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WO2003039858A1 - Caoutchouc lamine - Google Patents

Caoutchouc lamine Download PDF

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Publication number
WO2003039858A1
WO2003039858A1 PCT/JP2002/011486 JP0211486W WO03039858A1 WO 2003039858 A1 WO2003039858 A1 WO 2003039858A1 JP 0211486 W JP0211486 W JP 0211486W WO 03039858 A1 WO03039858 A1 WO 03039858A1
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WO
WIPO (PCT)
Prior art keywords
rubber
fluororubber
oxide
rubber laminate
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2002/011486
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English (en)
Japanese (ja)
Inventor
Kazuhisa Matsumoto
Katsusada Tokuhira
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Priority to JP2003541727A priority Critical patent/JP4731116B2/ja
Publication of WO2003039858A1 publication Critical patent/WO2003039858A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material

Definitions

  • the present invention relates to a laminate of a fluororubber (I) and a non-fluororubber (II). In the bonding between the fluororubber (I) and the non-fluororubber (II), vulcanization is performed without using an intermediate or an adhesive.
  • the present invention relates to a rubber laminate which adheres more firmly and is difficult to peel at high temperatures, a method for producing the same, and uses thereof. Background art
  • Fluororubber has excellent heat resistance, oil resistance, chemical resistance, weather resistance, etc. and is useful in industrial materials and other fields.
  • fluororubber is expensive, and its economical efficiency cannot be neglected when it is used for general purposes in these fields, so its use is expected to increase dramatically while having excellent performance. It is the present situation that cannot be expected.
  • silicone rubber, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acrylic rubber, acrylate-ethylene copolymer, ester acrylate-ethylene monoacetate biel A method of forming a heat-resistant oil-resistant hose or the like by laminating a copolymer and a fluororubber has been studied (see Japanese Patent Application Laid-Open Nos.
  • interfacial peeling may occur at temperatures of 100 ° C or higher, which is the environment in which heat-resistant and oil-resistant hoses are used. Is required.
  • An object of the present invention is to provide a rubber laminate in which a fluororubber (I) layer and a non-fluororubber (II) layer are firmly adhered by vulcanization and are difficult to peel at 100 ° C or more.
  • the present invention relates to a fluororubber (I) layer comprising a fluororubber compound (A) containing a fluororubber (I) and a vulcanizing agent, and a rubber compound (B) comprising a non-fluororubber (II) and a vulcanizing agent.
  • silicone rubber is preferable.
  • This rubber laminate can achieve an adhesive strength of 10 YOT or more at 10 Ot.
  • Organic peroxides are preferred as the vulcanizing agent in the fluororubber compound (A), and organic peroxides are also preferred as the vulcanizing agent in the non-fluororubber compound (B).
  • the metal oxide is preferably at least one selected from the group consisting of magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, iron oxide, zinc oxide and lead oxide, and particularly preferably magnesium oxide.
  • the metal oxide may be surface-treated with a surface treatment agent such as a wetting agent, a dispersant, or a coupling agent, for example, to improve dispersibility and water resistance.
  • the lower limit of the particle diameter of the metal oxide is 0.1 m, preferably 0.5 m or more, more preferably 1.0 / m or more. If the particle size is less than 0.1 lm, mixing with the rubber becomes difficult, and the rubber becomes hard and the elasticity tends to be impaired.
  • the upper limit of the particle size is 500 m, preferably 50 m or less, more preferably 10 m or less. If the particle size exceeds 500 m, the specific surface area of the particles tends to be small, and the adhesive strength tends to be low.
  • the fluororubber (I) is preferably a fluororubber having iodine, bromine, z or a double bond as a crosslinking point, and having a crosslinking point content of 0.05 to 5 mol%.
  • Such a rubber laminate is formed by simultaneously extruding the fluororubber (I) and the non-fluororubber (II) with an extruder to form a rubber laminate composed of an inner layer and an outer layer, or A rubber laminate consisting of an inner layer and an outer layer is formed by extruding the other rubber as an outer layer on an inner layer made of either (I) or the above non-fluororubber (II) by an extruder. Then, the obtained rubber laminate can be vulcanized and adhered between the layers to produce the rubber laminate.
  • fluororubber (I) in the present invention examples include vinylidene fluoride (VdF) Z hexafluoropropylene (HFP) copolymer, Vd F / tetrafluoroethylene (TFE) ZHFP copolymer, VdF / TF EZ perfluoro (alkyl vinyl ether) (PAVE) copolymer, VdFZ such as V dFZ black mouth trifluoroethylene (CTFE) copolymer, etc .; Perfectic refining elastomer; TFE / propylene VdF copolymer, HFPZ Ethylene ZV dF copolymer, etc.
