WO2011040576A1 - 架橋性フッ素ゴム組成物および架橋ゴム物品 - Google Patents
架橋性フッ素ゴム組成物および架橋ゴム物品 Download PDFInfo
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- WO2011040576A1 WO2011040576A1 PCT/JP2010/067161 JP2010067161W WO2011040576A1 WO 2011040576 A1 WO2011040576 A1 WO 2011040576A1 JP 2010067161 W JP2010067161 W JP 2010067161W WO 2011040576 A1 WO2011040576 A1 WO 2011040576A1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
Definitions
- the present invention relates to a crosslinkable fluororubber composition capable of obtaining a crosslinked rubber article excellent in flexibility at a low temperature and a crosslinked rubber article obtained therefrom.
- cross-linking fluoropolymer organic peroxide is mixed with fluororubber and heated to perform peroxide cross-linking, or as disclosed in Patent Document 1, radiation cross-linking is performed by irradiating fluororubber with radiation. How to do is known. At that time, in order to improve the crosslinking characteristics of the fluororubber and the characteristics of the obtained crosslinked rubber article, a polyfunctional compound has been conventionally blended as a crosslinking aid.
- triallyl isocyanurate has been preferably used conventionally (see Non-Patent Document 1 and Patent Document 1).
- triallyl isocyanurate as a crosslinking aid, the crosslinking rate of the fluororubber can be improved.
- a triazine ring skeleton excellent in heat resistance is introduced between the crosslinking points of the fluororubber, there is an advantage that a crosslinked rubber article excellent in heat resistance and mechanical properties can be obtained.
- fluororubber particularly fluororubber containing tetrafluoroethylene as a copolymer component, is inferior in flexibility at low temperatures and has a problem in sealing performance in a low temperature environment.
- an object of the present invention is to provide a crosslinkable fluororubber composition and a crosslinked rubber article capable of obtaining a crosslinked rubber article excellent in flexibility at a low temperature.
- the present invention provides the following.
- a crosslinkable fluororubber composition comprising a fluororubber and a compound represented by the following formula (A).
- X is a group represented by the following formula (X)
- Z is a group represented by the following formula (Z)
- Y is a perfluoro saturated hydrocarbon group or an etheric oxygen atom between the carbon-carbon atoms of the group.
- An inserted (x + z) -valent group x is an integer of 3 or more, z is an integer of 0 or more, and x + z is an integer of 3 or more.
- U is a monovalent group having one or more selected from the group consisting of unsaturated hydrocarbons, bromine atoms and iodine atoms
- R F is a linear perfluoroalkyl group having 1 to 20 carbon atoms.
- a is an integer of 0 to 20
- b is an integer of 1 to 200
- c is an integer of 3 to 200.
- b1, b2 and b3 are each independently an integer of 1 to 20.
- the ratio (Mw / Mn) of the mass average molecular weight (Mw) to the number average molecular weight (Mn) of the compound represented by the formula (A) is 1.0 to 2.0, [1] to [5 ]
- the crosslinkable fluororubber composition in any one of.
- the crosslinkable fluororubber composition according to any one of [1] to [6], which contains 1 to 50 parts by mass of the compound represented by the formula (A) with respect to 100 parts by mass of the fluororubber. .
- the group in which the fluororubber comprises a tetrafluoroethylene / propylene copolymer, a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, and a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer.
- the crosslinkable fluororubber composition of the present invention contains the compound represented by the above formula (A), it is excellent in crosslinkability such as peroxide crosslinkability and radiation crosslinkability, and has a high crosslinking speed.
- the crosslinked rubber article of the present invention obtained by crosslinking this crosslinkable fluororubber composition is excellent in flexibility at low temperature, has good low temperature properties, and further has strength, hardness, modulus, permanent compression. Excellent basic characteristics such as distortion.
- the compound represented by the formula (A) is also referred to as a compound (A).
- the group represented by the formula (X) is also referred to as a group (X). The same applies to other groups.
- the crosslinkable fluororubber composition of the present invention comprises a composition containing at least fluororubber and the following compound (A).
- X in the compound (A) is a monovalent group represented by the following formula (X).
- a is an integer of 0 to 20, preferably an integer of 0 to 10, particularly preferably 0 to 2.
- B is an integer of 1 to 200, preferably an integer of 1 to 100, particularly preferably an integer of 1 to 20.
- U is a monovalent group having one or more selected from the group consisting of unsaturated hydrocarbons, bromine atoms and iodine atoms. Specific examples of the case where U is a group having an unsaturated hydrocarbon include the following structures (U-1) to (U-13).
- (U-8), (U-9), (U-11), or (U-12) is preferable because of the structure in which an allyl group is bonded to N, (U-11), or (U-12) is particularly preferred.
- n represents an integer of 1 to 3.
- n represents an integer of 1 to 3. I (CH 2 ) n ⁇ I (CH 2 ) n C (O) O—CH 2 —
- Z in the compound (A) is a monovalent group represented by the following formula (Z).
- R F is a linear perfluoroalkyl group having 1 to 20 carbon atoms or a group in which an etheric oxygen atom is inserted between carbon-carbon atoms of the group, and the carbon number is particularly preferably 1 to 16.
- R F include the following groups.
- s represents an integer of 0 to 15
- C y F represents a perfluorocyclohexyl group
- t represents an integer of 0 to 15
- a d F represents a perfluorinated adamantane group
- t represents 0 to 15 Indicates an integer.
- Y in the compound (A) is a perfluoro saturated hydrocarbon group or a (x + z) -valent group in which an etheric oxygen atom is inserted between carbon-carbon atoms of the group.
- X + z which is the valence of the group (Y) is an integer of 3 or more, preferably 3 to 110, and particularly preferably 3 to 9.
