WO2002102892A1 - Composition elastomere ethylene/hexafluoropropylene - Google Patents

Composition elastomere ethylene/hexafluoropropylene Download PDF

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Publication number
WO2002102892A1
WO2002102892A1 PCT/JP2002/005577 JP0205577W WO02102892A1 WO 2002102892 A1 WO2002102892 A1 WO 2002102892A1 JP 0205577 W JP0205577 W JP 0205577W WO 02102892 A1 WO02102892 A1 WO 02102892A1
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WIPO (PCT)
Prior art keywords
vulcanization
ethylene
composition
composition according
hexafluoropropylene
Prior art date
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PCT/JP2002/005577
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English (en)
Japanese (ja)
Inventor
Hideya Saito
Masao Otsuka
Tatsuya Morikawa
Mitsuhiro Otani
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Daikin Industries, Ltd.
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Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to JP2003506359A priority Critical patent/JPWO2002102892A1/ja
Publication of WO2002102892A1 publication Critical patent/WO2002102892A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1009—Fluorinated polymers, e.g. PTFE
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C09K2200/062—Polyethylene

Definitions

  • the present invention relates to a method for vulcanization and processability when vulcanizing an E-HFP-based elastomer containing ethylene (E) and hexafluoropropylene (HFP) as essential constitutional units in a peroxide vulcanization system.
  • E E-HFP-based elastomer containing ethylene (E) and hexafluoropropylene (HFP) as essential constitutional units in a peroxide vulcanization system.
  • E E
  • HFP hexafluoropropylene
  • the vulcanizates obtained by peroxide vulcanization of this E-HFP elastomer composition are excellent in amine resistance, and are used in automotive oils, especially engine oils, transmission oils and differential oils. It is suitable as a material for oil seals.
  • Copolymers of ethylene (E) and hexafluoropropylene (HFP) exhibit elastomeric properties and, like other fluoroplastics and elastomers, have heat resistance, oil resistance, and chemical resistance (particularly, (Such as alkalinity).
  • E ethylene
  • HFP hexafluoropropylene
  • it is expected to be used as a material for oil seals for automobiles because of its excellent amine resistance and oil resistance.
  • properties that are electrically advantageous such as high electrical insulation, low dielectric loss tangent and dielectric constant, and low frequency dependence, and can be expected to be used in the field of electric and electronic components.
  • a so-called peroxide vulcanization method using an organic peroxide as a vulcanizing agent is most frequently used.
  • a vulcanization aid such as triaryl isocyanurate (TAIC) is commonly used for the purpose of improving vulcanizability.
  • TAIC triaryl isocyanurate
  • the vulcanization is usually carried out in the presence (for example, pamphlet of W094 / 24 175).
  • fillers such as carbon black, silica, and calcium metasilicate in practical compounding designs.
  • compounding formulations that use TA IC as a vulcanization aid do not necessarily exhibit sufficient vulcanizability, and such phenomena are caused by the use of fillers with small reinforcing properties, such as calcium metasilicate and barium sulfate.
  • the vulcanized product after press vulcanization has foaming marks and is not usable as a sealing material, because it is remarkably recognized in the prescribed formulation and the degree of vulcanization does not increase. Disclosure of the invention
  • the present invention provides a composition in which when vulcanizing an E-HFP-based elastomer with peroxide, the vulcanizability is remarkably improved, and no foaming phenomenon is observed even with a formulation containing a filler having a small reinforcing property.
  • the purpose is to do. That is, the present invention relates to an E-HFP-based elastomer composition comprising an E-HFP-based elastomer, a peroxide vulcanizing agent, and a vulcanization aid capable of generating a substituted or unsubstituted benzoyloxy radical.
