Composite material obtained by integrating a cured product of a curable liquid fluorine-containing composition with a fiber substrate, method for producing the same, and article using the composite material

Abstract

Provided are: a composite material having high strength and excellent chemical resistance and solvent resistance; and a method enabling production of the composite material relatively easily and industrially advantageously.　This composite material is obtained by integrally combining a fiber base material and a cured product of a liquid curable fluorine-containing composition containing a liquid curable fluorine-containing compound.　This method for producing a composite material comprises: a step for uniformly impregnating a fiber base material with a liquid curable fluorine-containing composition; a step for defoaming the fiber base material uniformly impregnated with the liquid curable fluorine-containing composition; and a step for curing the liquid curable fluorine-containing composition with which the defoamed fiber base material is uniformly impregnated.

Description

[Technical Field]

[0001] The present invention relates to a composite material in which a cured product of a curable liquid fluorine-containing composition containing a curable liquid fluorine-containing compound is integrated with a fibrous substrate, a method for producing the same, and articles using the composite material. [Background technology]

[0002] Composite materials made by combining various organic resins or rubber with fibers are highly strong and lightweight, and are therefore used in the automotive and aircraft industries.

[0003] As specific examples of such composite materials, Patent Document 1 discloses a composite material of silicone rubber and carbon fiber, Patent Document 2 discloses a composite material made of nitrile butadiene rubber, polyamide fiber, carbon fiber, etc., and Patent Document 3 discloses a composite material made of fluororubber, aramid fiber, rock wool, etc. The composite materials of Patent Documents 1 and 2 have insufficient solvent and chemical resistance because the rubber used does not have sufficient solvent and chemical resistance. The composite material of Patent Document 3 has high solvent and chemical resistance because it uses fluororubber. However, in the production of this composite material, in order to integrate the rubber and fiber, it is necessary to first swell the rubber with a solvent and then integrate the rubber and fiber using a mixer or heated roll, which makes it difficult to produce industrially advantageously. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-181717 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-100420 [Patent Document 3] Japanese Patent Application Publication No. 10-168429 Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, an object of the present invention is to provide a composite material that has high strength and excellent chemical and solvent resistance, and a method for producing the composite material relatively easily and industrially advantageously. [Means for solving the problem]

[0006] The present inventors have found that a composite material having high strength and excellent chemical resistance and solvent resistance can be produced relatively easily and industrially advantageously by impregnating a fibrous substrate with a curable liquid fluorine-containing composition and curing the composition to form a composite with the fibrous substrate, and have thus completed the present invention. Therefore, the present invention provides the following composite material, a method for producing the same, and an article using the composite material.

[0007] <1> A composite material obtained by integrating a fibrous substrate with a cured product of a curable liquid fluorine-containing composition containing a curable liquid fluorine-containing compound. <2> The curable liquid fluorine-containing compound is a curable perfluoro group-containing compound. <1> The composite material according to claim 1. <3> The curable perfluoro group-containing compound is a compound containing a divalent perfluoroalkylene structure and / or a perfluoropolyether structure. <2> The composite material according to claim 1. <4> The curable perfluoropolyether group-containing compound contains an alkenyl group. <3> The composite material according to claim 1. <5> The curable liquid fluorine-containing composition comprises (A) a curable polyfluoro compound having at least two alkenyl groups in one molecule and having a divalent perfluoroalkylene structure and / or a divalent perfluoropolyether structure in the main chain; (B) a crosslinking agent having two or more hydrosilyl groups in one molecule; (C) a hydrosilylation reaction catalyst, and (D) Reinforcing filler It includes <1> ~ <4> 10. The composite material according to claim 1 . <6> The composition further comprises (E) a hydrosilylation reaction inhibitor. <5> The composite material according to claim 1. <7> The fiber substrate is a carbon fiber substrate or a glass fiber substrate. <1> ~ <6> 10. The composite material according to claim 1 . <8> a step of uniformly impregnating a fibrous substrate with a curable liquid fluorine-containing composition; a step of degassing the fibrous substrate uniformly impregnated with the curable liquid fluorine-containing composition; and a step of curing the curable liquid fluorine-containing composition uniformly impregnated into the degassed fiber substrate; Contains <1> ~ <7> 10. A method for producing a composite material according to claim 1 . <9> <1> ~ <7> A rubber product having the composite material according to any one of claims 1 to 4 as a partial structure or an entire structure. <10> The composite material is a seal, diaphragm, protective sheet, or sheet punching. <9> A rubber product according to claim 1. [Effects of the Invention]

[0008] The composite material of the present invention has high strength and excellent chemical and solvent resistance, and is therefore useful as a sealing material, a diaphragm, a chemical-resistant protective sheet, and punched products thereof. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below, but the present invention is not limited thereto.

[0010] In a composite material obtained by integrating a fiber substrate with a cured product of the curable liquid fluorine-containing composition containing the curable liquid fluorine-containing compound of the present invention, the curable liquid fluorine-containing compound that is the main component (base polymer) in the curable liquid fluorine-containing composition is preferably a curable perfluoro group-containing compound, more preferably a curable perfluoropolyether group-containing compound, and even more preferably a curable alkenyl group-containing perfluoropolyether group-containing compound. The curable liquid fluorine-containing compound is contained in the curable liquid fluorine-containing composition in an amount of preferably from 60 to 95 mass %, particularly preferably from 65 to 93 mass %. In the composite material of the present invention, the curable liquid fluorine-containing composition may usually contain, in addition to the curable liquid fluorine-containing compound as the main component (base polymer), a crosslinking agent, a curing catalyst, a filler, etc.