- the group (Y) is a trivalent group
- the group (Y 3 -4) represents a perfluorocyclohexane-1,3,5-triyl group.
- Specific examples in the case where the group (Y) is a tetravalent group include groups (Y 4 -1) to groups (Y 4 -5).
- a specific example in the case where the group (Y) is a pentavalent group includes a group (Y 5 -1).
- the group (Y) is preferably a group (Y 3 -1) to a group (Y 3 -4).
- Compound (A) is a compound in which x group (X) and z group (Z) are bonded to group (Y). However, x is an integer greater than or equal to 3, z is an integer greater than or equal to 0, and (x + z) is an integer greater than or equal to 3. That is, the compound (A) is a compound in which three or more groups (X) are bonded to the group (Y) and the group (Z) is optionally bonded.
- the compound (A) has three or more groups (X) having a linear perfluoropolyether bond (the “— (CF 2 CF 2 O) b —” portion of the group (X)), Excellent flexibility. Further, this group (X) has U (hereinafter referred to as a reactive group (U)) which is a monovalent group having one or more selected from the group consisting of unsaturated hydrocarbons, bromine atoms and iodine atoms. is doing. Therefore, when the fluororubber composition containing the compound (A) is subjected to a crosslinking treatment, the compound (A) is bonded to the fluororubber and three-dimensionally cross-linked, so that it is stably taken into the fluororubber.
- U reactive group
- x is an integer of 3 or more, preferably 3 to 100, particularly preferably 3 to 8.
- Z is an integer of 0 or more, preferably 0 to 10, more preferably 0 to 1, and particularly preferably 0.
- (X + z) is an integer of 3 or more, preferably 3 to 110, more preferably 3 to 9, and particularly preferably 3 or 4.
- the compound (A) is preferably a compound represented by the following formula (A1).
- x1 is an integer of 3 or 4.
- Specific examples of the compound (A) when the group (Y) is a trivalent group include compounds (A 3 -1) to (A 3 -4).
- Specific examples of the group (Y) being a tetravalent group include compounds (A 4 -1) to (A 4 -10). Of these, (A 3 -1), (A 4 -1), or (A 4 -2) is preferable because the balance between crosslinkability and low temperature characteristics is good.
- a preferred specific example of the compound (A) is a compound represented by the following formula (A2).
- b1, b2 and b3 are each independently an integer of 1 to 20, preferably an integer of 1 to 10.
- the number average molecular weight (hereinafter also referred to as Mn) of the compound (A) is preferably 500 to 100,000, more preferably 1,000 to 20,000.
- Mn is less than 500, the low-temperature characteristics tend to be insufficient, and when it exceeds 100,000, the crosslinkability tends to decrease.
- the ratio of the mass average molecular weight (hereinafter also referred to as Mw) to the number average molecular weight (Mn) of the compound (A) (hereinafter also referred to as Mw / Mn) is preferably 1.0 to 2.0.
- Mn and Mw are values measured by gel permeation chromatography (hereinafter referred to as GPC), and Mw / Mn is a value obtained from Mn and Mw measured by GPC. .
- Compound (A) can be produced, for example, by producing compound (A0) by the method described in International Publication No. 2005/068534 and converting the terminal of the compound by a known method.
- Rd is a lower alkyl group.
- the values of x and z may change depending on the reaction conditions of the fluorination step in the production of (A0) (see, for example, [0043] and [0044] in JP2009-197210A). Therefore, the compound (A) may include a compound having x of 2 or less.
- the compound having x of 2 or less is not the compound (A) in the present invention, but when the compound (A) is used as a crosslinking aid for fluororubber, the compound having x of 2 or less is not separated.
- Compound (A) may be used as it is.
- the compound (A) may be referred to as an x-functional compound because it has x or more reactive groups (U).
- x when x is 3, it is referred to as a trifunctional compound, and when x is 4, it is referred to as a tetrafunctional compound.
- a by-product compound having x of 2 or less is also referred to as a monofunctional compound or a bifunctional compound.
- the compound (A) obtained by the reaction may be used as a solution after the reaction, or may be used after removing unnecessary solvents and raw materials by concentration or the like. Moreover, you may refine
- the content of the compound (A) is preferably 1 to 50 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the fluororubber.
- the most preferred amount is 10 to 50 parts by mass.
- flexibility in low temperature may be unable to be improved and the improvement effect of a low temperature characteristic may be small.
- a compound (A) may bleed out from the rubber
- the content of the compound (A) is 1 to 50 parts by mass with respect to 100 parts by mass of the fluororubber, a crosslinked rubber article having a high crosslinking rate and excellent low temperature characteristics can be easily obtained.
- Fluorine rubber is not particularly limited. Vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer, tetrafluoroethylene / propylene copolymer Tetrafluoroethylene / propylene / vinylidene fluoride copolymer, hexafluoropropylene / ethylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, vinylidene fluoride / tetrafluoroethylene / perfluoroalkyl vinyl ether Examples thereof include system copolymers.
- tetrafluoroethylene / propylene copolymer vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, or tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer is excellent in chemical resistance. It is preferably used for the reason.
- the fluorine content in the fluororubber is preferably 40% by mass or more, more preferably 50% by mass or more, and most preferably 55% by mass or more.
- a fluororubber having a fluorine content of 40% by mass or more can provide a crosslinked rubber article excellent in heat resistance, chemical resistance, electrical insulation and steam resistance.
- fluoro rubber on the market is “AFLAS150P” (trade name, manufactured by Asahi Glass Co., Ltd., tetrafluoroethylene / propylene copolymer).
- the crosslinkable fluororubber composition of the present invention can further contain an organic peroxide. Any organic peroxide that can easily generate radicals under heating can be used. Of these, those having a half-life of 1 minute and a temperature of 130 to 220 ° C. can be preferably used.