  • R, R ⁇ R 2 and R 3 are the same or an alkyl group containing 1 to 4 carbon atoms, an alkoxyl group or a halogen atom; n and m are the same or different and each is 0-5 And p and Q are the same or different, each of which is an integer of 0 to 4), and at least one of substituted or unsubstituted dibenzoylquinonedioxime compounds, particularly p, p'dibenzoylquinonedioxane. Kissim is preferably used.
  • composition of the present invention may further contain other vulcanization aids such as triaryl isocyanurate.
  • composition of the present invention is particularly remarkable in a formulation containing a filler having a small reinforcing property such as at least one selected from the group consisting of calcium metasilicate, barium sulfate, magnesium gayate and aluminum silicate.
  • a filler having a small reinforcing property such as at least one selected from the group consisting of calcium metasilicate, barium sulfate, magnesium gayate and aluminum silicate.
  • the E-HFP-based elastomer a copolymer of ethylene and hexafluoropropylene or a copolymer of ethylene, hexafluoropropylene and another fluorinated olefin is preferable.
  • fluorine-containing olefins At least one selected from the group consisting of monomers of tetrafluoroethylene, vinylidene fluoride, trifluoroethylene, trifluoroethylene, pentafluoropropylene and perfluoro (alkylbierether).
  • One type is suitably mentioned.
  • the E-HFP-based elastomer used can be produced by various polymerization methods, but a radical polymerization method is generally used.
  • the monomer composition in the elastomer is such that the molar ratio of E / HFP is 90/10 to 50Z50, preferably 7030 to 5050.
  • These may be copolymerized with another copolymerizable fluorine-containing olefin so that the content thereof is 0 to 15 mol%, preferably 0 to 10 mol%.
  • fluorinated olefins that can be copolymerized with ethylene and HFP include tetrafluoroethylene (TFE), vinylidene fluoride (VdF), trifluoroethylene (CTFE), trifluoroethylene, and pentafluoroethylene.
  • TFE tetrafluoroethylene
  • VdF vinylidene fluoride
  • CTFE trifluoroethylene
  • PAVE fluoropropylene and perfluoro (alkyl vinyl ether) monomers
  • PAVE perfluoro
  • the resulting copolymer must exhibit elastomeric properties.
  • radical polymerization initiator an organic peroxide or a persulfate, or a redox initiator obtained by combining these with a reducing agent is preferable.
  • an emulsion polymerization method is preferable, and a low-temperature polymerization method in which a polymerization reaction is performed at a polymerization temperature of up to 40 is particularly preferable.
  • E-HFP-based elastomers obtained by this low-temperature polymerization method have few branches and are therefore excellent in processability.
  • the present invention relates to an elastomer composition containing such an E-HFP-based elastomer, a peroxide vulcanizing agent and a specific vulcanization aid.
  • an organic peroxide which easily generates a peroxide radical in the presence of heat or a redox agent is preferably used.
  • specific examples include, for example, 1,1-bis (t-butyl carboxy) -1,3,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, DG t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxide) hexane,, ⁇ -bis (t-butyl oxide) 1-)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexine-3, benzoylperoxide, t-butylperoxybenzene, t-but
  • dialkyl-based, peroxyster-based, and particularly t-butyl benzoic benzoate and dicumyl peroxide are preferable in that the foaming of the vulcanized product is easily prevented.
  • the amount of the vulcanizing agent may be appropriately determined in consideration of the amount of active -o-o-bonds in the organic peroxide, the decomposition temperature, and the like.
  • the peroxide vulcanization which is 0.5 to 10 parts, preferably 1.0 to 5 parts per vulcanization, vulcanization is remarkably accelerated by using a vulcanization aid.
  • a compound capable of generating a substituted or unsubstituted benzoyloxy radical is used as such a vulcanization aid.
  • a vulcanization aid the following formula (I), (II) or (II):
  • R, RR 2 and R 3 are the same or different, and are all alkyl groups, alkoxyl groups or halogen atoms having 1 to 4 carbon atoms; n and m are the same or different, and are all integers of 0 to 5) P and q are the same or Differently, each of which is an integer of 0 to 4), and at least one kind of a substituted or unsubstituted dibenzoylquinonedioxime compound.