[0011] In the composite material of the present invention, the curable liquid fluorine composition preferably contains the following components (A) to (D):

[0012] [Component (A)] Component (A) is a curable liquid fluorine-containing compound that is the main component (base polymer) in the curable liquid fluorine-containing composition of the present invention, and is a curable polyfluoro compound having at least two alkenyl groups in one molecule and a divalent perfluoroalkylene structure and / or a divalent perfluoropolyether structure in the main chain. The curable polyfluoro compound of component (A) is preferably a linear polyfluoro compound containing alkenyl groups at both ends of the molecular chain. In this specification, the term "linear" means that the divalent perfluoroalkylene structure (perfluoroalkylene group) in the main chain is linear, or that the individual repeating units (perfluorooxyalkylene units) constituting the divalent perfluoropolyether structure in the main chain are bonded to each other in a linear fashion, and the individual repeating units constituting the perfluoropolyether structure may themselves be perfluorooxyalkylene units having a branched structure (for example, -CF(CF)CFO-).

[0013] The alkenyl group contained in component (A) preferably has 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and has a CH═CH- structure. Examples include vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, and hexenyl groups, with vinyl groups and allyl groups being particularly preferred.

[0014] The alkenyl group content of the linear polyfluoro compound of component (A) is preferably 0.005 to 0.3 mol / 100g, more preferably 0.007 to 0.2 mol / 100g. If the alkenyl group content is 0.005 mol / 100g or more, the degree of crosslinking of the composition is sufficient, and there is no risk of curing defects. On the other hand, if the alkenyl group content is 0.3 mol / 100g or less, there is no risk of the mechanical properties of the cured product (fluoropolyether rubber elastomer) obtained by curing the composition being impaired. The alkenyl group content in the curable polyfluoro compound of component (A) is 1 It can be calculated from H-NMR measurements.

[0015] The perfluoropolyether structure of component (A) is -C a F 2a O- (In the formula, a is a number from 1 to 6.) The polyfluoroethylene copolymer contains a large number of repeating units (perfluorooxyalkylene units) represented by the following formula (1), for example. -(C a F 2a O) b - (1) (In formula (1), a is a number from 1 to 6, and b is a number from 1 to 300, preferably a number from 1 to 200.)

[0016] Above-C a F 2a Examples of the repeating unit represented by O- include units represented by the following formulas. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2O- -C(CF3)2O-

[0017] Among these, the repeating units represented by the following formula are particularly preferred. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O-

[0018] The perfluoropolyether structure contained in the component (A) may be composed of one type of the above repeating unit, or may be composed of a combination of two or more types.

[0019] Preferred examples of the component (A) include linear polyfluoro compounds represented by the following general formula (2) and the following general formula (3). [ka] (In formula (2), R 1 and R 2 is an alkenyl group or an unsubstituted or substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, and R 1 are independent of each other, and R 2 are also independent of each other, and R 1 and R 2 At least two of the six R groups are alkenyl groups. 3 are each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, c and d are each a number from 1 to 150, the average value of c+d is 2 to 300, and e is a number from 1 to 6. [ka] (In formula (3), R 1 and R 2 is an alkenyl group or an unsubstituted or substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, and R1 are independent of each other, and R 2 are also independent of each other, and R 1 and R 2 At least two of the six R groups are alkenyl groups. 4 are each independently an alkylene group having 1 to 6 carbon atoms, and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with fluorine; c and d are each a number from 1 to 150, the average value of c+d is 2 to 300, and e is a number from 1 to 6.

[0020] where R 1 and R 2 Examples of the alkenyl groups contained in R include the same alkenyl groups as those exemplified as the alkenyl groups contained in component (A) above, and the monovalent hydrocarbon groups other than the alkenyl groups that do not have unsubstituted or substituted aliphatic unsaturated bonds are preferably those having 1 to 12 carbon atoms, and particularly preferably those having 1 to 10 carbon atoms, and specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenylethyl; and monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine. 1 and R 2 Among these, vinyl, allyl, methyl and ethyl groups are particularly preferred. In addition, R 1 are independent of each other, and R 2 are also independent of each other, and R 1 and R 2 Of the total six groups, two or more (2 to 6) are alkenyl groups, but R 1 and R 2 At least one of each (i.e., R 1 and R 2 It is preferred that each of the groups (1 to 3) is an alkenyl group, particularly a vinyl group or an allyl group.

[0021] R 3 The unsubstituted or substituted monovalent hydrocarbon group contained in R 1and R 2 Examples of the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond include the same groups as those listed above. 3 is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0022] R 4 is an alkylene group having 1 to 6 carbon atoms, preferably 2 to 6 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), and a hexamethylene group, with an ethylene group and a propylene group being particularly preferred.

[0023] R 5 are each independently a hydrogen atom or an optionally fluorine-substituted alkyl group having 1 to 4 carbon atoms, and specific examples of the optionally fluorine-substituted alkyl group having 1 to 4 carbon atoms include alkyl groups such as methyl, ethyl, propyl, and butyl, as well as groups in which some or all of the hydrogen atoms in these groups have been substituted with fluorine atoms, such as a trifluoromethyl group. Of these, a hydrogen atom is preferred.