- Specific examples thereof include 1,1-di (t-hexylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t- Butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butyl Peroxy) -hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexine-3, dibenzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2 , 5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-hexylperoxyisopropyl monocarbonate, etc
- the content of the organic peroxide is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and most preferably 0.5 to 4 parts by mass with respect to 100 parts by mass of the fluororubber. 3 parts by mass. Within this range, the crosslinking efficiency of the organic peroxide is high, and the amount of ineffective decomposition can be suppressed. However, in the case where the crosslinkable fluororubber composition is subjected to a crosslinking treatment by irradiation with radiation, the organic peroxide is not particularly required to be contained.
- the crosslinkable fluororubber composition of the present invention may further contain a polyfunctional compound as a crosslinking aid.
- Polyfunctional compounds include triallyl cyanurate, triallyl isocyanurate, triallyl isocyanurate prepolymer, trimethallyl isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl Trimellitate, m-phenylenediamine bismaleimide, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, dipropargyl terephthalate, diallyl phthalate, N, N ′, N ′′, N ′ ′′-tetra Examples thereof include vinyl group-containing siloxane oligomers such as allyl terephthalamide, polymethylvinylsiloxane, and polymethylphenylvinylsiloxane.
- a polyallyl compound is preferable, triallyl cyanurate, triallyl isocyanurate, or trimethallyl isocyanurate is more preferable, and triallyl isocyanurate is more preferable.
- a polyfunctional compound can be used 1 type or in combination of 2 or more types.
- the content thereof is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the compound (A). If the content of the polyfunctional compound is less than 0.1 parts by mass, the effect of addition is hardly obtained, and if it exceeds 20 parts by mass, the moldability may be impaired.
- the crosslinkable fluororubber composition of the present invention can contain a filler.
- a filler By containing the filler, the strength of the obtained crosslinked rubber article can be improved.
- carbon black is preferably used. Any carbon black can be used as long as it is used for blending rubber. Specific examples thereof include furnace black, acetylene black, thermal black, channel black, and graphite. Of these, furnace black is more preferable, and specific examples thereof include HAF-LS, HAF, HAF-HS, FEF, GPF, APF, SRF-LM, SRF-HM, and MT grades, and MT is most preferable.
- the content thereof is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the fluororubber.
- the content of the filler is less than 5 parts by mass, the effect of addition is hardly obtained, and when it exceeds 100 parts by mass, the elongation characteristics of the crosslinked rubber article may be deteriorated.
- the content of the filler is in the above range, the balance between strength and elongation of the obtained crosslinked rubber article is good.
- the crosslinkable fluororubber composition of the present invention can contain other additives such as reinforcing materials, processing aids, lubricants, lubricants, flame retardants, antistatic agents, and coloring agents.
- the reinforcing material examples include fluororesins such as polytetrafluoroethylene and ethylene / tetrafluoroethylene copolymer, glass fibers, carbon fibers, and white carbon.
- the content thereof is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the fluororubber.
- processing aid examples include alkali metal salts of higher fatty acids, and stearates or laurates are preferred.
- the content thereof is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, most preferably 100 parts by mass of the fluororubber. 1 to 5 parts by mass. If there are too many processing aids, blooming to the surface of the crosslinked rubber article may occur, the hardness of the crosslinked rubber article may be too high, and chemical resistance and steam resistance may be low. If the amount of processing aid is too small, the tensile strength of the crosslinked rubber article may be significantly reduced, and the elongation and the change in tensile strength after heat aging may be increased.
- the method for preparing the crosslinkable fluorororubber composition of the present invention is not particularly limited and can be prepared by a conventionally known method.
- a method of kneading the fluororubber, the compound (A) and, if necessary, an organic peroxide, carbon black, and other additives using a kneader such as a two-roll, Banbury mixer, kneader or the like is preferable.
- distributed each said component in the solvent is also employable.
- the order of mixing the above components is not particularly limited.
- Etc. are preferably blended and kneaded.
- the temperature range of 80 to 120 ° C. which is a temperature at which the crosslinking reaction does not occur, by cooling the kneader with water.
- the crosslinked rubber article of the present invention can be obtained by molding and crosslinking the crosslinkable fluororubber composition of the present invention by a conventionally known method such as extrusion molding, injection molding, transfer molding or press molding. Molding and crosslinking may be performed simultaneously or in separate steps.
- the crosslinked rubber articles (Primary cross-linked product) is obtained.
- the heating temperature is preferably 130 to 220 ° C, more preferably 140 to 200 ° C, and most preferably 150 to 180 ° C.
- the crosslinked rubber article (primary crosslinked product) is further heated in an oven or the like using electricity, hot air, steam or the like as a heat source as necessary to allow the crosslinking to proceed (also referred to as secondary crosslinking).
- the residue of the organic peroxide contained in the crosslinked rubber article is decomposed and volatilized to be reduced.
- the heating temperature during secondary crosslinking is preferably 150 to 280 ° C, more preferably 180 ° C to 260 ° C, and most preferably 200 to 250 ° C.
- the secondary crosslinking time is preferably 1 to 48 hours, more preferably 4 to 24 hours.
- the crosslinkable fluororubber composition of the present invention can be crosslinked by irradiating with ionizing radiation such as electron beam and ⁇ ray.
- ionizing radiation such as electron beam and ⁇ ray.
- the crosslinkable fluororubber composition of the present invention is dissolved and dispersed in an appropriate solvent to form a suspension solution, which is molded by coating or the like, and dried.
- the dose of ionizing radiation may be appropriately selected, but is preferably 1 to 300 kGy, and more preferably 10 to 200 kGy.