  • V d FZ non-perha stiff olefin-based elastomer TFEZP AVE copolymer, etc. perfluoroelastomer
  • TFEZ propylene copolymer HFP / ethylene copolymer, etc.
  • Non-perfluoroelastomer fluorosilicone rubber and the like.
  • the fluoro (alkyl vinyl ether) contains a plurality of ether bonds. May be used.
  • the molecular weight of the fluororubber (I) is preferably 20,000 to 300,000, and more preferably 50,000 to 200,000 in number average molecular weight.
  • VdF / HFP copolymer from the viewpoint of compatibility with the non-fluororubber (II) layer, VdF / HFP copolymer, VdFZTFE / HFP copolymer, VdFZTFEZPA VE copolymer, TFE / propylene / VdF copolymer, HFP Elastomers of ethylene / ethylene ZVdF copolymer, TFEZ propylene copolymer and HFPZ ethylene copolymer are preferred, and elastomers of VdFZHFP copolymer and VdF / TFE / HFP copolymer are particularly preferred.
  • crosslinkable group-containing unit a polyfunctional monomer having a plurality of vinyl groups and a aryl group, or an iodine or bromine-containing monomer may be copolymerized.
  • heat treatment or the like may be used to promote hydrofluoric acid to generate a double bond serving as a crosslinking point in the molecule.
  • iodine, bromine and those containing Z or a double bond are preferred, and among them, highly reactive iodine-containing fluororubber is more preferred.
  • the crosslinking point content in the fluororubber (I) is preferably 0.05 to 5 mol%, more preferably 0.15 to 3 mol%, and particularly preferably 0.25 to 2 mol%. is there. If the number of cross-linking points is less than this, sealing properties and adhesive strength will be insufficient, and if it is more than this, rubber properties such as elongation and flexibility will be reduced, and rubber properties will be lost.
  • the vulcanization system of the fluorororubber (I) is not particularly limited, but a rubber mixed with an organic peroxide as a cross-linking agent is more preferable in order to sufficiently perform vulcanization adhesion with the non-fluororubber (II).
  • the non-fluorororubber (II) in the present invention is, for example, polybutadiene, Len-butadiene copolymer, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, natural rubber, polyisoprene, propylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-propylene-gene Terpolymer, polychloroprene, chloroprene polymer, poly-1-butadiene, polybutadiene butadiene copolymer, chlorinated butyl rubber, chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated or In addition to brominated butyl rubber, acrylic rubber, silicone rubber, copolymers of epichlorohydrin with other unsaturated epoxides, acrylates and vinyl compounds, olefin compounds, benzene compounds, 0 !,] With 3-
  • acrylonitrile-butadiene copolymer acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acryl rubber, silicone rubber, and acrylic acid ester and vinyl compound, olefin compound, Copolymers with compounds, ⁇ -ethylenically unsaturated carboxylic acids, and the like are preferred, and silicone rubber, which has the best heat resistance, is more preferred.
  • Silicone rubbers include those which cure by condensation reaction, addition reaction, or organic peroxide.
  • the vulcanization system of the non-fluorinated rubber (II) is not particularly limited, but a rubber mixed with an organic peroxide as a crosslinking agent is more preferable in order to sufficiently perform the vulcanization adhesion with the fluororubber (I).
  • preferred vulcanizing agents to be mixed with the fluororubber (I) for example, organic peroxides, polyamine compounds, polyhydroxy compounds, and polythiol compounds are listed below, but are not limited thereto.
  • organic peroxide used for peroxide vulcanization generally, one that easily generates a peroxy radical in the presence of heat or an oxidation-reduction system is often used.
  • dialkyl compounds preferred are dialkyl compounds.
  • the amount used is usually 0.1 to 15 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the fluororubber (I).
  • a vulcanization aid or a co-vulcanizing agent may be used in combination.
  • the vulcanizing aid or co-vulcanizing agent is effective in principle as long as it has a reaction activity for the hydroxy radical and the polymer radical, and the type is not particularly limited.
  • Preferred examples include triaryl cyanurate, triallyl isocyanurate, triacryl formal, triallyl trimellitate, dipropargyl terephthalate, diallyl phthalate, tetraaryl terephthalamide, triallyl phosphate, and bismaleimide.