  • p, p 'dibenzoylquinone dioxime, dibenzoyl_1,4_naphthyl quinone dioxime, etc. can be exemplified, and in particular, it is easy to obtain and the price is low. Jopenzilquinone dioxime is preferred.
  • the amount of the specific vulcanization aid used in the present invention is 0.2 to 10 parts, preferably 0.5 to 5 parts, per 100 parts of E-HFP-based elastomer. If the amount is too large, the coloring becomes large, and if the amount is too small, the effect of suppressing foaming cannot be expected.
  • vulcanization aid in addition to the specific vulcanization aid, other conventionally known vulcanization aids may be used. Specific examples include TAIC, triaryl cyanurate, triallyl formal, triaryl trimellitate, N, N'-m-phenylenebismaleimide, dipropargyl terephthalate, diaryl phthalate, tetraaryl terephthalate amide And triaryl phosphate, and in particular, triallyl isocyanurate is preferred because the vulcanizate has high heat resistance. The combined amount may be selected within a range that does not impair the effects of the present invention.
  • Peroxide vulcanization can be carried out in the same manner as before.
  • an E-HFP-based elastomer and a vulcanizing agent, a vulcanizing aid, and other additives that can be mixed as appropriate are kneaded in a roll, put into a mold, pressurized, and subjected to primary vulcanization (press vulcanization).
  • primary vulcanization press vulcanization
  • secondary vulcanization oven vulcanization
  • the primary vulcanization conditions are a temperature of 100 to 200, a time of 5 to 60 minutes, and a pressure of about 2 to 1 OMPa.
  • the secondary vulcanization conditions are a temperature of 150 It is adopted from the range of about 30 minutes to 30 hours.
  • composition of the present invention a filler, a processing aid, an antioxidant, and the like can be further added as necessary.
  • the filler examples include metal oxides such as magnesium oxide, calcium oxide, zinc oxide, lead oxide, titanium oxide, iron oxide, silver oxide, chromium oxide, bismuth oxide, silicon oxide, aluminum oxide, and copper oxide; and water.
  • Magnesium oxide Metal hydroxides such as shim, aluminum hydroxide and calcium hydroxide; carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate; metal sulfides such as molybdenum disulfide, iron sulfide and copper sulfide; sulfuric acid Sulfates such as rusium, aluminum sulphate and barium sulphate; silicates such as magnesium manganate, calcium metasilicate, sodium silicate and aluminum silicate; other talcite, lytbon (a mixture of zinc sulphide and barium sulphate) ), Diatomaceous earth, graphite, power pump rack, lamp black, MT carbon black, fluorinated carbon, calcium fluoride, coke, fluororesin powder
  • Chromium oxide, silicon oxide, and iron oxide powder which are inorganic powders having a Mohs hardness of 6 or more described in JP-A-8-27343 and JP-A-8-151565; Polytetrafluoroethylene powder impregnated with carbon described in Japanese Patent Application Laid-Open No. Hei 7-188500; a fluororesin filled with a filler described in Japanese Patent Application Laid-Open No. 56-151 739 as a main component Fibers made of a material which is made of carbon fiber; a fiber of a material mainly composed of carbon fiber and fluororesin; calcium metasilicate or graphite described in Japanese Patent Publication No. 5-64177 is preferable; Carbon black and silicon oxide are preferred from the standpoint of remarkable improvements in strength and compression set.
  • a formulation using a filler having a small reinforcing strength as a filler is given.
  • the foaming phenomenon can be suppressed by using the above-mentioned specific vulcanization aid.
  • a small reinforcing property means that the ability to increase the strength of the vulcanizate is low.
  • Fillers with small reinforcing properties include calcium metasilicate and barium sulfate And at least one selected from the group consisting of magnesium silicate and aluminum silicate.
  • the compounding amount of the filler can be appropriately selected depending on the kind and the purpose of the compounding, and is usually 0 to 100 parts, preferably 10 to 60 parts per 100 parts of the elastomer.
  • Higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; edil stearate, butyl stearate; Higher fatty acid esters such as ethyl oleate and butyl oleate; higher fatty acid amines such as stearic acid; polyols such as ethylene glycol, glycerin, and methyl alcohol; aliphatic hydrocarbons such as petrolatum and paraffin; Wax, silicone oil, low molecular weight polyethylene Emissions, such as low molecular weight polypropylene.
  • Antioxidants include 4,4-bis ( ⁇ , dimethylpentyl) diphenylamine, phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, ⁇ - ( ⁇ -toluenesulfonylamide) diphene Nilamine, ⁇ , ⁇ '—-2-naphthyl- ⁇ -phenylenediamine, N, N'-diphenyl ⁇ -phenylenediamine, ⁇ -phenyl- ⁇ '1 ⁇ ⁇ sopropyl _ ⁇ -phenylenediamine , ⁇ —phenyl N '— (1,3-dimethylbutyl) — ⁇ -phenylenediamine, ⁇ -phenyl N' one (3-methacryloyloxy-1-hydroxypropyl) ⁇ -phenylenediamine, Examples include 2,2,4-trimethyl-11,2-dihydroquinoline polymer
  • the composition of the present invention can be obtained by a continuous molding process such as extrusion, transfer, calender, roll coating, brush coating, impregnation, etc., in addition to ordinary mold molding. It can be formed into molded products such as sheets, pipes, rods, tubes, angles, channels, drawn cloths, and coated boards. It can be formed into a deformed product, a special molded product, for example, a sponge-like rubber, etc. by various other known molding methods. It is also possible to perform primary processing on a film- or tape-shaped molded product, and to further process this by secondary processing such as lamination, pasting, and winding. The composition formed in this manner is vulcanized by the vulcanizing means as described above.
  • composition is applied to the surface of the substrate by application, impregnation, spraying, etc. in a solution form and then vulcanized, or vulcanized and bonded in a film or sheet form by laminating and vulcanizing.
  • a vulcanized film can also be formed by bonding and laminating a vulcanized film or sheet on the surface of a substrate, and various vulcanized rubber products can be provided.
  • the vulcanizates thus obtained have excellent heat resistance, oil resistance, amine resistance, and chemical resistance, and are used in various parts in the automotive, aircraft, semiconductor, food, and chemical industries.
  • Other suitable molded articles are listed below.
  • the elastomer obtained by the present invention has high heat resistance and excellent resistance to mainly amine-based additives (specifically, succinimides and metal dialkyl dicarbamates) added to automotive oils.
  • amine-based additives specifically, succinimides and metal dialkyl dicarbamates
  • the volume change is small with respect to the oil itself, it is suitable as a molded product of various members for automobile oil, for example, automatic transmission fluid (ATF), engine oil, and differential gear oil.
  • ATF automatic transmission fluid
  • It is suitable as a material for an elastomer molded article that can come into contact with oil, such as a wire covering material.
  • Oil seal for manual transmission gasket, o_ring, packing, oil seal for automatic transmission, gasket, o-ring, packing, oil seal for continuously variable transmission (belt type or toroidal type), gasket, o— Ring, packing,
  • CVTF hose EGR tube
  • continuous transmission belt or toroidal
  • Rubber materials for food processing equipment for example, heat exchanger gaskets, diaphragms, various seals such as O-rings, pipes, hoses, sanitary packing, valve packing, joints between mouths such as filling bottles and fillers) Packing used for filling),
  • Products such as alcoholic beverages and soft drinks, packing equipment, food sterilizing equipment, brewing equipment, water heaters, packing for various automatic food vending machines, gaskets, tubes, diaphragms, hoses, joint sleeves
  • Electrical insulation materials for example, insulation spacers for various electrical equipment, insulation tape used for the joint end of cables, materials used for heat-shrinkable tubes, etc.
  • the molded body obtained above can be used for manufacturing equipment such as semiconductors, liquid crystal panels, plasma display panels, plasma addressed liquid crystal panels, field emission display panels, and solar cell substrates, such as CVD equipment, etching equipment, and oxidation equipment.
  • manufacturing equipment such as semiconductors, liquid crystal panels, plasma display panels, plasma addressed liquid crystal panels, field emission display panels, and solar cell substrates, such as CVD equipment, etching equipment, and oxidation equipment.