- the crosslinked rubber article of the present invention is used in various fields such as automobiles and other transport machines, general equipment, electrical equipment, etc., sealing materials such as O-rings, sheets, gaskets, oil seals, bearing seals, diaphragms, cushioning materials, vibration-proof materials. It can be suitably used in a wide range as each member such as a wire covering material, industrial belts, tubes / hoses, sheets and the like. Especially, it has excellent flexibility at low temperature, and also has excellent basic properties such as strength, hardness, modulus, compression set, etc., and sealing materials such as O-rings, sheets, gaskets, oil seals, bearing seals, etc. Can be preferably used.
- Fluororubber Polymer 1 Tetrafluoroethylene / perfluoroalkyl vinyl ether binary copolymer (trade name “AFLAS PFE1000”, manufactured by Asahi Glass Co., Ltd., peroxide crosslinking type, fluorine content is 72 mass%)
- Polymer 2 Tetrafluoroethylene / propylene / vinylidene fluoride terpolymer (trade name “AFLAS 200P”, manufactured by Asahi Glass Co., Ltd., peroxide crosslinking type, fluorine content 60 mass%)
- Polymer 3 Tetrafluoroethylene / propylene binary copolymer (trade name “AFLAS 100S”, manufactured by Asahi Glass Co., Ltd., peroxide crosslinking type, fluorine content 57 mass%)
- Crosslinking aid -Crosslinking aid 1 A composition comprising as a main component the compound (A2 ') obtained in the following synthesis example, Mn being 2900, and Mw / Mn being 1.14.
- TAIC Triallyl isocyanurate (Nippon Kasei Co., Ltd.) (3) Organic peroxides Perbutyl P: ⁇ , ⁇ '-bis (t-butylperoxy) -p-diisopropylbenzene (trade name “Perkadox 14”, manufactured by NOF Corporation) Perhexa 25B: 3,5-dimethyl-2,5-di-t-butylperoxyhexane (trade name “Perhexa 25B”, manufactured by NOF Corporation) (4) Filler-MT carbon: carbon black (grade: MT carbon, manufactured by CANCARB) (5) Processing aid-Non-Sal SN-1: Sodium stearate (manufactured by NOF Corporation)
- the compound (A2 ′) was subjected to NMR analysis, HPLC analysis, and GPC analysis as follows under the temperature condition of room temperature (25 ° C.) to confirm that the compound (A2 ′) was produced.
- Tetramethylsilane was used as a reference substance for 1 H-NMR (300.4 MHz).
- CFCl 3 was used as a reference material for 19 F-NMR (282.7 MHz).
- CCl 2 FCClF 2 was used unless otherwise specified.
- composition ratio of the compounds contained in the composition was measured under the following conditions using an HPLC apparatus (Prominence, manufactured by Shimadzu Corporation). Specifically, in one cycle of analysis, the concentration of HFIP in the mobile phase was gradually increased from 0% to 100%, the compounds contained in the composition were separated, and the mass ratio was analyzed.
- Analytical column Normal phase silica gel column (manufactured by YMC, SIL-gel) Mobile phase: dichloropentafluoropropane (Asahi Glass AK-225G) and HFIP Mobile phase flow rate: 1.0 mL / min Column temperature: 37 ° C Detector: Evaporative light scattering detector ⁇ GPC analysis> According to the method described in JP-A-2001-208736, the number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by GPC under the following conditions to obtain Mw / Mn.
- Mn number average molecular weight
- Mw mass average molecular weight
- Analytical column Two PLgel MIXED-E columns (manufactured by Polymer Laboratories) connected in series Standard sample for molecular weight measurement: 4 perfluoropolyether having a Mw / Mn of less than 1.1 and a molecular weight of 2000 to 10,000
- Mobile phase flow rate 1.0 mL / min Column temperature: 37 ° C.
- Detector Evaporative light scattering detector
- the obtained crosslinking aid 1 was 7.0% by mass of the monofunctional compound, 30.8% by mass of the bifunctional compound, and 42.9% by mass of the trifunctional compound (A2 ′). It was found that the composition contained 18.1% by mass of a tetrafunctional compound and 1.2% by mass of a compound having a functional group number higher than that. Therefore, the proportion of the trifunctional or higher functional compound (A) effective for three-dimensional crosslinking was 62.2% by mass.
- the monofunctional and bifunctional compounds are compounds with a small number of functional groups, which are by-produced in the fluorination step, and are not compound (A), but were not separated, and the crosslinking aid 1 was used as it was.
- the number average molecular weight (Mn) of the crosslinking aid 1 was 2900, and Mw / Mn was 1.14. It was also confirmed that the crosslinking aid 1 did not have a —OCF 2 O— structure.
- Low temperature elastic recovery test In accordance with JIS K6261, a low temperature elastic recovery test was performed with a low temperature elastic recovery tester (TR tester, manufactured by Ueshima Seisakusho), and a TR-10 value was measured.
- Hardness Hardness (HS) was measured by durometer type A hardness test at 23 ° C. according to JIS K6253. A hardness of 60 to 90 indicates that it is suitable as a sealing material.
- Tensile strength Tensile strength (T B ) was measured at 23 ° C. in accordance with JIS K6251. If the tensile strength (T B ) is 10 MPa or more, it indicates that it is suitable as a sealing material.
- Elongation Elongation (E B ) was measured at 23 ° C.
- Example 1 100 parts by weight of polymer 1, 1 part by weight of perhexa 25B, 5 parts by weight of crosslinking aid 1, 20 parts by weight of MT-carbon, and 1 part by weight of non-sar SN-1 are kneaded with a biaxial roll, and peroxide crosslinkable.
- a fluororubber composition was obtained. The composition was molded into a sheet of 100 mm ⁇ 100 mm ⁇ 2 mm with a hot press at 170 ° C. (primary crosslinking). The sheet was further placed in a gear oven at 250 ° C. for 4 hours for secondary crosslinking. Four samples were punched from the obtained crosslinked rubber sheet with a No. 3 dumbbell, and the properties of the crosslinked rubber were measured.