  • a vulcanizing aid or co-vulcanizing agent it is not always necessary to use a vulcanizing aid or co-vulcanizing agent, but if used, it is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 100 to 100 parts by weight of the fluororubber (1). 0.3 to 5 parts by weight.
  • the polyamine compound used for polyamine vulcanization is a primary amine or a secondary amine that binds two or more basic nitrogen atoms in the molecule. In the case of the above, these are used in the form of a salt with reduced reactivity.
  • alkylenediamines such as ethylenediaminecarbamate, hexamethylenediaminecarbamate and 4,4-diaminecyclohexylmethanecarbamate; N, N, 1-dicinnamylidene-1,6-hexamethylenediamine; And Schiff's salt.
  • an aromatic polyamine compound having poor basicity can be used as a vulcanizing agent when used in combination with another basic compound.
  • Other basic compounds include, for example, diphenyl danzidine, di-O-triguanidine, diphenyl thiourea, 2-mercaptoimidazoline ⁇ ⁇ , a vulcanization accelerator for synthetic rubber, and one NH 3 and Z in the molecule.
  • a compound having —NH—, a divalent metal hydroxide, or the like is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the fluororubber (I).
  • Polyhydroxy compounds used for polyol vulcanization include phenolic hydroxyl groups,
  • a polyhydroxy compound having C-OH a dihydroxy compound represented by the formula: R f (CH 2 OH) 2 (where R f is a polyfluoroalkylene group or a perchlorofluoroalkylene group having 1 to 20 carbon atoms)
  • R f is a polyfluoroalkylene group or a perchlorofluoroalkylene group having 1 to 20 carbon atoms
  • alkali metal salts thereof, mixtures thereof, and the like are preferably used.
  • Specific examples include, for example, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) perfluoropropane, 2,2-bis (4-hydroxyphenyl) butane , 1,1-bis (4-hydroxyphenyl) methane, 4,4'-dihydroxyphenyl ether, H ⁇ CH 2 (CF 2 ) 3 CH 2 OH, HOCH 2 CF 2 C FH (CF 2 ) 3 CFHCF 2 CH 2 OH, H ⁇ CH 2 CH 2 CH 2 (CF 2 ) 3 CH 2 CH 2 CH 2 ⁇ H, HOCH 2 CF 2 CH 2 (CF 2 ) 3 CH 2 CF 2 CH 2 OH or an alkali metal salt thereof.
  • Polythiol compounds include, for example, dimercaptodimethyl ether, dimercaptomethyl sulfide, 1,6-hexanedithiol, ethylenebismercaptoacetate, 1,5-naphthalenedithiol, 4,4, dimercaptodiphenyl Nyl, 2-anilino-4,6-dithiol-S-triazine, 2-dibutylamino-4,6-dithiol-S-triazine, or their metal salts.
  • vulcanization aids and vulcanization accelerators tertiary amines, tri-substituted amidines, pen-substituted guanidines or salts of these compounds with organic or inorganic acids, quaternary ammonium salts, quaternary phosphonium salts or Nitrogen-containing cyclic polyethers can be used as needed.
  • vulcanization aids or vulcanization accelerators are described in JP-A-51-56854, JP-A-47-1387, JP-A-47-191, and JP-A-53-132858. You can use what is.
  • vulcanizing agents and vulcanizing aids mixed with the non-fluororubber (II) those generally used, including those used for the above fluororubber (I), can be used. .
  • the metal oxide mixed with at least one of the fluororubber (I) and the non-fluororubber (II) is magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, iron oxide, or oxide having relatively high surface activity. At least one selected from the group consisting of zinc and lead oxide is preferred, and magnesium oxide is preferred because of its higher surface activity.
  • the metal oxide may be surface-treated with a surface treatment agent such as a wetting agent, a dispersant, or a coupling agent, for example, to improve dispersibility and water resistance.
  • the lower limit of the particle diameter of the metal oxide is 0.1 m, preferably 0.5 m or more, more preferably 1.0 or more. If the particle size is less than 0.1 lm, mixing with rubber becomes difficult, and the rubber becomes hard and elasticity tends to be impaired.
  • the upper limit of the particle diameter is 500 m, preferably 50 m or less, more preferably 10 m or less. If the particle size exceeds 500 m, the specific surface area of the particles tends to be small, and the adhesive strength tends to be low.