  • Non-adhesive oil-resistant roll for copier Non-adhesive oil-resistant roll for copier,
  • the obtained emulsified dispersion is pulverized with hydrochloric acid, washed with ion-exchanged water, dried at 120 ° C. until a constant weight is reached, and then subjected to elastomeric property. 23.1 kg of E—HFP—TFE copolymer was obtained. The average polymerization rate was 5.5 gZhrZl liter / water.
  • the copolymer composition of this E-HFP-TFE elastomer was analyzed by 1 H-NMR, GPC, and other analytical methods, and the copolymer weight of ethylene was 53.9 mol%, HFP4 was 1.0 mol%, and TFE was 5.1 mol%. It was united. The glass transition temperature was +2, and the Mooney viscosities were ML (1 +4, lO Ot :) 143 and ML (1 +10, lO Ot) 132.
  • E-HFP-TFE elastomer obtained in the production example, t-butyl peroxybenzoate (Perbutyl Z, Nihon Yushi Co., Ltd.) as a peroxide curing agent 3.7 parts, vulcanization aid P, p '— dibenzoylquinone dioxime (Barnock DGM, manufactured by Ouchi Shinko Chemical Co., Ltd.) 3.4 6 parts and calcium metasilicate (NYAD # 400, manufactured by NYCO) as a small reinforcing filler 40 Parts were mixed and kneaded at room temperature using an open mouth to prepare a composition of the present invention. This composition had good adhesion to rolls and was easy to knead.
  • t-butyl peroxybenzoate Perbutyl Z, Nihon Yushi Co., Ltd.
  • vulcanization aid P p '— dibenzoylquinone dioxime
  • Barnock DGM manufactured by Ouchi Shinko Chemical Co.,
  • the resulting composition is placed in a mold, subjected to primary vulcanization by press vulcanization (150 ° C x 15 minutes), and then to secondary vulcanization by oven vulcanization (180 ° C x 4 hours) to produce a vulcanized product. did. In addition, the vulcanization characteristics at 150 were examined. Table 1 shows the results. The physical properties of the vulcanizate obtained, the presence or absence of foaming, and the heat resistance were measured by the following methods. Table 1 shows the results.
  • the surface of the obtained primary vulcanizate is visually observed.
  • a composition was prepared in the same manner as in Example 1 except that 2.5 parts of TAIC was blended in place of p, '-dibenzoylquinonedioxime as a vulcanization aid.
  • the vulcanization characteristics were examined in the same manner as described above. Table 1 shows the results.
  • Example 1 Comparative Example 1 Composition (parts by weight)
  • the resulting composition was placed in a mold, primary vulcanized by press vulcanization (150 at XI for 5 minutes), and then secondary vulcanized by oven vulcanization (180 t: x 4 hours). To produce a vulcanizate. In addition, the vulcanization characteristics of 15 were examined. Table 2 shows the results.
  • the obtained vulcanized product was examined for physical properties in the normal state, presence or absence of foaming, and heat resistance in the same manner as in Example 1. Table 2 shows the results.
  • a composition was prepared in the same manner as in Example 2, except that 3.46 parts of p, ⁇ '-dibenzoylquinonedioxime was used as a vulcanization aid and 1.0 part of TAIC was used in combination.
  • the vulcanization characteristics of the product were examined in the same manner as in Example 1. Table 2 shows the results.
  • Example 2 shows the results.
  • a composition was prepared in the same manner as in Example 2 except that 2.5 parts of TAIC was used in place of ⁇ , ⁇ ′-dibenzoylquinonedioxime as a vulcanization aid.
  • the vulcanization characteristics were examined in the same manner as in 1. Table 2 shows the results.
  • Example 2 primary vulcanization and secondary vulcanization were carried out in the same manner as in Example 1 to produce a vulcanizate for comparison.
  • the vulcanizate was examined for physical properties in a normal state, presence or absence of foaming, and heat resistance. Table 2 shows the results. Table 2
  • the present invention it is possible to provide a composition in which the vulcanizability at the time of peroxide vulcanization of an E-HFP-based elastomer is remarkably improved.
  • a foaming phenomenon during vulcanization can be suppressed even with a formulation containing a filler having a small reinforcing property.