- This crosslinked rubber article has a hardness (HS) of 61, a tensile strength (T B ) of 19.8 MPa, an elongation (E B ) of 232%, and a 100% tensile stress (M 100 ) of 9.0 MPa. Yes, the compression set was 30%, and the TR-10 value was -7.6 ° C.
- Examples 2 to 6, Comparative Examples 1 to 3 A crosslinked rubber sheet was prepared in the same manner as in Example 1 except that each compounding component was changed as shown in Table 1, and the characteristics of the crosslinked rubber article were measured in the same manner as described above.
- the crosslinked rubber articles of Examples 1 to 6 have normal physical properties equivalent to the crosslinked rubber articles of Comparative Examples 1 to 3, while having a low TR-10 value and flexibility at low temperatures. It was excellent. In addition, the TR-10 value decreased as the amount of the crosslinking aid 1 increased, resulting in improved flexibility at low temperatures.
- the crosslinked rubber articles of Comparative Examples 1 to 3 obtained by crosslinking a fluororubber composition not containing the crosslinking aid 1 (compound (A2)) are identical to those of Examples 1 to 6.
- the crosslinked rubber article obtained using fluororubber had a high TR-10 value and was inferior in flexibility at low temperatures.
- the crosslinked rubber article of the present invention is used in various fields such as automobiles and other transport machines, general equipment, electrical equipment, etc., sealing materials such as O-rings, sheets, gaskets, oil seals, bearing seals, diaphragms, cushioning materials, vibration-proof materials. It can be suitably used in a wide range as each member such as a wire covering material, industrial belts, tubes / hoses, sheets and the like.
- sealing materials such as O-rings, sheets, gaskets, oil seals, bearing seals, diaphragms, cushioning materials, vibration-proof materials. It can be suitably used in a wide range as each member such as a wire covering material, industrial belts, tubes / hoses, sheets and the like.
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Abstract
Description
(X-)x(Z-)zY ・・・(A)
Xは下式(X)で表わされる基であり、Zは下式(Z)で表わされる基であり、Yはペルフルオロ飽和炭化水素基または該基の炭素-炭素原子間にエーテル性酸素原子が挿入された(x+z)価の基であり、xは3以上の整数であり、zは0以上の整数であり、x+zは3以上の整数である。
U-(CF2)aO(CF2CF2O)b- ・・・(X)
RFO(CF2CF2O)c- ・・・(Z)
ただし、Uは、不飽和炭化水素、臭素原子及びヨウ素原子からなる群から選ばれる1種以上を持つ1価の基であり、RFは、炭素数が1~20の直鎖のペルフルオロアルキル基または該基の炭素-炭素原子間にエーテル性酸素原子が挿入された基であり、aは0~20の整数であり、bは1~200の整数であり、cは3~200の整数である。
[2] 前記式(A)で表わされる化合物が、下式(A1)で表わされる化合物である、[1]に記載の架橋性フッ素ゴム組成物。
(X-)x1Y ・・・(A1)
ただし、x1は、3又は4の整数である。
[3] 式(A1)におけるx1が3であり、Yが下式で表される基(Y3-1)~(Y3-4)のいずれかである[2]に記載の架橋性フッ素ゴム組成物。
[5] 前記式(A)で表わされる化合物の数平均分子量(Mn)が500~100,000である、[1]~[4]のいずれかに記載の架橋性フッ素ゴム組成物。
[6] 前記式(A)で表わされる化合物の数平均分子量(Mn)に対する質量平均分子量(Mw)の割合(Mw/Mn)が1.0~2.0である、[1]~[5]のいずれかに記載の架橋性フッ素ゴム組成物。
[7] 前記式(A)で表わされる化合物を、前記フッ素ゴム100質量部に対して1~50質量部含有する、[1]~[6]のいずれかに記載の架橋性フッ素ゴム組成物。
[8] 前記フッ素ゴムが、テトラフルオロエチレン/プロピレン系共重合体、フッ化ビニリデン/テトラフルオロエチレン/ヘキサフルオロプロピレン系共重合体、及びテトラフルオロエチレン/パーフルオロアルキルビニルエーテル系共重合体からなる群から選ばれる1種以上である、[1]~[7]のいずれかに記載の架橋性フッ素ゴム組成物。