  • the mixing amount of the metal oxide is preferably 4 to 100 parts by weight, more preferably 5 to 50 parts by weight, and more preferably 8 to 50 parts by weight, based on 100 parts by weight of the fluororubber (I) or the non-fluororubber (II). 40 parts by weight are particularly preferred. If the mixing amount is too small, the adhesive strength between the fluororubber (I) and the non-fluororubber (II) cannot be sufficiently obtained, and if it is too large, the molded article becomes too hard and loses flexibility.
  • the metal oxide may be mixed with only one of the fluororubber (I) and the non-fluororubber (II), or may be mixed with both. In particular, it is desirable to mix both in terms of further increasing the adhesive strength.
  • the mixing amount of the metal oxide in each rubber compound is 4 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the rubber, respectively. It is more preferably 8 to 40 parts by weight.
  • silicon oxide and its analogs which are sometimes classified as metal oxides, have a small effect of improving the vulcanization adhesive strength, and are not included in the metal oxides in the present invention. However, as will be described later, it is not excluded that the metal oxide is blended as a filler in addition to the metal oxide.
  • a filler may be added to the fluororubber (I) or the non-fluororubber (II).
  • Fillers include metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide; carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate; magnesium silicate Silicates such as calcium sulfate, calcium silicate, sodium silicate, and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate, and barium sulfate; metal sulfides such as synthetic talcite, molybdenum disulfide, iron sulfide, and copper sulfide; Diatomaceous earth, asbestos, lithobon (zinc sulfide / barium sulfide), dara fight, carbon black, carbon fluoride, calcium fluoride, coke, talc, mica powder, wollastonite, carbon fiber, aramide fiber, various kinds of whiskers
  • metal hydroxides
  • 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 amide and oleic acid amide; ethyl oleate Higher fatty acid esters such as stearyl amine and oleyl amine; petroleum waxes such as carnauba wax and ceresin wax; polyglycols such as ethylene glycol, glycerin and ethylene glycol; aliphatics such as petrolatum and paraffin.
  • 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 amide and oleic acid amide
  • ethyl oleate Higher fatty acid esters such as stearyl
  • Hydrocarbons silicone oils, silicone polymers, low molecular weight polyethylene, phthalates, phosphates, rosin, phenyl, dialkylamine (logenated), dialkylsulfonated (halogenated), Such as surface active agents, and the like.
  • plasticizers include fluoric acid derivatives and sebacic acid derivatives.
  • softening agents include lubricating oils, process oils, coal tar, castor oil, and calcium stearate.
  • antiaging agents include phenylenediamine. , Phosphonates, quinolines, cresols, phenols, dithiol metal salts, etc., as well as acid acceptors, coloring agents, ultraviolet absorbers, flame retardants, oil resistance improvers, Foaming agent, scorch inhibitor, sticky Additives, lubricants and the like can be arbitrarily added.
  • Molded articles are produced by heating and compressing in a mold, pressing the composition into a heated mold, extruding with an extruder and steam heating, using a fluoro rubber (I) and a non-fluoro rubber (II).
  • a fluoro rubber (I) and a non-fluoro rubber (II) After fractionation with a calender or the like, a known method such as a method of laminating as an inner layer and an outer layer, winding around a mandrel, fixing with a cloth or the like from the outside, and heating with steam or the like to crosslink. Further, secondary vulcanization by heat treatment of the molded article may be performed to improve the properties.
  • the rubber laminate of the present invention can be manufactured by the following method.
  • a rubber consisting of an inner layer and an outer layer is simultaneously extruded by an extruder, and the fluororubber (I) and the non-fluororubber (II) kneaded by a mixer such as a cooling roll, a Banbury mixer, an intermixer, etc.
  • a mixer such as a cooling roll, a Banbury mixer, an intermixer, etc.
  • an extruder extrudes the other rubber as an outer layer to form a rubber laminate comprising an inner layer, and if necessary, a fiber reinforcement layer and an outer layer.
  • the case where the above-mentioned fiber reinforcing layer is applied is suitable for use in a turbo air hose.
  • a fiber reinforcing layer may be provided on the inner layer or the outer layer of the rubber laminate of the present invention, if necessary, or another rubber layer may be formed.
  • the fluorororubber (I) layer and the non-fluororubber (II) layer may be either an inner layer or an outer layer of the rubber laminate depending on the application, and may have any layer structure.
  • a highly heat-resistant rubber layer is placed on the inner layer.
  • a rubber layer with high heat resistance is placed on the inner and outer layers, and a rubber layer with low heat resistance is placed in between, The reverse is also possible.