[0024] Furthermore, c and d are each a number from 1 to 150, preferably a number from 1 to 100, and the average value of c+d is 2 to 300, preferably 2 to 200. Furthermore, e is a number from 1 to 6, preferably a number from 1 to 4.

[0025] Specific examples of the linear polyfluoro compound represented by the above general formula (2) include those represented by the following formula: In this regard, Me represents a methyl group, and Et represents an ethyl group. [ka] (In the formula, c1 and d1 are each a number from 1 to 150.) [ka] (In the formula, c1 and d1 are each a number from 1 to 150.) [ka] (In the formula, c1 and d1 are each a number from 1 to 150.)

[0026] Specific examples of the linear polyfluoro compound represented by the general formula (3) include those represented by the following formula: [ka] (In the formula, c2 and d2 are each a number from 1 to 150.) [ka] (In the formula, c2 and d2 are each a number from 1 to 150.)

[0027] In the present invention, viscosity can be measured using a rotational viscometer (for example, BL type, BH type, BS type, cone-plate type, rheometer, etc.), and the viscosity (23°C) of the linear polyfluoro compounds represented by the above general formulas (2) and (3) is preferably 500 to 100,000 mPa·s, and more preferably 1,000 to 50,000 mPa·s, as measured according to JIS K7117-1. If the viscosity is 500 mPa·s or higher, there is no risk of the storage stability of the composition being impaired, and if it is 100,000 mPa·s or lower, there is no risk of the extensibility of the composition being impaired.

[0028] The degree of polymerization (or molecular weight) of a linear polyfluoro compound, which reflects the number of repetitions of the perfluorooxyalkylene units constituting the main chain perfluoropolyether structure, can be determined, for example, as the polystyrene-equivalent number-average degree of polymerization (or number-average molecular weight) in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. The number-average degree of polymerization (or number-average molecular weight) of the linear polyfluoro compound is 19 It can also be calculated from F-NMR.

[0029] These linear polyfluoro compounds can be used alone or in combination of two or more. That is, among the linear polyfluoro compounds represented by the above general formulas (2) and (3), one can be used alone or in combination of two or more, and further, linear polyfluoro compounds represented by the above general formulas (2) and (3) can also be used in combination.

[0030] [(B) Component] Component (B) is an addition-reactive crosslinking agent having two or more hydrosilyl groups (SiH groups) in one molecule, and is preferably a fluorine-containing organohydrogenpolysiloxane that has a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, or a divalent perfluoroalkylene group or a divalent perfluorooxyalkylene group in one molecule, and further has two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and does not have an epoxy group or an alkoxy group directly bonded to a silicon atom in one molecule, and functions as a crosslinking agent for component (A).

[0031] The above-mentioned monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups and divalent perfluorooxyalkylene groups are groups that are introduced from the viewpoints of compatibility with the above-mentioned component (A), dispersibility, uniformity after curing, etc.

[0032] Examples of the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group include groups represented by the following general formula (4) or (5). C f F 2f+1 - (4) (In formula (4), f is a number from 1 to 10, preferably a number from 3 to 7.) [ka] (In formula (5), g is a number from 1 to 50, and preferably a number from 2 to 30.)

[0033] Furthermore, examples of the divalent perfluoroalkylene group or divalent perfluorooxyalkylene group include groups represented by the following general formulas (6) to (8). -C h F 2h - (6) (In formula (6), h is a number from 1 to 20, preferably a number from 2 to 10.) [ka] (In formula (7), i and j are each a number of 1 or more, preferably a number of 1 to 100, and the average value of i+j is 2 to 200, preferably 2 to 100.) -CF2O-(CF2CF2O) k (CF2O) l -CF2- (8) (In formula (8), k and l each represent a number from 1 to 50, preferably a number from 1 to 30, and the average value of k+l is 2 to 100, preferably 2 to 60. The repeating units may be bonded to each other randomly.)

[0034] Furthermore, these perfluoroalkyl groups, perfluorooxyalkyl groups, perfluoroalkylene groups, or perfluorooxyalkylene groups are preferably linked to the silicon atoms constituting the polysiloxane via a divalent linking group. The divalent linking group is preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 13 carbon atoms, particularly 2 to 8 carbon atoms, which may contain an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples include alkylene groups, arylene groups, and combinations thereof, as well as those in which these groups are interposed with one or more structures selected from the group consisting of an ether-bonded oxygen atom, an amide bond, a carbonyl bond, an ester bond, and a diorganosilylene group such as a dimethylsilylene group, and examples thereof include the following groups having 2 to 13 carbon atoms: -CH2CH2- -CH2CH2CH2- -CH2CH2CH2OCH2- -CH2CH2CH2-NH-CO- -CH2CH2CH2-N(Ph)-CO- -CH2CH2CH2-N(CH3)-CO- -CH2CH2CH2-N(CH2CH3)-CO- -CH2CH2CH2-N(CH(CH3)2)-CO- -CH2CH2CH2-O-CO- -CH2CH2-Si(CH3)2-Ph'-N(CH3)-CO- -CH2CH2CH2-Si(CH3)2-Ph'-N(CH3)-CO- (wherein Ph is a phenyl group and Ph' is a phenylene group.)

[0035] In the fluorine-containing organohydrogenpolysiloxane of component (B), the monovalent or divalent fluorine-containing organic group and the monovalent substituent bonded to the silicon atom other than the hydrogen atom directly bonded to the silicon atom are unsubstituted or substituted alkyl or aryl groups having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, and decyl; aryl groups such as phenyl, tolyl, and naphthyl; and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as chlorine atoms, cyano groups, or the like, such as chloromethyl, chloropropyl, and cyanoethyl. Among these, methyl groups are preferred. Furthermore, epoxy and alkoxy groups are not included.