[9] さらに、有機過酸化物を含有する、[1]~[8]のいずれかに記載の架橋性フッ素ゴム組成物。
[10] [1]~[9]のいずれかに記載の架橋性フッ素ゴム組成物を架橋してなることを特徴とする架橋ゴム物品。
[11] 前記架橋ゴム物品がシール材である[10]に記載の架橋ゴム物品。
本発明の架橋性フッ素ゴム組成物は、フッ素ゴムと、下記化合物(A)とを少なくとも含む組成からなるものである。
(X-)x(Z-)zY ・・・(A)
まず、本発明の架橋性フッ素ゴム組成物に用いる化合物(A)について説明する。この化合物(A)は、本発明の架橋性フッ素ゴム組成物において架橋助剤として機能するものである。
U-(CF2)aO(CF2CF2O)b- ・・・(X)
Br(CH2)n-
Br(CH2)nC(O)O-CH2-
I(CH2)n-
I(CH2)nC(O)O-CH2-
U-CF2O(CF2CF2O)b- ・・・(X1)
RFO(CF2CF2O)c- ・・・(Z)
CF3(CF2)s-
Cy F-(CF2)t-
Ad F-(CF2)t-
(X-)x1Y ・・・(A1)
ただし、x1は、3又は4の整数である。
(RdOC(O)-CF2O(CF2CF2O)b-)x(Z-)zY・・・(A0)
また、(A0)の製造のフッ素化工程の反応条件に応じて、xとzの値が変化することがある(特開2009-197210号公報の[0043]、[0044]等を参照)。そのため、化合物(A)には、xが2以下の化合物が含まれる場合がある。その場合、xが2以下の化合物は、本発明における化合物(A)ではないが、化合物(A)をフッ素ゴムの架橋助剤として使用する際に、xが2以下の化合物を分離せずに化合物(A)をそのまま使用しても良い。
なお、本明細書において、化合物(A)は、反応基(U)をx個以上有することから、x官能の化合物という場合がある。化合物(A)において、xが3の場合には3官能の化合物、xが4の場合には4官能の化合物等という。また、副生物であるxが2以下の化合物は、1官能の化合物及び2官能の化合物ともいう。
次に、本発明の架橋性フッ素ゴム組成物に用いるフッ素ゴムについて説明する。
本発明の架橋性フッ素ゴム組成物は、更に有機過酸化物を含有させることができる。有機過酸化物としては、加熱下、容易にラジカルを発生するものであればいずれも使用できる。なかでも、半減期が、1分となる温度が130~220℃であるものが好ましく使用できる。その具体例としては、1,1-ジ(t-ヘキシルパーオキシ)-3,5,5-トリメチルシクロへキサン、2,5-ジメチルへキサン-2,5-ジヒドロパーオキシド、ジ-t-ブチルパーオキシド、t-ブチルクミルパーオキシド、ジクミルパーオキシド、α,α’-ビス(t-ブチルパーオキシ)-p-ジイソプロピルベンゼン、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)-へキサン、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)-へキシン-3、ジベンゾイルパーオキシド、t-ブチルパーオキシベンゼン、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)へキサン、t-ブチルパーオキシマレイン酸、t-ヘキシルパーオキシイソプロピルモノカーボネート等が挙げられ、好ましくはα,α’-ビス(t-ブチルパーオキシ)-p-ジイソプロピルベンゼンである。有機過酸化物は、1種又は2種以上を組み合わせて用いることができる。
本発明の架橋性フッ素ゴム組成物は、架橋助剤として多官能性化合物を更に含有させてもよい。多官能性化合物としては、トリアリルシアヌレート、トリアリルイソシアヌレート、トリアリルイソシアヌレートプレポリマー、トリメタリルイソシアヌレート、1,3,5-トリアクリロイルヘキサヒドロ-1,3,5-トリアジン、トリアリルトリメリテート、m-フェニレンジアミンビスマレイミド、p-キノンジオキシム、p,p'-ジベンゾイルキノンジオキシム、ジプロパルギルテレフタレート、ジアリルフタレート、N,N',N’',N’’’-テトラアリルテレフタールアミド、ポリメチルビニルシロキサン、ポリメチルフェニルビニルシロキサン等のビニル基含有シロキサンオリゴマー等が挙げられる。なかでも、多アリル化合物が好ましく、トリアリルシアヌレート、トリアリルイソシアヌレート、又はトリメタリルイソシアヌレートがより好ましく、トリアリルイソシアヌレートがさらに好ましい。化合物(A)とトリアリルイソシアヌレートとを併用することにより、架橋ゴム物品からのブリードアウトをより効果的に抑えることができる。多官能性化合物は、1種又は2種以上を組み合わせて用いることができる。多官能性化合物を含有する場合、その含有量は、化合物(A)100質量部に対し、好ましくは0.1~20質量部であり、より好ましくは0.2~10質量部である。多官能性化合物の含有量が0.1質量部未満であると添加効果がほとんど得られず、20質量部を超えると成形性が損なわれることがある。
本発明の架橋性フッ素ゴム組成物の調製方法としては、特に限定はなく、従来公知の方法により調製できる。好ましくは、フッ素ゴム、上記化合物(A)及び、必要に応じて有機過酸化物、カーボンブラック、その他添加剤を、2本ロール、バンバリーミキサー、ニーダー等の混練機を用いて混練する方法が好ましい。また、上記各成分を溶剤に溶解、分散した状態で混練して調製する方法も採用できる。
本発明の架橋ゴム物品は、上記本発明の架橋性フッ素ゴム組成物を、押出成形、射出成形、トランスファー成形、プレス成形等の従来公知の方法で成形し、架橋することで得られる。成形と架橋は同時に行ってもよく、それぞれ別工程で行ってもよい。
以下の実施例、比較例で使用した配合成分は、以下の通りである。
・ポリマー1:テトラフルオロエチレン/パーフルオロアルキルビニルエーテル系2元共重合体(商品名「AFLAS PFE1000」、旭硝子社製、過酸化物架橋タイプ、フッ素含有量は72質量%)
・ポリマー2:テトラフルオロエチレン/プロピレン/フッ化ビニリデン3元共重合体(商品名「AFLAS 200P」、旭硝子社製、過酸化物架橋タイプ、フッ素含有量60質量%)
・ポリマー3:テトラフルオロエチレン/プロピレン2元共重合体(商品名「AFLAS 100S」、旭硝子社製、過酸化物架橋タイプ、フッ素含有量57質量%)
(2)架橋助剤
・架橋助剤1:以下の合成例で得られた化合物(A2’)を主成分とし、Mnは2900であり、Mw/Mnは1.14である組成物 ・TAIC:トリアリルイソシアヌレート(日本化成社製)
(3)有機過酸化物
・パーブチルP:α,α’-ビス(t-ブチルパーオキシ)-p-ジイソプロピルベンゼン(商品名「パーカドックス14」、日油社製)