  • oil resistance In this case, a rubber layer having high oil resistance is naturally disposed on the side where oil resistance is required.
  • the rubber laminate of the present invention has an adhesive strength at 10 ° C (strength at the time of interfacial peeling or cohesive failure) of 0.7 NZmm or more, and further has high adhesive strength even at a high temperature of 1.5 N / mm or more. Can be provided. Even at a high temperature of 140, it is possible to provide a rubber laminate having an adhesive strength of 0.4 NZmm or more, more preferably 1.0 NZmm or more at 180 ° C, and an adhesive strength of 0.3 NZmm or more and even 0.8 N / mm or more. Of course, the upper limit of adhesive strength is cohesive failure.
  • the non-fluorororubber (II) is made of silicone rubber and the vulcanization system is not used.
  • the peroxide vulcanization system it is surprisingly possible to obtain a relatively large rubber laminate having an interlayer adhesion strength of, for example, 0.4 NZmm or more at 10 O: and 0.6 N / mm or more. I also found out.
  • a rubber laminate in which a silicone rubber layer made of a silicone rubber compound mixed with an agent is directly bonded by peroxide vulcanization is also useful when used at a relatively low temperature.
  • composition and materials of the fluororubber compound (A) are the same as those described above, and the silicone rubber compound (B1) has the same composition and materials as those of the non-fluororubber compound except that silicone rubber is used as the non-fluorine rubber. Is the same.
  • the same conditions and treatments as described above are also applied to the method for producing the rubber laminate, except that the vulcanization system is a peroxide vulcanization system.
  • Rubber laminate (1) Rubber laminate (1)
  • Vulcanizing agent Peroxide vulcanizing agent
  • Metal oxides magnesium oxide, zinc oxide, iron oxide, calcium oxide, titanium oxide, aluminum oxide
  • Non-fluororubber (II) layer
  • Non-fluorine rubber Silicone rubber
  • Vulcanizing agent peroxide vulcanizing agent
  • Vulcanizing agent Peroxide vulcanizing agent
  • Metal oxides magnesium oxide, zinc oxide, iron oxide, calcium oxide, titanium oxide, aluminum oxide
  • Non-fluororubber (II) layer
  • Non-fluorine rubber Silicone rubber
  • Vulcanizing agent Peroxide vulcanizing agent
  • Metal oxides magnesium oxide, zinc oxide, iron oxide, calcium oxide, titanium oxide, aluminum oxide
  • Vulcanizing agent Peroxide vulcanizing agent
  • Non-fluororubber ( ⁇ ) layer
  • Non-fluorine rubber Silicone rubber
  • Vulcanizing agent Peroxide vulcanizing agent
  • Vulcanizing agent peroxide vulcanizing agent
  • Non-fluorinated rubber (II) layer
  • Non-fluorine rubber Silicone rubber
  • Vulcanizing agent Peroxide vulcanizing agent
  • Metal oxide magnesium oxide
  • the rubber laminate of the present invention can sufficiently withstand use under severe conditions, and has various uses.
  • an engine body of an automobile engine a main motion system, and a valve train.
  • System lubrication / cooling system, fuel system, intake / exhaust system, etc., drive system transmission system, etc., chassis steering system, brake system, etc. basic electrical components of control components, control system components, equipment components, etc.
  • Gaskets such as cylinder-head gaskets, cylinder-head force bar gaskets, roll-pan packings, general gaskets, etc., seals such as seal rings, packing, timing belt covers, gaskets, etc., hoses such as control hoses, etc. Anti-vibration rubber for engine mounts, etc. Shaft seals such as crankshaft seals and camshaft seals.
  • Fuel hoses such as fuel pump oil seals, diaphragms, valves, etc., filler (neck) hoses, fuel supply hoses, fuel return hoses, vapor (X Vapo) hoses, fuel tank in-tank hoses, filler seals, tanks Packing, In-tank fuel pump mount, etc.
  • CAC complex air control equipment
  • Manifold intake manifold packing, exhaust manifold packing, etc. EGR (exhaust circulation) diaphragm, control hose, emission control hose, etc., BPT diaphragm, etc., AB valve afterburn prevention valve seat, etc. , Throttle throttle packing, Turbo oil hose (supply), Tapo oil hose (return), Turbo air hose, Interlock hose, Yubinshaft seal etc.
  • Transmission-related bearing seals oil seals, O-rings, packings, torque converter hoses, etc. AT transmission oil hoses, ATF hoses, 0-rings, packings, etc.
