JP2018070701A - Fluorine-containing curable composition and rubber article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing curable composition which is easy to mold with low viscosity and gives a cured product excellent in heat resistance, chemical resistance, solvent resistance, and mechanical strength and particularly excellent in light transmissivity.SOLUTION: The fluorine-containing curable composition contains (a) a fluorine-containing polymer represented by formula (1) and having a number average molecular weight of 1,000-100,000, (b) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule, and (c) a hydrosilylation reaction catalyst. (Rf is a perfluoroalkylene group or a divalent perfluoropolyether group.)SELECTED DRAWING: None

Description

  The present invention is a low-viscosity, easy-to-mold, excellent heat resistance, chemical resistance, solvent resistance and mechanical strength, and in particular, a fluorine-containing curable composition that gives a cured product excellent in light transmittance, and the composition The present invention relates to a rubber article obtained by curing a product.

  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 A cured product having excellent heat resistance, chemical resistance, solvent resistance, mold release, water repellency, oil repellency, weather resistance, and the like can be obtained from the composition containing the organosilicon compound and the hydrosilylation reaction catalyst. Are known from Japanese Patent No. 2990646 (Patent Document 1), Japanese Patent Application Laid-Open No. 2011-201940 (Patent Document 2), and the like.

  The polymers described in Patent Document 1 and Patent Document 2 have sufficient performance in most applications. However, each polymer has an amide group-aromatic ring bond, and a near ultraviolet ray derived from the bond. Since it shows strong light absorption in the region, it is not suitable for an environment where optical transparency is required, such as an optical semiconductor sealing material application.

  By the way, although the hydrosilylation reaction catalyst is used for the fluorine-containing curable composition shown in the said patent document 1 or patent document 2, since this catalyst shows favorable catalyst activity, all the components are made into one composition. In the case of a so-called one-component composition that is handled, it is necessary to add a reaction control agent in order to obtain sufficient storage stability. On the other hand, the curability is sacrificed by the addition of the control agent, and high-temperature heat treatment is necessary to sufficiently advance the curing. Therefore, in order to apply the fluorine-containing composition, a heating process is required, which limits the production line, and it is difficult to apply to a member having poor heat resistance.

  The fluorine-containing curable compositions shown in Patent Document 1 and Patent Document 2 described above are, for example, linear having at least two alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain. A so-called two-component composition such as a perfluoropolyether compound and a hydrosilylation catalyst as a main agent and other components as a curing agent can also be used. In this case, it is not necessary to add a reaction control agent for obtaining storage stability, and it is possible to cure at a low temperature near room temperature. The process becomes complicated.

  On the other hand, photo-curable hydrosilylation catalyst that activates the catalyst by UV light irradiation in silicone elastomer material, photo-curing property that has both sufficient storage stability when not irradiated with light and good curability when irradiated with light Compositions are known (Patent Document 3 and Patent Document 4). By applying the photoactive hydrosilylation catalyst to a one-component type fluorine-containing composition, a heating step and a two-component mixing step are not required, and a photocurable fluorine-containing composition exhibiting sufficient storage stability and curability. Although the fluorine-containing curable composition shown in Patent Document 1 or Patent Document 2 exhibits strong light absorption in the near ultraviolet region derived from the amide group-aromatic ring bond as described above, photocuring is possible. It is difficult to put the functional fluorine-containing composition into practical use.

  As described above, in order to obtain a cured product that requires heat resistance, chemical resistance, solvent resistance, mold releasability, water repellency, oil repellency, weather resistance and also requires light transmission and / or photocurability. In addition, a fluorine-containing composition having excellent light transmittance has been desired.

Japanese Patent No. 2990646 JP 2011-201940 A Special table 2011-511768 gazette JP 2010-47646 A

  Therefore, the present invention is a fluorine-containing curable composition that gives a cured product having a low viscosity, easy to mold, excellent in heat resistance, chemical resistance, solvent resistance and mechanical strength, particularly excellent in light transmittance, and the The object is to provide a rubber article obtained by curing the composition.

  As a result of diligent research to achieve the above object, the inventors of the present invention have at least two alkenyl groups in one molecule as the fluorinated polymer having an alkenyl group of the base polymer, and the following general formula (1) By using a fluorine-containing polymer having a number average molecular weight of 1,000 to 100,000 having a specific polymer terminal structure that does not have an amide group-aromatic ring bond in the polymer terminal structure, Discovered that a fluorine-containing curable composition that gives a cured product that is easy to mold, has excellent heat resistance, chemical resistance, solvent resistance and mechanical strength, and in particular has excellent light transmittance, and completed the present invention. did.

That is, the present invention provides the following fluorine-containing curable composition and rubber article.
[1]
(A) The following general formula (1)

(In the formula (1), Rf is a perfluoroalkylene group or a divalent perfluoropolyether group, R ¹ and R ² are each independently a vinyl group or an alkyl group having 1 to 4 carbon atoms, and R ³ is An alkylene group having 3 to 6 carbon atoms, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, or (It is a C1-C4 alkyl group optionally substituted with fluorine.)
A fluorine-containing polymer having a number average molecular weight of 1,000 to 100,000 represented by:
(B) Fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: The molar ratio of hydrosilyl group (SiH group) in component (b) to alkenyl group in component (a) An amount of 0.4 to 5, and (c) hydrosilylation reaction catalyst: a fluorine-containing curable composition containing a catalytic amount.

[2]
In general formula (1), R ¹ and R ² are methyl groups, R ³ is a trimethylene group, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , The fluorine-containing curable composition according to [1], wherein R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms.

[3]
Furthermore, (d) Silica-type filler: The fluorine-containing curable composition as described in [1] or [2] which contains 1-100 mass parts with respect to 100 mass parts of (a) component.