・パーヘキサ25B:3,5-ジメチル-2,5-ジ-t-ブチルパーオキシへキサン(商品名「パーヘキサ25B」、日油社製)
(4)充填剤
・MTカーボン:カーボンブラック(グレード:MTカーボン,CANCARB社製) (5)加工助剤
・ノンサール SN-1:ステアリン酸ナトリウム(日油社製)
スターラーチップを投入した100mLの丸底フラスコを充分に窒素置換した。以下の化合物(A0-1)を主成分とする組成物の20.0gと、ジクロロペンタフルオロプロパンの20gとを丸底フラスコに入れ、激しく撹拌した。1時間後、丸底フラスコの上部に設置した滴下漏斗より、CH2=CHCH2NH2の1.5gとジクロロペンタフルオロプロパンの20gの混合物を0.5時間かけてゆっくりと滴下した。滴下終了後、50℃に昇温して6時間撹拌を継続して室温まで冷却した。
1H-NMR(300.4MHz)の基準物質としては、テトラメチルシランを用いた。また、19F-NMR(282.7MHz)の基準物質としては、CFCl3を用いた。また、溶媒としては、特に記載しない限り、CCl2FCClF2を用いた。
組成物に含まれる化合物の組成比を、HPLC装置(島津製作所社製、Prominence)を用い、下記の条件にて測定した。具体的には、分析1サイクルにて、移動相中のHFIPの濃度を0%から100%に徐々に増加させ、組成物に含まれる化合物を分離し、質量比を分析した。
分析カラム:順相系シリカゲルカラム(ワイエムシー社製、SIL-gel)
移動相:ジクロロペンタフルオロプロパン(旭硝子社製、アサヒクリンAK-225G)およびHFIP
移動相流速:1.0mL/分
カラム温度:37℃
検出器:蒸発光散乱検出器
〈GPC分析〉
特開2001-208736号公報に記載の方法にしたがって、下記の条件にてGPCにより数平均分子量(Mn)および質量平均分子量(Mw)を測定し、Mw/Mnを求めた。
移動相:ジクロロペンタフルオロプロパン(旭硝子社製、アサヒクリンAK-225SECグレード1)とヘキサフルオロイソプロピルアルコールとの混合溶媒(ジクロロペンタフルオロプロパン/ヘキサフルオロイソプロピルアルコール=99/1体積比)、
分析カラム:PLgel MIXED-Eカラム(ポリマーラボラトリーズ社製)を2本直列に連結したもの
分子量測定用標準試料:Mw/Mnが1.1未満であり、分子量が2000~10000のペルフルオロポリエーテルの4種およびMw/Mnが1.1以上であり、分子量が1300のペルフルオロポリエーテルの1種
移動相流速:1.0mL/分
カラム温度:37℃
検出器:蒸発光散乱検出器
1H-NMRスペクトル δ(ppm):7.09,5.92,5.38~5.20,3.72
19F-NMRスペクトル δ(ppm):-54.0,-77.6,-88.2~-92.0,-135.0~-139.0
以下の実施例、比較例の架橋ゴム物品の、TR-10値、硬度(HS)、引張り強度(TB)、伸び(EB)、圧縮永久歪み、100%引張応力(M100)の測定は、以下に示す方法により行った。
・硬度:JIS K6253に準拠し、23℃でデュロメータータイプA硬度試験にて硬度(HS)を測定した。硬度が60~90であると、シール材として適することを示す。
・引張り強度:JIS K6251に準拠して23℃にて引張り強度(TB)を測定した。引張り強度(TB)が10MPa以上であると、シール材として適することを示す。
・伸び:JIS K6251に準拠して23℃にて伸び(EB)を測定した。伸び(EB)は160%以上であると、シール材として適することを示す。
・圧縮永久歪み:JIS K6262に従い,200℃で70時間の圧縮永久歪みを測定した。
・100%引張応力(モジュラス):JIS K6251に準拠して23℃にて100%引張応力(M100)を測定した。100%引張応力(M100)は2~17MPaであると、シール材として適することを示す。
ポリマー1の100質量部、パーヘキサ25Bの1質量部、架橋助剤1の5質量部、MT-カーボンの20質量部、ノンサール SN-1の1質量部を二軸ロールによって混練し、パーオキシド架橋性フッ素ゴム組成物を得た。該組成物を170℃の熱プレスで100mm×100mm×2mmのシート状に成形した(一次架橋)。このシートを更に、250℃のギアオーブンに4時間入れ、二次架橋した。
得られた架橋ゴムシートより、第3号ダンベルで試料を4枚打ち抜き、架橋ゴムの特性を測定した。またJIS K6250に準拠し、低温弾性回復試験用試料を4個作製して、低温弾性回復試験を行った。結果を表1に示す。この架橋ゴム物品の硬度(HS)は61であり、引張り強度(TB)は19.8MPaであり、伸び(EB)232%であり、100%引張応力(M100)は9.0MPaであり、圧縮永久歪みは、30%であり、TR-10値は-7.6℃であった。
各配合成分を表1に示すように変えた以外は、実施例1と同様にして架橋ゴムシートを作成し、上記と同様に架橋ゴム物品の特性を測定した。
これに対し、架橋助剤1(化合物(A2))を含まないフッ素ゴム組成物を架橋して得られた比較例1~3の架橋ゴム物品は、実施例1~6に比べて、同一のフッ素ゴムを用いて得られた架橋ゴム物品のTR-10値が高く、低温下での柔軟性に劣るものであった。
なお、2009年10月1日に出願された日本特許出願2009-229424号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (11)
- フッ素ゴムと、下式(A)で表わされる化合物を含むことを特徴とする架橋性フッ素ゴム組成物。
(X-)x(Z-)zY ・・・(A)
Xは下式(X)で表わされる基であり、Zは下式(Z)で表わされる基であり、Yはペルフルオロ飽和炭化水素基または該基の炭素-炭素原子間にエーテル性酸素原子が挿入された(x+z)価の基であり、xは3以上の整数であり、zは0以上の整数であり、x+zは3以上の整数である。
U-(CF2)aO(CF2CF2O)b- ・・・(X)
RFO(CF2CF2O)c- ・・・(Z)
ただし、Uは、不飽和炭化水素、臭素原子及びヨウ素原子からなる群から選ばれる1種以上を持つ1価の基であり、RFは、炭素数が1~20の直鎖のペルフルオロアルキル基または該基の炭素-炭素原子間にエーテル性酸素原子が挿入された基であり、aは0~20の整数であり、bは1~200の整数であり、cは3~200の整数である。 - 前記式(A)で表わされる化合物が、下式(A1)で表わされる化合物である、請求項1に記載の架橋性フッ素ゴム組成物。
(X-)x1Y ・・・(A1)
ただし、x1は、3又は4の整数である。 - 前記式(A)で表わされる化合物の数平均分子量(Mn)が500~100,000である、請求項1~4のいずれか1項に記載の架橋性フッ素ゴム組成物。
- 前記式(A)で表わされる化合物の数平均分子量(Mn)に対する質量平均分子量(Mw)の割合(Mw/Mn)が1.0~2.0である、請求項1~5のいずれか1項に記載の架橋性フッ素ゴム組成物。