[0036] The structure of the fluorine-containing organohydrogenpolysiloxane of component (B) may be cyclic, linear, three-dimensional network, or a combination thereof. The number of silicon atoms in this fluorine-containing organohydrogenpolysiloxane is not particularly limited, but is usually 2 to 60, preferably 3 to 30, and more preferably 4 to 30. Furthermore, component (B) has two or more, preferably three or more, SiH groups per molecule, and the SiH group content is preferably 0.0001 to 0.02 mol / g, and more preferably 0.0002 to 0.01 mol / g.

[0037] Examples of the component (B) include those represented by the following general formulas (9) to (15). [ka] In formula (9), each A is independently a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom constituting the polysiloxane via a divalent hydrocarbon group which may have an oxygen atom, a nitrogen atom, or a silicon atom. Examples of the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group include groups represented by the above general formula (4) or (5). R 6 are each independently an unsubstituted or substituted alkyl group or aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. m is a number from 2 to 6, preferably 3 to 6, n is a number from 1 to 4, preferably 1 to 3, and m+n is a number from 4 to 10, preferably 4 to 9. However, -(Si(H)(R 6 )O)- and -(Si(A)(R 6 The bonding order of )O)- is not limited. [ka] (In formula (10), A's are each independently the same as A's above, and R 6 are independent of each other, and the above R 6 In addition, o is a number from 2 to 50, preferably a number from 3 to 30. [ka] (In formula (11), A's are each independently the same as A's above, and R 6 are independent of each other, and the above R 6 where o is a number from 2 to 50, preferably a number from 3 to 30, p is a number from 1 to 40, preferably a number from 1 to 20, and o+p is a number from 4 to 60, preferably a number from 4 to 50. However, -(Si(H)(R 6 )O)- and -(Si(A)(R 6 The bonding order of )O)- is not limited. [ka] (In formula (12), A's are each independently the same as A's above, and R 6 are independent of each other, and the above R 6 where o is a number from 2 to 50, preferably a number from 3 to 30, q is a number from 1 to 40, preferably a number from 1 to 20, and o+q is a number from 4 to 60, preferably a number from 4 to 50. However, -(Si(H)(R 6 )O)- and -(Si(R 6 The order of bonding of )2O)- is not limited. [ka] (In formula (13), A's are each independently the same as A's above, and R 6 are independent of each other, and the above R 6 where o is a number from 2 to 50, preferably a number from 3 to 30, p is a number from 1 to 40, preferably a number from 1 to 20, q is a number from 1 to 40, preferably a number from 1 to 20, and o+p+q is a number from 5 to 60, preferably a number from 5 to 50. However, -(Si(H)(R 6 )O)-, -(Si(A)(R 6 )O)- and -(Si(R 6 The order of bonding of )2O)- is not limited. [ka] In formula (14), D is a divalent perfluoroalkylene group or a divalent perfluorooxyalkylene group bonded to adjacent silicon atoms via an oxygen atom, an alkylene group, or a divalent hydrocarbon group which may have an oxygen atom or a nitrogen atom. Examples of the divalent perfluoroalkylene group or the divalent perfluorooxyalkylene group include any of the groups represented by the above general formulae (6) to (8). Each A is independently the same as the above A, and R 6 are independent of each other, and the above R 6 In addition, r is a number from 0 to 3, s is a number from 0 to 3, and r+s is a number from 2 to 6, preferably a number from 3 to 5. [ka] (In formula (15), A is the same as A above, and R 6 are independent of each other, and the above R 6 is the same as

[0038] Specific examples of component (B) include the following compounds. These compounds may be used alone or in combination of two or more. In the following formulas, Me represents a methyl group, and Ph represents a phenyl group.

[0039] [ka] (wherein f' is a number from 1 to 10.) [ka] (In the formula, g' is a number from 1 to 50.) [ka] (In the formula, g' is a number from 1 to 50.) [ka] (wherein f' is a number from 1 to 10.) [ka] (In the formula, f' is a number from 1 to 10, and g' is a number from 1 to 50.) [ka] (In the formula, f' is a number from 1 to 10, and g' is a number from 1 to 50.) [ka] (In the formula, f' is a number from 1 to 10, and g' is a number from 1 to 50.) [ka] (In the formula, f' is a number from 1 to 10, and g' is a number from 1 to 50.) [ka] (In the formula, f' is a number from 1 to 10, and h' is a number from 1 to 20.) [ka] (In the formula, g' is a number from 1 to 50, and h' is a number from 1 to 20.) [ka] (In the formula, f' is a number from 1 to 10, and g' is a number from 1 to 50.) [ka] (In the formula, f' is a number from 1 to 10, g' is a number from 1 to 50, i' and j' are each a number from 1 to 100, and i'+j' is a number from 2 to 200.) [ka] (In the formula, f' is a number from 1 to 10, g' is a number from 1 to 50, k' and l' are each a number from 1 to 50, and k'+l' is a number from 2 to 100.)

[0040] This component (B) may be used alone or in combination of two or more. The amount of component (B) is such that the silicon-bonded hydrogen atoms (SiH groups) in component (B) are 0.5 to 3 moles, preferably 0.6 to 2 moles, per mole of alkenyl groups (particularly alkenyl groups in component (A)) contained in the composition of the present invention (molar ratio). If the number of SiH groups is less than 0.5 moles, the degree of crosslinking will be insufficient, while if it is more than 3 moles, the storage stability will be impaired and the heat resistance of the cured product obtained after curing will be reduced.

