissolved in an appropriate solvent. Is preferably used by being dissolved in the linear polyfluoro compound of component (A).

  (C) Although the usage-amount of a component may be a catalyst amount, it is preferable to mix | blend 0.1-500 ppm (in platinum group metal atom conversion) with respect to 100 mass parts of (A) component.

[(D) component]
The fluorine-containing amide compound which is the component (D) of the present invention gives moderate storage stability by suppressing the curing of the composition of the present invention at room temperature, and gives the cured product obtained from the composition good surface characteristics. It is for providing and what is represented by following General formula (1) is preferable.

[式中、Ｒｆ¹は１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基である。また、Ｒ¹は水素原子、又は置換もしくは非置換の１価炭化水素基である。]

[Wherein, Rf ¹ represents a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group. R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. ]

Examples of Rf ¹ in the general formula (1) include those represented by the following general formula.
C _k F _{2k + 1} −
(In the formula, k is an integer of 1 to 20, preferably 5 to 15.)

（式中、ｆは１〜３０、好ましくは２〜１０、ｈは１〜３の整数である。）

(In the formula, f is 1 to 30, preferably 2 to 10, and h is an integer of 1 to 3.)

As R ¹ in the general formula (1), in addition to a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms is preferable. Group, butyl group, hexyl group, cyclohexyl group, octyl group and other alkyl groups; vinyl group, allyl group and other alkenyl groups; phenyl group, tolyl group and other aryl groups; benzyl group, phenylethyl group and other aralkyl groups, etc. A substituted monovalent hydrocarbon group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as fluorine, a silyl group such as an alkylsilyl group, an alkoxyalkylsilyl group or an alkoxysilyl group, an epoxy group, or the like. Can be mentioned. Of these, an allyl group and an aryl group are preferable.

The fluorine-containing amide compound represented by the general formula (1) can be obtained by the following method. That is, it is synthesized by reacting a compound having an acid fluoride group at one end represented by the following general formula (8) with a primary amine represented by the following general formula (9) in the presence of an acid acceptor such as triethylamine. be able to. Incidentally, R ¹ in the general formula (8) Rf ¹ and the general formula in (9) in denote the same as Rf ¹ and R ¹ above.

Specific examples of the component (D) having Rf ¹ and R ¹ include those represented by the following structural formula. These compounds may be used alone or in combination of two or more.

  (D) The compounding quantity of component is 0.01-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.05-5 mass parts, More preferably, it is the range of 0.1-2 mass parts. . If the amount is less than 0.01 parts by mass, the curing rate of the composition may not be sufficiently controlled, and the storage stability may be inferior, and the surface properties of the resulting cured product may be inferior. When it exceeds 10 parts by mass, the curability is inhibited, and the physical properties of the obtained cured product are deteriorated.

[Other ingredients]
In the composition of the present invention, in addition to the above components (A) to (D), a plasticizer, a viscosity modifier, a flexibility imparting agent, an inorganic filler, a hydrosilylation reaction catalyst, in order to enhance its practicality Various compounding agents such as a control agent, an adhesion promoter, an adhesion assistant, and a silane coupling agent can be added as necessary. The blending amount of these additives is arbitrary as long as the object of the present invention is not impaired and the properties of the composition and the physical properties of the cured product are not impaired.

  As a plasticizer, a viscosity modifier, and a flexibility imparting agent, a polyfluoromonoalkenyl compound represented by the following general formula (10) and / or a linear poly represented by the following general formulas (11) and (12) A fluoro compound can be used in combination.

（式中、ｗは１以上の整数、ｔは上記と同じ、かつ上記（Ａ）成分のＲｆ²基に関するｐ＋ｑ（平均）及びｒの和、並びにｕ及びｖの和のいずれの和よりも小さい。）］ Rf ³ − (X ′) _a CH═CH ₂ (10)
[Wherein, X ′ and a are the same as above, and Rf ³ is represented by the following general formula (13).

(Wherein, w is an integer of 1 or more, t is the same as above, and smaller than any of the sum of p + q (average) and r and the sum of u and v for the Rf ² group of component (A)) .)]

_{D-O- (CF 2 CF 2} CF 2 O) c -D (11)
(Wherein D is a group represented by the formula: C _s F _{2s + 1} — (s is 1 to 3), c is an integer of 1 to 200, and Rf ^{2 of the} component (A). Less than the sum of p + q (average) and r and the sum of u and v
D—O— (CF ₂ O) _d (CF ₂ CF ₂ O) _e —D (12)
(In the formula, D is the same as above, d and e are each an integer of 1 to 200, and the sum of d and e is p + q (average) and r for the Rf ² group of the component (A)). Or the sum of u and v.)

  Specific examples of the polyfluoromonoalkenyl compound represented by the general formula (10) include, for example, the following (note that m below satisfies the above requirements).