- 前記式(A)で表わされる化合物を、前記フッ素ゴム100質量部に対して1~50質量部含有する、請求項1~6のいずれか1項に記載の架橋性フッ素ゴム組成物。
- 前記フッ素ゴムが、テトラフルオロエチレン/プロピレン系共重合体、フッ化ビニリデン/テトラフルオロエチレン/ヘキサフルオロプロピレン系共重合体、及びテトラフルオロエチレン/パーフルオロアルキルビニルエーテル系共重合体からなる群から選ばれる1種以上である、請求項1~6のいずれか1項に記載の架橋性フッ素ゴム組成物。
- さらに、有機過酸化物を含有する、請求項1~8のいずれか1項に記載の架橋性フッ素ゴム組成物。
- 請求項1~9のいずれかに記載の架橋性フッ素ゴム組成物を架橋してなることを特徴とする架橋ゴム物品。
- 前記架橋ゴム物品がシール材である請求項10に記載の架橋ゴム物品。
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JP2011534337A JP5614551B2 (ja) | 2009-10-01 | 2010-09-30 | 架橋性フッ素ゴム組成物および架橋ゴム物品 |
RU2012117739/05A RU2539009C2 (ru) | 2009-10-01 | 2010-09-30 | Сшиваемая фторкаучуковая композиция и сшитое каучуковое изделие |
CN201080045043.1A CN102575079B (zh) | 2009-10-01 | 2010-09-30 | 交联性氟橡胶组合物及交联橡胶物品 |
EP10820691.3A EP2484722B1 (en) | 2009-10-01 | 2010-09-30 | Crosslinkable fluororubber composition and crosslinked rubber article |
KR1020127007991A KR101729353B1 (ko) | 2009-10-01 | 2010-09-30 | 가교성 불소 고무 조성물 및 가교 고무 물품 |
US13/427,355 US8426527B2 (en) | 2009-10-01 | 2012-03-22 | Crosslinkable fluororubber composition and crosslinked rubber article |
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US13/427,355 Continuation US8426527B2 (en) | 2009-10-01 | 2012-03-22 | Crosslinkable fluororubber composition and crosslinked rubber article |
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JP (1) | JP5614551B2 (ja) |
KR (1) | KR101729353B1 (ja) |
CN (1) | CN102575079B (ja) |
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WO2015146851A1 (ja) * | 2014-03-25 | 2015-10-01 | 旭硝子株式会社 | フッ素ゴム成形品 |
KR20160004743A (ko) | 2014-07-04 | 2016-01-13 | 박현우 | 조사가교 불소고무 컴파운드와 이를 이용한 절연전선 및 그 제조방법 |
WO2019009250A1 (ja) | 2017-07-05 | 2019-01-10 | Agc株式会社 | 含フッ素弾性共重合体組成物および架橋ゴム物品 |
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CN104641425A (zh) * | 2012-06-26 | 2015-05-20 | 纳幕尔杜邦公司 | 用于修复电信号承载缆线的组合物 |
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WO2019054293A1 (ja) * | 2017-09-14 | 2019-03-21 | 三菱電線工業株式会社 | 未架橋ゴム組成物並びにそれを用いて製造されるゴム製品及びその製造方法 |
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JP2021105179A (ja) * | 2018-03-29 | 2021-07-26 | 三菱電線工業株式会社 | 未架橋ゴム組成物並びにそれを用いて製造されるゴム製品及びその製造方法 |
JP2020070326A (ja) * | 2018-10-30 | 2020-05-07 | 三菱電線工業株式会社 | 未架橋フッ素ゴム組成物及びそれを用いて製造されるゴム製品 |
JP2019214743A (ja) * | 2019-09-19 | 2019-12-19 | 三菱電線工業株式会社 | ゴム製品及びその製造方法 |
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Also Published As
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KR20120078706A (ko) | 2012-07-10 |
TW201127886A (en) | 2011-08-16 |
EP2484722B1 (en) | 2013-12-11 |
TWI491648B (zh) | 2015-07-11 |
US8426527B2 (en) | 2013-04-23 |
JPWO2011040576A1 (ja) | 2013-02-28 |
JP5614551B2 (ja) | 2014-10-29 |
US20120202950A1 (en) | 2012-08-09 |
CN102575079A (zh) | 2012-07-11 |
RU2539009C2 (ru) | 2015-01-10 |
EP2484722A1 (en) | 2012-08-08 |
KR101729353B1 (ko) | 2017-04-21 |
EP2484722A4 (en) | 2013-04-24 |
CN102575079B (zh) | 2014-07-30 |
RU2012117739A (ru) | 2013-11-10 |
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