[0041] [(C) component] The hydrosilylation catalyst, component (C), is a catalyst that promotes the addition reaction between components (A) and (B). This hydrosilylation catalyst is generally a noble metal (particularly a platinum group metal) or a compound thereof, and it is preferable to use platinum or a platinum compound, which is relatively easy to obtain.

[0042] Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid with olefins such as ethylene, complexes of chloroplatinic acid with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. Other known hydrosilylation reaction catalysts besides platinum or its compounds include rhodium, ruthenium, iridium, and palladium compounds, such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO) 12 Examples include IrCl(CO)(PPh3)2, Pd(PPh3)4, etc. In the above formula, Ph is a phenyl group.

[0043] When using these catalysts, if they are solid catalysts, they can be used in a solid state; however, in order to obtain a more uniform cured product, it is preferable to use a solution of chloroplatinic acid or a complex in an appropriate solvent such as toluene or ethanol, which is then dissolved in the linear polyfluoro compound of component (A).

[0044] The component (C) may be used alone or in combination of two or more types. The amount of these catalysts used is not particularly limited, and the desired curing rate can be obtained with any amount of catalyst. From an economical standpoint or to obtain a good cured product, the amount is usually 0.1 to 2,000 ppm, preferably 0.1 to 500 ppm, and particularly preferably 0.5 to 200 ppm (calculated as the mass of platinum group metal atoms) relative to the mass of component (A), but this amount can be increased or decreased as appropriate depending on the desired curing rate.

[0045] The conditions for the above addition reaction (hydrosilylation reaction) can be selected appropriately, and the reaction may be carried out at room temperature, but can also be carried out by heating to 50 to 200°C to accelerate the reaction.

[0046] [(D) component] Component (D) is a reinforcing filler. Examples of the reinforcing filler include silica powders such as fumed silica (fumed silica or dry silica), precipitated silica (wet silica), spherical silica (fused silica), sol-gel silica, and silica aerogel; silica powders (surface-treated silica powders) obtained by treating the surface of the silica powder with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, and the like; and silica powders obtained by further treating the surface-treated silica powders with organosilanes or organosiloxanes having a monovalent perfluoroalkyl group represented by the above general formula (4) or a monovalent perfluorooxyalkyl group represented by the above general formula (5). Examples of reinforcing or semi-reinforcing fillers include quartz powder, fused quartz powder, diatomaceous earth, and calcium carbonate. Of these, fumed silica is particularly preferred from the viewpoint of improving mechanical strength and dispersion stability of each component. Furthermore, from the viewpoint of improving dispersibility, fumed silica treated with a silicon compound surface treatment agent such as silane is preferred, and in particular, fumed silica hydrophobized with silicon compounds having hydrolyzable groups, such as organochlorosilanes such as dimethyldichlorosilane and trimethylchlorosilane, silazane compounds such as hexamethyldisilazane, and cyclic silazanes such as hexamethylcyclotrisilazane is preferred.

[0047] In this hydrophobic treatment, the silica powder whose surface has been treated with a surface treatment agent is preferably one that has been treated directly in the powder state in advance, and the usual treatment method can be a well-known technique, for example, by placing the untreated silica powder and the treatment agent in a mechanical kneading device sealed at atmospheric pressure or in a fluidized bed, mixing them at room temperature or by heat treatment in the presence of an inert gas as needed, optionally using a catalyst and water to promote hydrolysis, and then drying to prepare the resulting mixture. The amount of the surface treatment agent to be added should be equal to or greater than the amount calculated from the area that the surface treatment agent can cover on the surface of the silica powder.

[0048] The specific surface area of ​​the silica powder by the BET method was set at 50m to improve the mechanical properties. 2 / g or more, and further, when silica powder is blended into the composition, the viscosity increases significantly, making blending difficult. 2 / g or less is preferable.

[0049] The component (D) may be used alone or in combination of two or more types.

[0050] Furthermore, the bulk density of the reinforcing filler is preferably 30 to 80 g / L. If the bulk density of the reinforcing filler is less than 30 g / L, the viscosity of the composition increases, which may make it difficult to blend, while if it exceeds 80 g / L, a sufficient reinforcing effect may not be imparted.

[0051] The amount of this reinforcing filler to be blended is 10 to 40 parts by mass, and more preferably 15 to 30 parts by mass, per 100 parts by mass of component (A). If it is less than 10 parts by mass, no improvement in mechanical strength is observed, and if it is more than 40 parts by mass, the viscosity increases significantly, which may make blending difficult.

[0052] [(E) component] Component (E) is a hydrosilylation reaction inhibitor, an optional component that can be incorporated as needed. Examples of hydrosilylation addition reaction inhibitors include acetylenic alcohols such as 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, and phenylbutynol; reaction products of chlorosilanes having a monovalent perfluoroalkyl group represented by the general formula (4) or a monovalent perfluorooxyalkyl group represented by the general formula (5) with acetylenic alcohols; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, triallyl isocyanurate; polyvinyl siloxanes; and organophosphorus compounds. The addition of these inhibitors can maintain appropriate curing reactivity and storage stability. Component (E) may be used alone or in combination. The amount of the additives to be added may be any amount within the range that does not impair the object of the present invention.