[4]
In the general formula (1), the divalent perfluoropolyether group of Rf is represented by the following formula (2)

(In Formula (2), g is an integer of 1-6, and h is an integer of 20-600.)
The fluorine-containing curable composition according to any one of [1] to [3], which is a group having a structure represented by:
[5]
In the general formula (1), the divalent perfluoropolyether group of Rf is represented by the following formulas (3) to (5).

(In Formula (3), Y is a fluorine atom or a trifluoromethyl group, and p, q, and r are integers satisfying p ≧ 0, q ≧ 0, 0 ≦ p + q ≦ 600, and 0 ≦ r ≦ 6, respectively. (However, p = q = r = 0 is excluded.)

(In Formula (4), Y is a fluorine atom or a trifluoromethyl group, and v and w are integers satisfying 0 ≦ v ≦ 300, 0 ≦ w ≦ 300, and 1 ≦ v + w ≦ 600, respectively. (Repeating units may be combined randomly.)

(In Formula (5), z is an integer of 1 ≦ z ≦ 600.)
[4] The fluorine-containing curable composition according to [4], which is a group having a structure selected from the group consisting of structures represented by:

[6]
The component (b) contains one or more monovalent perfluoroalkyl group, monovalent perfluoropolyether group, divalent perfluoroalkylene group, or divalent perfluoropolyether group in one molecule. The fluorine-containing curable composition according to any one of [1] to [5], which is an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms.

[7]
A rubber article comprising a cured product of the fluorine-containing curable composition according to any one of [1] to [6].

  According to the present invention, there is provided 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 gives a cured product particularly excellent in light transmittance. be able to. In addition, rubber articles obtained by curing the above composition are useful as rubber members for automobiles, chemical equipment, chemical plants, etc., sealing materials for alkaline cleaning liquid containers, and optical semiconductor sealants. It can also be used as a photocurable composition that does not require heating.

2 is a ¹ H-NMR spectrum of an amino group-containing vinylsilane prepared in Synthesis Example 1. FIG. 2 is a ¹ H-NMR spectrum of a fluorine-containing polymer prepared in Synthesis Example 2.

The fluorine-containing curable composition of the present invention is
(A) a fluorine-containing polymer having at least two alkenyl groups in one molecule and having a number average molecular weight of 1,000 to 100,000 represented by the following general formula (1):
(B) A fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule, and (c) a hydrosilylation reaction catalyst.

（式（１）中、Ｒｆはパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｒ¹及びＲ²はそれぞれ独立に、ビニル基又は炭素数１〜４のアルキル基、Ｒ³は炭素数３〜６のアルキレン基、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＲ¹⁴はそれぞれ独立に、水素原子、またはフッ素置換されていてもよい炭素数１〜４のアルキル基である。） [(A) component]
The component (a) of the present invention is a fluorine-containing polymer having a number average molecular weight of 1,000 to 100,000 and having at least two alkenyl groups in one molecule represented by the following general formula (1) It is.

(In the formula (1), Rf is a perfluoroalkylene group or a divalent perfluoropolyether group, R ¹ and R ² are each independently a vinyl group or an alkyl group having 1 to 4 carbon atoms, and R ³ is An alkylene group having 3 to 6 carbon atoms, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, or (It is a C1-C4 alkyl group optionally substituted with fluorine.)

In the general formula (1), R ¹ and R ² are each independently a vinyl group or 1 to 4 alkyl groups, that is, vinyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. And a group selected from a tert-butyl group, preferably a vinyl group or a methyl group.

In the general formula (1), R ³ is a linear or branched alkylene group having 3 to 6 carbon atoms (for example, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group). ), A hexamethylene group, and the like. Those having a carbon number less than the lower limit are difficult to synthesize, while those having a carbon number exceeding the upper limit are easily oxidized and thus have poor heat resistance. Preferably R ³ is a propylene group, in particular a trimethylene group.

In the above general formula (1), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or fluorine. It is a C1-C4 alkyl group (for example, a methyl group, a trifluoromethyl group etc.) which may be substituted. R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ facilitate the production of the fluoropolymer of the above general formula (1). Therefore, a hydrogen atom is preferable.

Examples of the perfluoroalkylene group represented by Rf in the general formula (1) include linear or branched divalent perfluoroalkylene groups having 2 to 10 carbon atoms, preferably about 2 to 6 carbon atoms.
The divalent perfluoropolyether group has the following formula:

(In the formula, g is an integer of 1 to 6.)
Examples thereof include those represented by the following formula (2) including a large number of repeating units (perfluorooxyalkylene units) represented by: The repeating units (perfluorooxyalkylene units) constituting the divalent perfluoropolyether group are usually linked in a straight chain, but each repeating unit (perfluorooxyalkylene unit) ) Itself may be linear or branched (eg, —CF (CF ₃ ) CF ₂ O—, etc.).

（式（２）中、ｇは１〜６の整数であり、ｈ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。）

(In Formula (2), g is an integer of 1-6, h is 20-600, Preferably it is 30-400, More preferably, it is an integer of 30-200.)

General formula above

As the repeating unit represented by, for example, a unit represented by the following formula and the like can be mentioned.

  Among these, the unit represented by the following formula is particularly preferable.

  The divalent perfluoropolyether group represented by Rf may be composed of one of these repeating units, or may be composed of a combination of two or more.

  The divalent perfluoropolyether group may be a combination of a perfluorooxyalkylene unit repeating structure and a perfluoroalkylene group, and is represented by, for example, the following formulas (3) to (5). It preferably has a structure selected from the group consisting of structures.

（式（３）中、Ｙはフッ素原子又はトリフルオロメチル基であり、ｐ，ｑ及びｒは、それぞれｐ≧０、ｑ≧０、０≦ｐ＋ｑ≦６００、及び０≦ｒ≦６を満たす整数である。但し、ｐ＝ｑ＝ｒ＝０を除く。）

(In Formula (3), Y is a fluorine atom or a trifluoromethyl group, and p, q, and r are integers satisfying p ≧ 0, q ≧ 0, 0 ≦ p + q ≦ 600, and 0 ≦ r ≦ 6, respectively. (However, p = q = r = 0 is excluded.)