Specific examples of the linear polyfluoro compound represented by the above general formulas (11) and (12) include the following (for example, the following n or the sum of n and m satisfies the above requirements) To do.)
CF ₃ O— (CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF _{3
CF 3 - [(OCF 2 CF} 2) n (OCF 2) m] -O-CF 3
(M + n = 1 to 200, m = 1 to 200, n = 1 to 200)

  The compounding amount of the polyfluoro compound of the general formulas (10) to (12) is 1 to 100 parts by mass with respect to 100 parts by mass of the polyfluorodialkenyl compound of the general formula (2) as the component (A) in the composition. 300 parts by mass, preferably 50 to 250 parts by mass. Further, the viscosity (23 ° C.) is desirably in the range of 5 to 100,000 mPa · s, similarly to the polyfluorodialkenyl compound.

  Inorganic fillers such as fumed silica, colloidal silica, quartz powder, fused quartz powder, diatomaceous earth, calcium carbonate and other reinforcing or semi-reinforcing fillers, titanium oxide, iron oxide, carbon black, cobalt aluminate and the like Heat resistance improver such as pigment, titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, manganese carbonate, etc., heat conductivity enhancer such as alumina, boron nitride, silicon carbide, metal powder Further, a conductivity imparting agent such as carbon black, silver powder, and conductive zinc white can be added.

  Examples of the control agent for the hydrosilylation reaction catalyst include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl. Acetylenic alcohols such as -1-penten-3-ol and phenylbutynol, and a reaction product of chlorosilane having the above monovalent fluorine-containing substituent and acetylenic alcohol, 3-methyl-3-penten-1-yne 3,5-dimethyl-3-hexen-1-in, triallyl isocyanurate, etc., or polyvinyl siloxane, organophosphorus compounds, etc., and the addition thereof can keep the curing reactivity and storage stability moderately. .

  Further, adhesion promoters such as carboxylic acid anhydrides and titanate esters, adhesion assistants and / or silane coupling agents can be added.

  The manufacturing method in particular of the composition of this invention is not restrict | limited, It can manufacture by knead | mixing above-described (A)-(D) component and another arbitrary component. At that time, if necessary, a mixing apparatus such as a planetary mixer, a loss mixer, and a Hobart mixer, and a kneading apparatus such as a kneader and a three-roll can be used.

  Regarding the composition of the composition of the present invention, all the above-mentioned components (A) to (D) may be handled as one composition depending on the use, or may be configured as a so-called one-component type, or a two-component type. The two may be mixed at the time of use.

  The curing conditions of the composition of the present invention are preferably 1 to 30 minutes at 100 to 200 ° C. as a primary cure. If it is less than 100 ° C., the curing time becomes long, so that the industrial productivity may be inferior. If it exceeds 200 ° C., there is a risk of scorch generation, so 100 to 200 ° C. is preferable, and further 120 to 170 ° C. Is preferred. The curing time in that case may be appropriately selected as the time for completing the crosslinking reaction. Moreover, in order to stabilize the physical property of this composition, it is preferable to carry out secondary cure by heat processing for about 1 to 24 hours at 100-230 degreeC. The secondary cure is less effective at less than 100 ° C and may be thermally decomposed at more than 230 ° C. More preferably, it is suitable at 150 to 200 ° C. for 1 to 20 hours.

  The composition of this invention can be utilized for various uses. That is, since the fluorine content is high, the solvent resistance and chemical resistance are excellent, and the moisture permeability is low, and since it has low surface energy, it is excellent in 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, O-rings for injectors, or rubber parts for automobiles such as sealing materials such as oil seals and gaskets for cylinder heads; diaphragms for valves, valves, O-rings, packings , Oil seals, gaskets, etc. for chemical plants Parts: Rubber parts for inkjet printers such as diaphragms, valves, O-rings, packings, gaskets, and rubber parts for semiconductor production lines; analysis of diaphragms for pumps, O-rings, packings, valves, joints, etc. Rubber parts for physics and chemistry equipment And rubber parts for medical equipment; tent film materials, sealants, molded parts, extruded parts, coating materials, copying machine roll materials, moisture-proof coating materials for electric sensors, potting materials for sensors, sealing materials for fuel cells, laminated rubber cloths; or aircraft It is useful for aircraft rubber parts such as O-rings for fluid piping such as engine oil, jet fuel, hydraulic oil, and skid roll, face seals, packings, gaskets, diaphragms, and valves.

  In particular, as a rubber product comprising a cured product of the above curable perfluoropolyether rubber composition, for automobiles, chemical plants, inkjet printers, semiconductor production lines, analytical / physical equipment, medical equipment, It can be suitably used for aircraft or fuel cells, and is preferably used as a diaphragm, valve, O-ring, oil seal, gasket, packing, joint or face seal.