[0053] [Other ingredients] In order to enhance its practical utility, the fluorine-containing curable composition of the present invention may, as necessary, contain, in addition to the above components (A) to (E), optional components such as a filler other than component (D), an adhesion aid (adhesion improver) capable of imparting self-adhesion to a cured product of the composition, a plasticizer, a viscosity modifier, a flexibility-imparting agent, inorganic pigments such as titanium oxide, iron oxide, carbon black, and cobalt aluminate, heat resistance improvers such as titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate, thermal conductivity imparters such as alumina, boron nitride, silicon carbide, and metal powders, and conductivity imparters such as carbon black, silver powder, and conductive zinc oxide. The amounts of these additives to be added are arbitrary as long as the object of the present invention is not impaired.

[0054] As the plasticizer, viscosity modifier, and flexibility-imparting agent, a non-reactive (non-functional) linear polyfluoro compound represented by the following general formulas (20) and (21), which does not have functional groups (alkenyl groups and hydrosilyl groups) involved in the hydrosilylation addition reaction in the molecule, and / or a polyfluoromonoalkenyl compound represented by the following general formula (22) can be used.

[0055] F-(CF2CF2CF2O) w -J (20) (In equation (20), J is C x F 2x+1 - (x is a number from 1 to 3), and w is a number from 1 to 500, preferably a number from 2 to 300.

[0056] J-{(OCF(CF3)CF2) y -(OCF2CF2) z -(OCF2) α}-OJ (21) (In formula (21), J is the same as above, y and z each represent a number from 0 to 300, preferably a number from 0 to 150, except when both y and z are 0. In addition, α represents a number from 1 to 300, preferably a number from 1 to 150. The repeating units may be bonded to each other randomly.)

[0057] Rf-(L) β -CH=CH2(22) [In formula (22), Rf is represented by the following general formula (23): F-[CF(CF3)CF2O] γ -C δ F 2δ - (twenty three) (In formula (23), γ is a number from 1 to 200, preferably a number from 1 to 150, and δ is a number from 1 to 3.) is a group represented by L is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 11 -M- [Note that the left end of each of these groups is bonded to Rf and the right end is bonded to a carbon atom. 11is a hydrogen atom, a methyl group, a phenyl group, or an allyl group, and M is -CH2-, a group represented by the following structural formula (24) or a group represented by the following structural formula (25). [ka] (Dimethylphenylsilylene group shown at the o-, m-, or p-position, with the left end bonded to a nitrogen atom and the right end bonded to a carbon atom.) [ka] (The left end is bonded to a nitrogen atom, and the right end is bonded to a carbon atom.) and β is 0 or 1.

[0058] Specific examples of the linear polyfluoro compound represented by the above general formula (20) or (21) include the following. F-(CF2CF2CF2O) w' -CF2CF3 (W' is a number between 1 and 200.) CF3-{(OCF(CF3)CF2) y' -(OCF2) α'}-O-CF3 (y' is a number from 1 to 200, and α' is a number from 1 to 200. The repeating units may be bonded randomly.) CF3-{(OCF2CF2) z' -(OCF2) α'}-O-CF3 (z' is a number from 1 to 200, and α' is a number from 1 to 200. The repeating units may be bonded randomly.)

[0059] The linear polyfluoro compounds represented by the above general formula (20) or (21) may be used singly or in combination of two or more kinds.

[0060] Specific examples of the polyfluoromonoalkenyl compound represented by the above general formula (22) include the following. [ka] (where γ' is a number between 1 and 200.)

[0061] The polyfluoromonoalkenyl compounds represented by the above general formula (22) may be used singly or in combination of two or more kinds.

[0062] In the fiber substrate used in the composite material of the present invention, examples of fibers constituting the fiber substrate include glass fiber, carbon fiber, aramid fiber, polyethylene fiber, Zylon fiber, boron fiber, basalt fiber, metal fiber, polyamide fiber, polyethylene fiber, silicon carbide fiber, polyester fiber, ceramic fiber, alumina fiber, mineral fiber, rock fiber, slag fiber, polyoxymethylene fiber, aromatic polyamide fiber, polyparaphenylene benzobisoxazole fiber, plant fiber, cellulose fiber, and lignin fiber. Among these fibers, glass fiber and carbon fiber are preferred in terms of the mechanical strength of the resulting composite. These fibers may be used alone or in combination of two or more.

[0063] The above-mentioned fibers may be surface-treated, may be treated with a treatment agent, may be treated with a sizing agent, or may be plated with a metal.

[0064] Examples of the sizing agent include surfactants such as ionic surfactants, nonionic surfactants, and amphoteric surfactants, mineral oil, animal and vegetable oils, etc. More specifically, alkylene glycol compounds, ester compounds, phenyl ether compounds, polyolefin compounds, polyether compounds, polyethylene glycol compounds, silicone compounds, amide compounds, sulfonate compounds, carboxylate compounds, phosphate compounds, fluorine compounds, and combinations of two or more of these can be used.

[0065] The treating agent may be a silicone resin, a urethane resin, an epoxy resin, a silane coupling agent, a polyamide, a fluororesin, or a combination of two or more of these.