(In Formula (4), Y is a fluorine atom or a trifluoromethyl group, and v and w are integers satisfying 0 ≦ v ≦ 300, 0 ≦ w ≦ 300, and 1 ≦ v + w ≦ 600, respectively. (Repeating units may be combined randomly.)

(In Formula (5), z is an integer of 1 ≦ z ≦ 600.)

  Specific examples of Rf in the general formula (1) (formulas (6) to (14)) are shown below.

(In the formula (8), p1, q1 and r1 are integers satisfying p1 ≧ 0, q1 ≧ 0, 0 ≦ p1 + q1 ≦ 200, particularly 2 ≦ p1 + q1 ≦ 150 and 0 ≦ r1 ≦ 6, respectively.)

(In formulas (9) and (10), p2 and q2 are integers satisfying 1 ≦ p2 ≦ 100, 1 ≦ q2 ≦ 100, and 2 ≦ p2 + q2 ≦ 200, respectively.)

(In the formulas (11) to (14), v1, v2, w1, and z1 are 2 ≦ v1 ≦ 200, 1 ≦ v2 ≦ 100, 1 ≦ w1 ≦ 100, 2 ≦ v2 + w1 ≦ 200, 1 ≦ z1 ≦ 200, respectively. (Each repeating unit may be bonded at random.)

The fluorine-containing polymer of the general formula (1) has a polystyrene-equivalent number average molecular weight of 1,000 to 100,000 in gel permeation chromatography (GPC), and particularly 3,000 to 30,000. preferable. If the number average molecular weight is less than 1,000, the required chemical resistance cannot be satisfied. On the other hand, if the number average molecular weight exceeds 100,000, it causes a problem in compatibility with other components, which is not preferable.
In addition, the measurement of the gel permeation chromatography (GPC) in this invention was performed on the following conditions.
[Measurement condition]
Developing solvent: Hydrochlorofluorocarbon (HCFC) -225
Flow rate: 1 mL / min.
Detector: Evaporative light scattering detector Column: TSKgel Multipore HXL-M manufactured by Tosoh Corporation
7.8 mmφ × 30 cm 2 column temperature used: 35 ° C.
Sample injection amount: 100 μL (HCFC-225 solution with a concentration of 0.3 mass%)

  Specific examples of the fluorine-containing polymer of component (a) include those shown below (formulas (15) to (20)), but the present invention is not limited thereto.

(In the formulas (15) to (17), p, q and r are integers satisfying p ≧ 0, q ≧ 0, 0 ≦ p + q ≦ 600 and 0 ≦ r ≦ 6, respectively, where p = q = Except r = 0)

(In the formulas (18) to (20), v and w are integers satisfying 0 ≦ v ≦ 300, 0 ≦ w ≦ 300, and 1 ≦ v + w ≦ 600, respectively. Each repeating unit is bonded at random. You can.)

  The fluorine-containing polymer represented by the general formula (1) of the present invention can be produced, for example, by the steps shown below.

  In the first step, a halogenated silane having a halogen atom on the silicon atom and a halogen atom on the silicon atom, such as 3-chloropropyldimethylchlorosilane, and a Grignard reagent having a vinyl group, such as vinylmagnesium chloride, are added. It is made to react and it is set as halogenated alkyl vinyl silanes, such as 3-chloropropyl dimethyl vinyl silane, by introduce | transducing a vinyl group on a silicon atom. When 3-chloropropylmethyldichlorosilane or 3-chloropropyltrichlorosilane is used as the halogenated silane instead of 3-chloropropyldimethylchlorosilane, 3-chloropropylmethyldivinylsilane or 3-chloropropyltrivinylsilane is obtained, respectively. It is done. The reaction is preferably carried out by dropping a halogenated silane into a tetrahydrofuran solution of vinylmagnesium chloride. The reaction temperature may be about 20 to 75 ° C. Since the reaction is exothermic, if the temperature is too high, the reaction is carried out while cooling. After completion of the dropwise addition, stirring is further performed for 30 minutes to 10 hours to complete the reaction. After completion of the reaction, the magnesium salt produced by the reaction is dissolved in dilute hydrochloric acid, and the organic layer is recovered and purified to obtain a halogenated alkylvinylsilane such as chloroalkylvinylsilane, which is an intermediate of the target product.

  In the second step, the vinyl silane obtained in the first step, such as 3-chloropropyldimethylvinylsilane, is substituted with an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with fluorine, or unsubstituted. By reacting cyclohexylamine, for example, cyclohexylamine, an amino group-containing vinylsilane that is an intermediate of the target product can be obtained. The substituent on the carbon atom of cyclohexylamine may be any group that does not absorb light from the visible region to the near ultraviolet region. When cyclohexylamine has a substituent, the boiling point of the organosilicon compound obtained by the reaction is high, and the efficiency of purification is lowered. Therefore, unsubstituted cyclohexylamine is preferable. The reaction is carried out by mixing cyclohexylamine substituted or unsubstituted with hydrogen atoms and 3-chloropropyldimethylvinylsilane and heating at a temperature of 70 to 150 ° C. for 1 to 20 hours. After completion of the reaction, the hydrochloride is removed and further purified to obtain an amino group-containing vinylsilane that is an intermediate of the target product.

  In the third step, the fluorine-containing polymer represented by the general formula (1) is obtained by reacting the amino group-containing vinylsilane obtained in the second step with the compound represented by the following general formula (6). It is done.