  In using the composition of the present invention, the composition can be selected according to its use and purpose by using an appropriate fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, Fluorinert (manufactured by 3M), Parr. It may be used by dissolving it in a desired concentration in fluorobutyl methyl ether, perfluorobutyl ethyl ether or the like. In particular, it is preferable to use a solvent in thin film coating applications.

  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, in the following example, a part shows a mass part. Moreover, a viscosity shows the measured value in 23 degreeC (based on JISK6249).

[Example 1]
Fluorine-containing organohydrogensiloxane represented by the following formula (15) (Si-H group content 0) on 100 parts of a polymer represented by the following formula (14) (viscosity 10,000 mPa · s, vinyl group content 0.012 mol / 100 g) .821 mol / 100 g) 1.61 parts, a toluene solution of a platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5 mass%) 0.20 parts, a fluorine-containing amide compound represented by the following formula (16): 50 parts were sequentially added and mixed to be uniform. Then, the composition was prepared by performing defoaming operation. In the following formulae, Me represents a methyl group.

  Next, after filling the obtained composition into a cartridge, it was extruded onto a flat plate (50 mm × 50 mm × 2 mm) made of Teflon (registered trademark of DuPont), and the thickness of the composition layer was adjusted to 250 μm using a bar coater. It applied so that it might become. The Teflon flat plate coated with the above composition was cured by heating for 1 hour in a drier set at 150 ° C. The surface of the cured film was flat and no wrinkles or streaks were observed. Further, when the cured film was peeled off from the Teflon flat plate and the thicknesses of the four end portions and the central portion were measured with a film thickness meter, a constant value was shown within the error range. Table 1 shows the observation results and film thickness measurement results on the surface of the cured film.

[Example 2]
A composition was prepared in the same manner as in Example 1, except that 0.50 part of the fluorinated amide compound represented by the following formula (17) was used instead of the fluorinated amide compound represented by the formula (16) in Example 1. Were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
A composition was prepared in the same manner as in Example 1 except that 0.20 part of a 50% toluene solution of ethynylcyclohexanol was added to the formulation of Example 2, and the same evaluation as in Example 1 was performed. . The results are shown in Table 1.

[Comparative Example 1]
A composition was prepared in the same manner as in Example 1 except that 0.50 part of a 50% toluene solution of ethynylcyclohexanol was used instead of the fluorine-containing amide compound represented by the formula (16) in Example 1. Evaluation similar to Example 1 was performed. The results are shown in Table 1.

＊凹凸が激しく測定可能な平坦部がないため

* Because there are no flat parts that can be measured severely

Claims (6)

(A) Linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain 100 parts by mass (B) Directly bonded to a silicon atom in one molecule Fluorine-containing organohydrogensiloxane having two or more hydrogen atoms (A) Amount of 0.5 to 3.0 moles as Si-H groups per mole of alkenyl group of component (C) Platinum group compound Platinum group metal atom 0.1-500ppm in conversion
(D) Fluorine-containing amide compound represented by the following general formula (1)

[Wherein, Rf ¹ represents a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group. R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. ]
A curable perfluoropolyether rubber composition containing 0.01 to 10 parts by mass. (A) component is the following general formula (2)
_{CH 2 = CH- (X) a} -Rf 2 - (X ') a -CH = CH 2 (2)
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ² -CO- (Y is -CH ₂ - or the following structural formula (3)

O, m or p-dimethylsilylphenylene group represented by the formula: R ² is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —. , —CH ₂ OCH ₂ — or —CO—NR ² —Y′— (Y ′ is —CH ₂ — or the following structural formula (4)

O, m or p-dimethylsilylphenylene group represented by the formula (I), R ² is the same group as described above. a is independently 0 or 1.
Rf ² is a divalent perfluoropolyether group represented by the following general formula (5) or (6).

(Wherein p and q are each an integer of 1 to 150, and the average of the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3. is there.)

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)]
The curable perfluoropolyether rubber composition according to claim 1, which is a linear polyfluoro compound having a branch represented by the formula:   The component (B) fluorine-containing organohydrogensiloxane is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent perfluoroalkyl group in one molecule. The curable perfluoropolyether rubber composition according to claim 1 or 2, which has a fluorooxyalkylene group.   A rubber product comprising a cured product of the curable perfluoropolyether rubber composition according to any one of claims 1 to 3.   The rubber product according to claim 4, which is used for automobiles, chemical plants, inkjet printers, semiconductor production lines, analytical / physical equipment, medical equipment, aircraft or fuel cells. The rubber product according to claim 4 or 5, which is a diaphragm, valve, O-ring, oil seal, gasket, packing, joint or face seal.