[0066] The use of the treating agent allows for the introduction of functional groups onto the surface of the fiber. The reinforcing fiber preferably has, on its surface, an amide group, an alkylene group, an alkoxycarbonyl group, an acyl group, an acetyl group, an acetal group, an allene group, an isonitrile group, an imide group, a urethane group, a urea group, an epoxy group, an enol group, an enamine group, an oxime group, a carboxyl group, a carbonate group, a carboxylic acid halide group, a glycidyl group, an acid anhydride group, a cyano group, a hydroxyl group, a sulfonyl group, a sulfo group, a hydrocarbon group, a halogen group, an N-oxide group, an N-hydroxy group, a nitro group, a nitroso group, an azo group, a diazo group, an azide group, an oxo group, a phenyl group, a phosphino group, a thio group, an S-oxide group, a thioxy group, a peroxy group, a ketone group, a benzoyl group, a hemiacetal group, a formyl group, a thiol group, or a combination of two or more of these groups.

[0067] From the viewpoint of the mechanical strength of the resulting composite, the average fiber length of the above fibers is preferably 5 mm or more, more preferably 50 mm or more, and even more preferably 100 mm or more.

[0068] The form of the fibers may be continuous fiber, long fiber, short fiber, etc., with continuous fiber being particularly preferred. The form of the product (fiber substrate) formed using the fibers is not particularly limited, and includes a unidirectional fiber sheet in which fibers are aligned in one direction, two or more unidirectional fiber sheets stacked at different angles, those randomly oriented in two dimensions, those in which reinforcing fibers are molded into fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics, and strand-like products such as braids. In addition, when stacking, it is preferable to stack multiple layers with different layer directions, stack alternately, or arrange them symmetrically in the thickness direction. The product (fiber substrate) formed using the fibers is preferably a sheet because of its excellent tensile properties.

[0069] When the fiber base material is a sheet, the thickness of the sheet is preferably 0.01 to 5 mm, more preferably 0.05 to 4 mm, and even more preferably 0.1 to 3 mm, from the viewpoint of the mechanical strength of the resulting composite.

[0070] [Method of manufacturing the composite] The complex of the present invention comprises: (1) a step of uniformly impregnating a fibrous substrate with a curable liquid fluorine-containing composition; (2) a step of degassing the fibrous substrate uniformly impregnated with the curable liquid fluorine-containing composition; (3) a step of curing the curable liquid fluorine-containing composition uniformly impregnated into the fibrous base material after degassing; The composition can be produced by a production method including the steps of:

[0071] In step (1), methods for uniformly impregnating the fibrous substrate with the curable liquid fluorine-containing composition include a method of simply impregnating fibers with a sufficient amount of the curable liquid fluorine-containing composition in a container for a certain period of time and then pulling them up, or a method of homogenizing the composition by passing it between rolls during impregnation or pulling it up, but when the amount is small, the fluorine-containing rubber composition and fibers can be placed in a tray and the fibers can be uniformly impregnated with the composition while being kneaded by hand.The fibrous substrate used in this step is preferably in the form of a sheet, but may also be in the form of a mesh, and may be a single layer or multiple layers of the same or two or more types.

[0072] In step (2), it is important to degas the fibrous substrate uniformly impregnated with the curable liquid fluorine-containing composition in order to remove any air bubbles remaining between the fibers constituting the fibrous substrate and to impregnate the liquid material (curable liquid fluorine-containing composition) into even the finest parts. The degassing operation can be carried out by, for example, leaving the fibrous substrate under reduced pressure for a certain period of time. As a means for reducing the pressure, a vacuum chamber device linked to a vacuum pump will suffice. It is desirable to leave the fibrous substrate in a vacuum chamber at -0.05 to -1.0 MPa until no air bubbles remain; however, in the case of thick materials or fine fibers, the air bubbles are difficult to crush, so there is no problem in finishing the degassing and removing the material when there is no change in the state of bubble generation.

[0073] In step (3), the curable liquid fluorine-containing composition uniformly impregnated into the degassed fiber substrate can be cured by leaving it at high temperature under atmospheric pressure, known as HAV vulcanization (Hot Air Vulcanization), but when high dimensional accuracy is required, it is preferable to prepare a mold of the desired shape and press it under pressure and heat using a rubber press commonly used for rubber molding, which allows for easy processing similar to that of general rubber molding. Pressing conditions are generally 130 to 170°C for 5 minutes or more, with pressure set to suit the shape and mold.

[0074] The composite material of the present invention has high strength and excellent chemical and solvent resistance, and is therefore useful as a sealing material, a diaphragm, a protective sheet, a punched sheet product, and the like. Furthermore, the method for producing a composite material of the present invention is useful because it allows sealing materials, diaphragms, protective sheets, punched sheet products, etc. to be produced relatively easily and with good productivity. [Example]

[0075] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0076] [Compositions used in Examples and Comparative Examples] <Rubber composition> A Perfluoropolyether-based curable liquid fluorine-containing rubber composition: SIFEL3405A / B (Shin-Etsu Chemical Co., Ltd., two-component composition) B Perfluoropolyether-based curable liquid fluorine-containing rubber composition: SIFEL3590-N (manufactured by Shin-Etsu Chemical Co., Ltd., one-component type composition) C Curable liquid silicone rubber composition: KE1950-40A / B (Shin-Etsu Chemical Co., Ltd., two-component composition) (for comparison) D Millable fluoroelastomer: Dyneon SFM-70A for compression molding (3M Japan Ltd. FKM full compound, non-flowable raw rubber-like fluoroelastomer) (for comparison)

[0077] <Fiber base material> I Carbon cloth I: Tarpee Carbon Cloth C-540 (1.8 mm thick sheet, manufactured by Hagiwara Kogyo Co., Ltd.) II Carbon cloth II: CK6261C (manufactured by Toray Industries, Inc.) III Glass cloth: 2116 107 (manufactured by Nitto Boseki Co., Ltd.)