（式（２１）中、Ｒｆはパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｘはフッ素、塩素等のハロゲン、又は炭素数１〜４のアルコキシ基である。）

(In formula (21), Rf is a perfluoroalkylene group or a divalent perfluoropolyether group, and X is a halogen such as fluorine or chlorine, or an alkoxy group having 1 to 4 carbon atoms.)

  To the carbonyl group equivalent of the perfluorodicarbonyl compound represented by the general formula (21), 1.0 to 1.2 molar equivalent of amino group-containing vinylsilane is added to the carbonyl compound and stirred for 30 minutes to 3 hours. As a result, the fluorine-containing polymer represented by the general formula (1) is produced.

  When X is halogen, the reaction temperature is in the range of 20 to 100 ° C, preferably 35 to 60 ° C, and more preferably 35 to 45 ° C. In order to enhance the compatibility between the perfluorodihalide and the amino group-containing vinylsilane, a solvent such as 1,3-bistrifluoromethylbenzene may be added. After completion of the reaction, 1.2 molar equivalents or more of calcium carbonate is added and heated to 100 to 150 ° C. to remove halide ions as calcium halide. Next, the solid matter is removed by filtration and purified by removing the unreacted amino group-containing vinyl silane and the solvent to obtain the fluorine-containing polymer represented by the general formula (1) as the target product.

  When X is an alkoxy group, the reaction temperature is in the range of 100 to 200 ° C, preferably 100 to 150 ° C, more preferably 120 to 150 ° C. In order to enhance the compatibility between the perfluorodihalide and the amino group-containing vinylsilane, a solvent such as 1,3-bistrifluoromethylbenzene may be added. After completion of the reaction, 1.2 molar equivalents or more of calcium carbonate is added and heated to 100 to 150 ° C. to remove halide ions as calcium halide. Next, the solid matter is removed by filtration and purified by removing the unreacted amino group-containing vinyl silane and the solvent to obtain the fluorine-containing polymer represented by the general formula (1) as the target product.

  (A) The fluorine-containing polymer of a component can also be used by 1 type, or can also be used in combination of 2 or more type.

[Component (b)]
The component (b) fluorine-containing organosilicon compound is a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms (that is, a hydrosilyl group represented by SiH) in one molecule. It acts as a component cross-linking agent (and chain extender). The fluorine-containing organosilicon compound as the component (b) is not particularly limited, but in consideration of compatibility with the component (a), dispersibility, uniformity after curing, etc., one or more components per molecule Monovalent or divalent fluorine-containing organic group (specifically, the monovalent fluorine-containing organic group includes a perfluoroalkyl group and a monovalent perfluoropolyether group (for example, one end is a fluorine atom or a perfluoroalkyl group). The divalent fluorine-containing organic group such as a perfluorooxyalkylene unit repeating structure blocked with a group is a divalent perfluoroalkylene group or a divalent perfluoropolyether group (for example, perfluorooxyalkylene). Etc.) having a repeating unit structure or a combination of a perfluorooxyalkylene unit repeating structure and a perfluoroalkylene group). At least 2 hydrogen atoms bonded to atom, preferably an organic silicon compound having 3 or more (e.g., linear, branched, siloxane cyclic structure such as, silalkylenes, silphenylene, silane compounds) are preferred.

（式（２２）中、ａは１〜１０、好ましくは２〜８の整数である。）

Examples of the monovalent fluorine-containing organic group include groups represented by the following formulas.

(In the formula (22), a is an integer of 1 to 10, preferably 2 to 8.)

(In the formulas (23) to (28), k is an integer of 1 to 6, and n and m are integers that satisfy 0 ≦ m ≦ 100, 0 ≦ n ≦ 100, and 0 ≦ m + n ≦ 100, respectively. Each repeating unit may be bonded at random.)

  Examples of the divalent fluorine-containing organic group include groups represented by the following formula.

(In formulas (29) and (30), g is an integer of 1 to 10, preferably 2 to 8.)

(In Formula (31), Y is a fluorine atom or a trifluoromethyl group, and p, q, and r are p ≧ 0, q ≧ 0, 0 ≦ p + q ≦ 600, particularly 2 ≦ p + q ≦ 200, and 0, respectively. ≦ r ≦ 6, except r = p = q = 0.)

(In Formula (32), Y is a fluorine atom or a trifluoromethyl group, and v and w are integers satisfying 0 ≦ v ≦ 300, 0 ≦ w ≦ 300, and 1 ≦ v + w ≦ 600, respectively. (Repeating units may be combined randomly.)

(In Formula (33), z is an integer of 1 ≦ z ≦ 600.)

  The monovalent or divalent fluorine-containing organic group may be directly bonded to the silicon atom, but may be bonded to the silicon atom via a divalent linking group. Here, as the divalent linking group, an alkylene group, an arylene group, or a combination thereof may be used, or an ether bond oxygen atom, an amide bond, a carbonyl bond, or the like may be interposed therebetween. The divalent linking group preferably has 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms, and specific examples include groups represented by the following formulas. In the following formulae, Ph and Ph 'are a phenyl group, and cHx is a cyclohexyl group.

  In addition, since light transmittance is impaired, it is desirable that the divalent linking group does not include an amide group-aromatic ring bond.

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

  The fluorine-containing organosilicon compound as component (b) may be linear, branched or cyclic, and may have a three-dimensional network structure. The number of silicon atoms in the molecule of the fluorine-containing organosilicon compound is not particularly limited, but is usually preferably 2 to 60, particularly about 3 to 30.

  Examples of such a fluorine-containing organosilicon compound include an organosilicon compound having a siloxane structure and / or a silalkylene structure, which is represented by the following formula. More than one species may be used in combination.