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Abstract

La présente invention concerne une composition élastomère éthylène/hexafluoropropylène qui comprend un élastomère éthylène/hexafluoropropylène, un agent de vulcanisation peroxyde et un composé d'aide à la vulcanisation capable de générer un radical benzoyloxy (in)saturé. Ce composé d'aide à la vulcanisation est, par exemple, un dioxime p,p'-benzoylquinone. Dans cette composition, l'élastomère éthylène/hexafluoropropylène présente une adaptation considérablement améliorée pour la vulcanisation avec le peroxyde. Même lorsque cette composition contient un liant de renfort modéré, on observe aucun phénomène de moussage dans cette dernière.
PCT/JP2002/005577 2001-06-15 2002-06-06 Composition elastomere ethylene/hexafluoropropylene WO2002102892A1 (fr)

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JP2003506359A JPWO2002102892A1 (ja) 2001-06-15 2002-06-06 エチレン−ヘキサフルオロプロピレン系エラストマー組成物

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JP2001-181982 2001-06-15
JP2001181982 2001-06-15

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JP2008195040A (ja) * 2007-02-15 2008-08-28 Tokai Rubber Ind Ltd 燃料系ゴムホース
JP2008195039A (ja) * 2007-02-15 2008-08-28 Tokai Rubber Ind Ltd 耐熱エアーホース
WO2012111751A1 (fr) * 2011-02-17 2012-08-23 Nok株式会社 Composition de caoutchouc fluoré et procédé de fabrication d'un caoutchouc fluoré réticulé
WO2015178309A1 (fr) * 2014-05-23 2015-11-26 ダイキン工業株式会社 Composition de caoutchouc fluoré, et article moulé en caoutchouc fluoré
EP4086307A1 (fr) * 2021-05-04 2022-11-09 KACO GmbH + Co. KG Mélange de caoutchouc fluoré, joint d'étanchéité à partir d'un tel mélange de caoutchouc fluoré, ainsi que bague d'étanchéité d'arbre pourvue de corps d'étanchéité

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008195040A (ja) * 2007-02-15 2008-08-28 Tokai Rubber Ind Ltd 燃料系ゴムホース
JP2008195039A (ja) * 2007-02-15 2008-08-28 Tokai Rubber Ind Ltd 耐熱エアーホース
WO2012111751A1 (fr) * 2011-02-17 2012-08-23 Nok株式会社 Composition de caoutchouc fluoré et procédé de fabrication d'un caoutchouc fluoré réticulé
CN103108913A (zh) * 2011-02-17 2013-05-15 Nok株式会社 氟橡胶组合物及氟橡胶交联体的制造方法
JP5288071B2 (ja) * 2011-02-17 2013-09-11 Ｎｏｋ株式会社 フッ素ゴム組成物及びフッ素ゴム架橋体の製造方法
KR101450005B1 (ko) 2011-02-17 2014-10-15 엔오케이 가부시키가이샤 불소고무 조성물 및 불소고무 가교체의 제조방법
CN103108913B (zh) * 2011-02-17 2014-12-24 Nok株式会社 氟橡胶组合物及氟橡胶交联体的制造方法
WO2015178309A1 (fr) * 2014-05-23 2015-11-26 ダイキン工業株式会社 Composition de caoutchouc fluoré, et article moulé en caoutchouc fluoré
JP2016000806A (ja) * 2014-05-23 2016-01-07 ダイキン工業株式会社 フッ素ゴム組成物及びフッ素ゴム成形品
EP4086307A1 (fr) * 2021-05-04 2022-11-09 KACO GmbH + Co. KG Mélange de caoutchouc fluoré, joint d'étanchéité à partir d'un tel mélange de caoutchouc fluoré, ainsi que bague d'étanchéité d'arbre pourvue de corps d'étanchéité

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