[0078] <Evaluation> (Tear strength) Test pieces were punched out from the sheets obtained in the following Examples and Comparative Examples using a No. 4 dumbbell, and the tear strength was measured using a tensile tester for measuring rubber properties. (Toluene swelling and ethanol swelling) The test piece was placed in a reagent bottle containing 100 ml of toluene or ethanol and immersed at 23°C for 24 hours. If there was no swelling of the rubber or separation from the fiber, it was judged as ◯; if any change was observed, it was judged as ×.

[0079] Example 1, 2, Reference example 1 and Comparative Example 1> In order to confirm the differences between different fiber types as shown in the table below, test samples of the composite materials were prepared using rubber composition A as the curable liquid fluorine-containing composition and fiber substrates I, II, and III (no fiber substrate was used in Comparative Example 1). Test samples were prepared as follows: Each fiber substrate (fiber sheet) was cut into a 9 cm square, and placed in a stainless steel container containing a sufficient amount of liquid material (rubber composition A) for impregnation. The liquid material was carefully impregnated into each fiber substrate using both hands wearing polyethylene gloves. After the impregnation was completed, each fiber substrate impregnated with the liquid material together with the stainless steel container was placed in a vacuum chamber and subjected to vacuum degassing until no new bubbles were generated. Next, the composites (each degassed fiber substrate) were placed in a 10cm square, 2mm or 1mm thick mold and cured in a 100-ton pressure and heat press (150°C) for rubber molding to prepare test samples. 1、2 It was possible to easily produce a composite sheet with high tear strength. In Comparative Example 1, a rubber sheet was produced using only rubber composition A without a fiber substrate, and its tear strength was higher than that of Examples 1 and 2. 1、2 It was about 1 / 20 to 1 / 80 of the original.

[0080] [Table 1]

[0081] Example 3 and Comparative Examples 2 and 3> Example 3 In Example 1, a sheet was produced in the same manner as in Example 2, except that rubber composition B was used instead of rubber composition A as the curable liquid fluorine-containing composition. , 2 and Reference Example 1 It was possible to easily produce a composite sheet with high tear strength similar to that of the previous example. Comparative Example 2 is Example 3 The curable liquid fluorine-containing composition of Example 1 was replaced with a curable liquid silicone rubber composition. 3 However, it was confirmed that the sheet swelled significantly when immersed in toluene and had poor chemical resistance. Comparative Example 3 is Example 3 Instead of the curable liquid fluorine-containing composition described above, a general Millable-type fluoroelastomer (a non-flowable raw rubber-like fluoroelastomer) was used. Dissolving Millable-type fluoroelastomer in a solvent to turn it into a liquid poses a risk of fire, so a three-layer laminate of rubber-fiber substrate-rubber was passed through two rubber rolls to form an integrated sheet, which was then pressurized and heated at 170°C, but air bubbles accumulated at the interface between the fiber substrate and the rubber, causing it to easily peel off.

[0082] [Table 2]

Claims

1. A composite material is formed by integrating a cured product of a heat-curable liquid fluorine-containing composition containing a curable liquid fluorine-containing compound containing a perfluoropolyether structure with a carbon fiber substrate, and the perfluoropolyether structure contains a repeating unit represented by --CF(CF 3 )CF 2 O--.

2. A composite material is obtained by integrating a cured product of a heat-curable liquid fluorine-containing composition containing a curable liquid fluorine-containing compound containing a perfluoropolyether structure with a carbon fiber substrate, and the curable liquid fluorine-containing compound contains an alkenyl group.

3. The curable liquid fluorine-containing composition comprises (A) a curable liquid fluorine-containing compound, which is a curable polyfluoro compound having at least two alkenyl groups in one molecule and a divalent perfluoropolyether structure containing a repeating unit represented by —CF(CF 3 )CF 2 O— in the main chain; (B) a crosslinking agent having two or more hydrosilyl groups in one molecule; (C) a hydrosilylation reaction catalyst, and (D) Reinforcing filler The composite of claim 1 comprising:

4. The curable liquid fluorine-containing composition comprises (A) a curable liquid fluorine-containing compound, which is a curable polyfluoro compound having at least two alkenyl groups in one molecule and a divalent perfluoropolyether structure in the main chain; (B) a crosslinking agent having two or more hydrosilyl groups in one molecule; (C) a hydrosilylation reaction catalyst, and (D) Reinforcing filler The composite of claim 2 comprising:

5. 5. The composite material according to claim 3, wherein the composition further comprises (E) a hydrosilylation reaction inhibitor.

6. A step of uniformly impregnating a carbon fiber substrate with a curable liquid fluorine-containing composition; A step of degassing the carbon fiber substrate uniformly impregnated with the curable liquid fluorine-containing composition; and A step of curing the curable liquid fluorine-containing composition uniformly impregnated into the carbon fiber substrate after degassing; A method for producing a composite material according to claim 1 or 2, comprising:

7. A rubber product having, as a partial structure or entire structure, a composite material formed by integrating a cured product of a heat-curable liquid fluorine-containing composition containing a curable liquid fluorine-containing compound having a perfluoropolyether structure with a carbon fiber substrate.

8. 8. The rubber product of claim 7, wherein the composite material is a seal, a diaphragm, a protective sheet, or a sheet punching.

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