  The amount of component (b) is usually the amount of hydrosilyl group (ie, SiH group) in component (b) relative to 1 mole of alkenyl group such as vinyl group, allyl group, cycloalkenyl group and the like contained in component (a). The amount is such that the total molar ratio is 0.4 to 5, and preferably 0.8 to 3. If the amount of the hydrosilyl group in 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. Moreover, this (b) component may be used 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, compounds of these transition metals, and the like are preferably used. In the present invention, it is preferable to use platinum or a platinum compound that is relatively easily available.

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 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 , RhCl (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 a so-called catalytic amount. However, from an economic standpoint or in order to obtain a good cured product, the total amount of the composition In terms of the mass of the platinum group metal, it is preferably 0.1 to 1,000 ppm, more preferably about 0.1 to 500 ppm.

In this invention, the following can be used as an arbitrary component as needed.
[Component (d)]
In the present invention, a silica-based filler can be further used as the component (d). Silica-based fillers include pulverized silica obtained by pulverizing quartz or glass, fused silica that is once melted and then formed into spherical particles, wet silica (precipitated silica) produced by adding mineral acid to sodium silicate, silane Examples thereof include dry silica (fumed silica or fumed silica) produced by burning a compound. Among these, from the viewpoint of improving the mechanical strength, BET specific surface area of 30 m ² / g or more, preferably silica-based filler 50 to 400 m ² / g is preferably used. In addition, wet silica and dry silica correspond to this, but dry silica with little adsorbed moisture is suitable. In consideration of wettability with the polymer component, it is more preferable that the surface of the silica-based filler is hydrophobized. If the surface of the silica-based filler is not hydrophobized, there is a risk that a sufficient mechanical strength cannot be obtained, or that the viscosity of the composition becomes abnormally high.

  (D) When using a component, it is preferable that the compounding quantity shall be 1-100 mass parts with respect to 100 mass parts of (a) component, especially 1-40 mass parts. 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 may be increased and workability may be impaired.

[Other ingredients]
In addition to the above-described components (a) to (c) and the optional component (d), various conventionally known additives are blended in the composition of the present invention within a range not impairing the effects of the present invention. be able to. Examples of the additive include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl-1-pentyne- Acetylene alcohol such as 3-ol and phenylbutynol, a reaction product of chlorosilane having a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group and an acetylenic alcohol, 3-methyl-3-pentene-1 -In, 3,5-dimethyl-3-hexen-1-in, triallyl isocyanurate, polyvinylsiloxane, pigments such as iron oxide, cerium oxide, carbon black, etc. Coloring agents, dyes, antioxidants, oily compounds partially or entirely modified with fluorine, and the like can be mentioned. In addition, the addition amount of these arbitrary components can be made arbitrary in the range which does not prevent the effect of this invention.

[how to 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 (c) are handled as one composition depending on the application, or, for example, the above (a) ), (C) component as one composition and components (a), (b) as the other composition, so-called two-component type, which may be 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- 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 standing at room temperature or heating, as in the case of conventional fluorine-containing curable compositions. It can also be photocured by using a hydrosilylation catalyst that converts to By such curing, a rubber article having excellent characteristics can be obtained.

  The fluorine-containing curable composition of the present invention has solvent resistance, chemical resistance, acid resistance, and amine resistance in the same manner as a curable composition using a conventional linear fluorine-containing polymer as a base polymer (main agent). It is excellent and has low moisture permeability and low surface energy. Therefore, it has excellent releasability and water repellency and can be used for various applications. For example, rubber parts for automobiles that require oil resistance, specifically diaphragms for fuel regulators, diaphragms for pulsation dampers, diaphragms for oil pressure switches, diaphragms for EGR, canister valves, power control, etc. Valves such as valves, O-rings such as O-rings for quick connectors and O-rings for injectors, or sealing materials such as oil seals and gaskets for cylinder heads, or pressure sensor protective materials and vibration isolation Can be suitably used for the intended material. Also, rubber parts for chemical plants, specifically pump diaphragms, valves, O-rings, hoses, packings, seals such as oil seals, gaskets, rubber parts for inkjet printers, rubber for semiconductor production lines Parts, specifically diaphragms for equipment in contact with chemicals, sealing materials such as valves, O-rings, packings, gaskets, valves that require low friction and wear resistance, rubber parts for analysis, physics and chemistry equipment, etc. Specifically, it can be suitably used as a diaphragm for a pump, a valve, a seal part (O-ring, packing, etc.), a rubber part for a medical device, specifically a pump, a valve, and a joint. Furthermore, tent film materials, sealants, molded parts, extruded parts, coating materials, copying machine roll materials, electrical moisture-proof coating materials, sensor potting materials, laminated rubber cloth, aircraft engine oil, jet fuel, hydraulic oil, It is useful for O-rings for fluid piping such as skid rolls, face seals, packings, gaskets, diaphragms, valves, aircraft rubber parts, sealants for alkaline cleaning liquid containers, sealants for optical semiconductor elements, and the like.

  Further, since the fluorine-containing curable composition of the present invention is superior in light transmittance from the ultraviolet region to the visible region as compared with the conventional fluorine-containing curable composition, by using an appropriate hydrosilylation catalyst, It can be used as a photocurable composition that does not require heat curing for molding, and can be easily applied to members having poor heat resistance.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Me represents a methyl group.

[Synthesis Example 1]
175 g of 3-chloropropyldimethylchlorosilane was added dropwise to 800 mL of a tetrahydrofuran solution (1.6 mol / L) of vinylmagnesium chloride in a 2 L flask over 30 minutes. During the dropping, the temperature inside the flask was raised to 65 ° C. After completion of dropping, stirring was continued for 4 hours to complete the reaction. The contents of the flask were poured into dilute hydrochloric acid for liquid separation, washed twice with water, and the organic layer was recovered. This was distilled to obtain 123 g of 3-chloropropyldimethylvinylsilane as a product of the first step. The boiling point of 3-chloropropyldimethylvinylsilane was 80 ° C. at 40 mmHg.

Separately, cyclohexylamine was charged into a 300 mL flask and the internal temperature was heated to 130 ° C. The said intermediate body and 50 g of 3-chloropropyl dimethyl vinyl silanes were dripped there over 40 minutes. After completion of the dropping, the reaction was completed by stirring for about 6 hours at an internal temperature of 130 to 135 ° C. A white solid precipitated after the reaction. The reaction mixture was cooled to 27 ° C. and 200 g of a 30% aqueous solution of sodium hydroxide was added. After stirring for about 3 hours, the mixture was separated and the organic layer was recovered and distilled to obtain 36 g of a colorless and transparent fraction having a boiling point of 125 to 130 ° C./3 mmHg. When the fraction was analyzed by ¹ H-NMR, it was found to be an amino group-containing vinylsilane represented by the following formula (34). FIG. 1 shows a ¹ H-NMR spectrum of an amino group-containing vinyl silane.

¹ H-NMR
δ0.0-0.1 (-SiCH ₃ ) 6H
δ 0.5-0.6 (—SiCH ₂ CH ₂ CH ₂ —) 2H
_{δ0.9-1.3 (-NH-CH (CH 2} CH 2) 2 CH 2) (axial) 5H
δ1.4-1.5 (—SiCH ₂ CH ₂ CH ₂ —) 2H
δ1.5-1.9 (—NH—CH (CH ₂ CH ₂ ) ₂ CH ₂ ) (equational) 6H
_{δ2.3-2.4 (-NH-CH (CH 2} CH 2) 2 CH 2) 1H
δ 2.5-2.6 (—SiCH ₂ CH ₂ CH ₂ —) 2H
δ5.6-6.2 (-SiCH = CH ₂₎ 3H

（ｐ’＋ｑ’の平均値＝３５）
で表されるパーフルオロポリエーテル１００ｇ及び１，３−ビストリフルオロメチルベンゼン４０ｇを２００ｍＬフラスコに仕込み、合成例１にて得られたアミノ基含有ビニルシラン７．５ｇ、トリエチルアミン３．４ｇ、及び１，３−ビストリフルオロメチルベンゼン１０ｇの混合液を３０分かけて滴下した。滴下中、フラスコ内部は４５℃まで昇温した。滴下終了後３０分撹拌して反応終了とし、炭酸カルシウム４．０ｇを加えて１００℃に加熱して４時間撹拌した。次いで、窒素バブリングを行いながら１４０℃／２ｍｍＨｇで揮発分を除いた。冷却後、パーフルオロヘキサン１００ｇと合成ケイ酸アルミニウムの粉末１．５ｇを加えて撹拌し、濾過により固形物を除き、パーフルオロヘキサンを留去することで、下記式（３６）で表される含フッ素ポリマー９５ｇを得た。図２に、含フッ素ポリマーの¹Ｈ−ＮＭＲスペクトルを示す。 [Synthesis Example 2]
Following formula (35)

(Average value of p ′ + q ′ = 35)
100 g of perfluoropolyether and 40 g of 1,3-bistrifluoromethylbenzene are charged into a 200 mL flask and 7.5 g of amino group-containing vinylsilane obtained in Synthesis Example 1, 3.4 g of triethylamine, and 1,3 -A mixed liquid of 10 g of bistrifluoromethylbenzene was added dropwise over 30 minutes. During the dropping, the temperature inside the flask was raised to 45 ° C. After completion of dropping, the reaction was terminated by stirring for 30 minutes, 4.0 g of calcium carbonate was added, and the mixture was heated to 100 ° C. and stirred for 4 hours. Next, volatile components were removed at 140 ° C./2 mmHg while performing nitrogen bubbling. After cooling, 100 g of perfluorohexane and 1.5 g of synthetic aluminum silicate powder were added and stirred, the solid matter was removed by filtration, and the perfluorohexane was distilled off, thereby containing the compound represented by the following formula (36). 95 g of fluoropolymer was obtained. FIG. 2 shows the ¹ H-NMR spectrum of the fluorine-containing polymer.

（ｐ’＋ｑ’の平均値＝３５）

(Average value of p ′ + q ′ = 35)

The vinyl value of the fluoropolymer was measured by ¹ H-NMR and found to be 2.86 × 10 ⁻⁴ mol / g.

¹ H-NMR
δ0.0-0.1 (-SiCH ₃ ) 6H
δ 0.4-0.6 (—SiCH ₂ CH ₂ CH ₂ —) 2H
δ0.9-2.3 (—SiCH ₂ CH ₂ CH ₂ —N—CH (CH ₂ CH ₂ ) ₂ CH ₂ ) 12H
δ 3.0-3.6 (—SiCH ₂ CH ₂ CH ₂ —) 2H
δ3.8-4.2 (—N—CH (CH ₂ CH ₂ ) ₂ CH ₂ ) 1H
δ5.5-6.2 (—SiCH═CH ₂ ) 3H

[Synthesis Example 3]
Following formula (37)

(Average value of p ′ + q ′ = 90)
100 g of perfluoropolyether and 40 g of 1,3-bistrifluoromethylbenzene are charged into a 200 mL flask, 3.1 g of amino group-containing vinylsilane obtained in Synthesis 1, 1.4 g of triethylamine and 1,3-bistri A liquid mixture of 10 g of fluoromethylbenzene was added dropwise over 30 minutes. During the dropping, the temperature inside the flask was raised to 35 ° C. After completion of dropping, the reaction was completed by stirring for 1 hour, 1.6 g of calcium carbonate was added, and the mixture was heated to 100 ° C. and stirred for 4 hours. Next, volatile components were removed at 140 ° C./2 mmHg while performing nitrogen bubbling. After cooling, 100 g of perfluorohexane and 1.5 g of synthetic aluminum silicate powder were added and stirred, the solid matter was removed by filtration, and the perfluorohexane was distilled off, thereby containing the compound represented by the following formula (38). 100 g of fluoropolymer was obtained.

（ｐ’＋ｑ’の平均値＝９０）

(Average value of p ′ + q ′ = 90)

^When the vinyl value of the fluoropolymer was measured by ¹ H-NMR, it was 1.20 × 10 ⁻⁴ mol / g.

[Synthesis Example 4]
Following formula (39)

(Average value of p ′ + q ′ = 90)
100 g of perfluoropolyether and 40 g of 1,3-bistrifluoromethylbenzene are charged into a 200 mL flask, 3.1 g of amino group-containing vinylsilane obtained by synthesis, 1.4 g of triethylamine and 1,3-bistrifluoro 10 g of methylbenzene was added and stirred at 150 ° C. for 2 hours. Next, volatile components were removed at 140 ° C./2 mmHg while performing nitrogen bubbling. After cooling, 100 g of perfluorohexane and 1.5 g of synthetic aluminum silicate powder were added and stirred, the solid matter was removed by filtration, and the perfluorohexane was distilled off, thereby containing the compound represented by the above formula (38). 96 g of fluoropolymer was obtained.

^When the vinyl value of the fluoropolymer was measured by ¹ H-NMR, it was 1.20 × 10 ⁻⁴ mol / g.

[Example 1]
The following formula (38) obtained in Synthesis Example 3 above.

(Average value of p ′ + q ′ = 90)
100 parts by mass of a polymer represented by the formula (vinyl group content 0.0120 mol / 100 g, number average molecular weight = 15,900), Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd., dry-processed surface with dichlorodimethylsilane) Silica) 20 parts by mass was mixed with a planetary mixer at 120 ° C. for 1 hour. Thereafter, a three-roll mill treatment was performed. In 100 parts by mass of 120 parts by mass of the obtained mixture, the following formula (40)

2.4 parts by mass of a fluorine-containing organosilicon compound represented by formula (SiH group / vinyl group = 1.2 mol / mol), toluene of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ 0.2 parts by mass of a solution (platinum concentration: 0.5% by mass) and 0.3 parts by mass of a 60% by mass toluene solution of 1-ethynyl-1-hydroxycyclohexane were mixed to obtain a fluorine-containing curable composition. The following measurements were made using this composition.

Initial rubber properties of cured product:
The composition was subjected to press crosslinking (primary crosslinking) at 150 ° C. for 10 minutes and oven crosslinking (secondary crosslinking) at 150 ° C. for 1 hour to prepare a cured sheet (170 mm × 130 mm × 2 mm). The initial physical properties (hardness, tensile strength, elongation at break) (initial value) of the obtained cured sheet before the following heat resistance test (initial value) were measured according to JIS K6253-3: 2012 and JIS K6251: 2010.

Heat-resistant:
The cured sheet was stored at a temperature of 150 ° C. for 1,000 hours, and then the hardness, tensile strength, and elongation at break were measured. By calculating the amount of change from the initial value of the measured value after storage at 150 ° C. for 1,000 hours, the amount of change in hardness (points), the amount of change in tensile strength (%), the amount of change in elongation at break (%) )It was determined.
In addition, the measurement result of the rubber physical property of the cured product and the measurement result of the heat resistance are shown in Table 1.

[Comparative Example 1]
Following formula (41)

(Average value of p ′ + q ′ = 90)
100 parts by mass of a polymer represented by the formula (vinyl group content 0.0121 mol / 100 g, number average molecular weight = 15,800), Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd., dry-treated with dichlorodimethylsilane on the surface) Silica) 20 parts by mass was mixed with a planetary mixer at 120 ° C. for 1 hour. Thereafter, a three-roll mill treatment was performed. In 100 parts by mass of 120 parts by mass of the obtained mixture, the following formula (40)

2.4 parts by mass of a fluorine-containing organosilicon compound represented by formula (SiH group / vinyl group = 1.2 mol / mol), toluene of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ 0.2 parts by mass of a solution (platinum concentration: 0.5% by mass) and 0.3 parts by mass of a 60% by mass toluene solution of 1-ethynyl-1-hydroxycyclohexane were mixed to obtain a fluorine-containing curable composition. Using this composition, the rubber properties and heat resistance of the cured product were measured by the method described above.

[Comparative Example 2]
Following formula (42)

(Average value of p ′ + q ′ = 90)
100 parts by mass of a polymer represented by the formula (vinyl group content 0.0119 mol / 100 g, number average molecular weight = 15,800), Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd., dry-processed surface with dichlorodimethylsilane) Silica) 20 parts by mass was mixed with a planetary mixer at 120 ° C. for 1 hour. Thereafter, a three-roll mill treatment was performed. In 100 parts by mass of 120 parts by mass of the obtained mixture, the following formula (40)

2.4 parts by mass of a fluorine-containing organosilicon compound represented by formula (SiH group / vinyl group = 1.2 mol / mol), toluene of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ 0.2 parts by mass of a solution (platinum concentration: 0.5% by mass) and 0.3 parts by mass of a 60% by mass toluene solution of 1-ethynyl-1-hydroxycyclohexane were mixed to obtain a fluorine-containing curable composition. Using this composition, the rubber properties and heat resistance of the cured product were measured by the method described above.

[Example 2]
The following formula (36) obtained in Synthesis Example 2 above.

(Average value of p ′ + q ′ = 35)
In 100 parts by mass of a polymer represented by formula (vinyl group amount 0.0286 mol / 100 g, number average molecular weight = 6,500), the following formula (40)

6.9 parts by mass of a fluorine-containing organosilicon compound represented by the formula (SiH group / vinyl group = 1.2 mol / mol), toluene of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ 0.4 parts by mass of a solution (platinum concentration: 0.5% by mass) and 0.5 parts by mass of a 60% by mass toluene solution of 1-ethynyl-1-hydroxycyclohexane were mixed to obtain a fluorine-containing curable composition. The following measurements were made using this composition.

Optical transparency:
The composition was poured into a 2 mm thick gap made of two glass plates and oven-crosslinked at 150 ° C. for 1 hour to prepare a cured sheet (50 mm × 50 mm × 2 mm). The transparency of the obtained cured sheet was measured using an ultraviolet-visible near-infrared spectrophotometer UV-3600 manufactured by Shimadzu Corporation. The measurement results are shown in Table 2.

[Comparative Example 3]
Following formula (43)

(Average value of p ′ + q ′ = 35)
In 100 parts by mass of the polymer represented by formula (vinyl group amount 0.0302 mol / 100 g, number average molecular weight = 6,500), the following formula (40)

7.3 parts by mass of a fluorine-containing organosilicon compound represented by the formula (SiH group / vinyl group = 1.2 mol / mol), toluene of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ 0.4 parts by mass of a solution (platinum concentration: 0.5% by mass) and 0.6 parts by mass of a 60% by mass toluene solution of 1-ethynyl-1-hydroxycyclohexane were mixed to obtain a fluorine-containing curable composition. Using this composition, light transmittance was measured by the method described above.

[Comparative Example 4]
Following formula (44)

(Average value of p ′ + q ′ = 35)
In 100 parts by mass of the polymer represented by formula (vinyl group amount 0.0276 mol / 100 g, number average molecular weight = 6,500), the following formula (40)

6.6 parts by mass of a fluorine-containing organosilicon compound represented by the formula (SiH group / vinyl group = 1.2 mol / mol), toluene of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ 0.4 parts by mass of a solution (platinum concentration: 0.5% by mass) and 0.5 parts by mass of a 60% by mass toluene solution of 1-ethynyl-1-hydroxycyclohexane were mixed to obtain a fluorine-containing curable composition. Using this composition, light transmittance was measured by the method described above.

  The fluorine-containing polymer that is the base polymer of the fluorine-containing curable composition of the present invention does not have a phenyl group with good heat resistance and has a cyclohexyl group instead. The cured product of Example 1 had the same heat resistance as the cured products of Comparative Examples 1 and 2. It can be seen that the fluoropolymer used in Example 1 has the same heat resistance as the conventional fluoropolymer used in Comparative Examples 1 and 2.

  As is apparent from Table 2, the cured product using the base polymer having no aromatic-amide bond in Example 2 is the same as the base polymer having an aromatic-amide bond in the conventional Comparative Examples 3 and 4. Compared with the cured product used, it was excellent in light transmittance from visible light to ultraviolet region.

  From the above results, from the fluorine-containing curable composition of the present invention, while having the same heat resistance as the cured product obtained from the conventional fluorine-containing curable composition, and from the visible light to the ultraviolet region, it is made light transmissive. It became clear that an excellent cured product was obtained.

  Therefore, the fluorine-containing curable composition of the present invention can be used for the use of conventional fluorine-containing curable compositions, but for optical semiconductor sealing agents having better light transmittance in visible light. Is also available. Moreover, since it has the outstanding light transmittance in an ultraviolet region, it is easy to apply to a member with poor heat resistance as a photocurable composition that does not require heat curing at a high temperature for molding.

Claims (7)

(A) The following general formula (1)

(In the formula (1), Rf is a perfluoroalkylene group or a divalent perfluoropolyether group, R ¹ and R ² are each independently a vinyl group or an alkyl group having 1 to 4 carbon atoms, and R ³ is An alkylene group having 3 to 6 carbon atoms, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, or (It is a C1-C4 alkyl group optionally substituted with fluorine.)
A fluorine-containing polymer having a number average molecular weight of 1,000 to 100,000 represented by:
(B) Fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: The molar ratio of hydrosilyl group (SiH group) in component (b) to alkenyl group in component (a) An amount of 0.4 to 5, and (c) hydrosilylation reaction catalyst: a fluorine-containing curable composition containing a catalytic amount. In general formula (1), R ¹ and R ² are methyl groups, R ³ is a trimethylene group, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , The fluorine-containing curable composition according to claim 1, wherein R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms.   Furthermore, (d) Silica type filler: The fluorine-containing curable composition of Claim 1 or 2 which contains 1-100 mass parts with respect to 100 mass parts of (a) component. In the general formula (1), the divalent perfluoropolyether group of Rf is represented by the following formula (2)

(In Formula (2), g is an integer of 1-6, and h is an integer of 20-600.)
The fluorine-containing curable composition according to any one of claims 1 to 3, which is a group having a structure represented by: In the general formula (1), the divalent perfluoropolyether group of Rf is represented by the following formulas (3) to (5).

(In Formula (3), Y is a fluorine atom or a trifluoromethyl group, and p, q, and r are integers satisfying p ≧ 0, q ≧ 0, 0 ≦ p + q ≦ 600, and 0 ≦ r ≦ 6, respectively. (However, p = q = r = 0 is excluded.)

(In Formula (4), Y is a fluorine atom or a trifluoromethyl group, and v and w are integers satisfying 0 ≦ v ≦ 300, 0 ≦ w ≦ 300, and 1 ≦ v + w ≦ 600, respectively. (Repeating units may be combined randomly.)

(In Formula (5), z is an integer of 1 ≦ z ≦ 600.)
The fluorine-containing curable composition according to claim 4, which is a group having a structure selected from the group consisting of structures represented by:   The component (b) contains one or more monovalent perfluoroalkyl group, monovalent perfluoropolyether group, divalent perfluoroalkylene group, or divalent perfluoropolyether group in one molecule. The fluorine-containing curable composition according to any one of claims 1 to 5, which is an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms.   A rubber article comprising a cured product of the fluorine-containing curable composition according to any one of claims 1 to 6.

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