  • Coating materials for various sensors Car air conditioner ring, packing, cooler hose, etc.
  • vehicles other than automobiles for example, oil, chemical, heat, steam, or weather-resistant packing, air-rings, hoses, other sealing materials, diaphragms, valves, etc.
  • the fluorororubber (I) shown in Table 1 and the non-fluororubber (II) (silicone rubber) shown in Table 2 were compounded according to the formulations in Tables 1 and 2, respectively, and kneaded at 40 ° C. Each unvulcanized rubber sheet (1.2 mm thick) was prepared. These sheets were brought into contact with each other in the combination shown in Table 3, press-vulcanized at 170 for 10 minutes, cut into a width of 25 mm, and cut according to JISK 6256-1993. A mold release test was performed. Table 3 shows the results.
  • FKM1 VdF / TFE / HFP (50/20/30 mol%) copolymer fluororubber containing about 0.20 mol% of iodine manufactured by Daikin Industries, Ltd. Mooney viscosity is 50 (ML 1 + 10, 100 ° C)
  • FKM2 VdF / TFE / HFP (50Z20 / 30 mol%) copolymer fluororubber containing about 0.36 mol% of iodine manufactured by Daikin Industries, Ltd.
  • the viscosity is 61 (ML 1 + 10, 100 ° C)
  • FKM3 VdF / TFE / HFP (50/20/30 mol%) copolymer fluororubber containing about 0.53 mol% of iodine manufactured by Daikin Industries, Ltd. Mooney viscosity is 76 (ML 1 + 10, 100 ° C)
  • FKM4 Iodine-free VdFZHFP (78Z22 mol%) copolymer fluororubber manufactured by Daikin Industries, Ltd. Contains polyol vulcanizing agent and vulcanization aid. The viscosity is 50 (ML 1 + 10, 100 ° C)
  • Silicone rubber Silicone rubber compound manufactured by Shin-Etsu Chemical Co., Ltd.
  • Vulcanizing agent 1 Perhexa 25B (trade name: Poxyxide (2,5-dimethyl-2,5-di (t-butylperoxy) hexane) manufactured by NOF CORPORATION)
  • Vulcanizing agent 2 Shin-Etsu Chemical Industry Co., Ltd. C-3 (trade name: contains about 20% of dicumyl peroxide)
  • TAI C Triaryl isocyanurate manufactured by Nippon Kasei Co., Ltd.
  • Magnesium oxide Kyowa Mag 150 manufactured by Kyowa Chemical Industry Co., Ltd. (trade name)
  • Zinc oxide Zinc flower special name (trade name) manufactured by Sakai Chemical Industry Co., Ltd.
  • Iron Oxide Tenpaku-in red handle (trade name) manufactured by Nippon Benzo Kogyo Co., Ltd.
  • Lead oxide Lisage (trade name) manufactured by Lead Chemical Company
  • Oxydani calcium CML # 35 (trade name) manufactured by Omi Chemical Industry Co., Ltd.
  • Aluminum oxide alumina AL-45-1 (trade name) manufactured by Showa Denko Co., Ltd.
  • Titanium oxide manufactured by Sakai Chemical Industry Co., Ltd. Of R—650 (product name)
  • MT carbon Ribonbon Black ThermaxN-990 (trade name) manufactured by Cancarb Co., Ltd.
  • Calcium hydrochloride Caldic 2000 (trade name) manufactured by Omi Chemical Industry Co., Ltd.
  • Colorant KE- manufactured by Shin-Etsu Chemical Co., Ltd. Co 1 or BR (Product name: 50% iron oxide)
  • Formulation f 100 1.5 10 ⁇ ⁇ ⁇ ⁇ 4 10 ⁇ Formulation g 100 1.5 8 4 10
  • the fluororubber (I) layer and the non-fluororubber (II) layer adhere firmly by vulcanization, and the rubber laminated body which is difficult to peel at high temperature is obtained. Further, according to the present invention, it is possible to maintain a heat resistance, an oil resistance, a chemical resistance, and a weather resistance, which are characteristics of the fluororubber, and to use the fluororubber as a heat and oil resistant rubber hose.
  • a laminate of the (I) layer and the non-fluororubber ( ⁇ ) layer can be obtained.

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  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un caoutchouc laminé que l'on forme en soumettant à une liaison par vulcanisation directe : une couche de fluorocaoutchouc (1) comprenant un composé de fluorocaoutchouc (A) contenant un fluorocaoutchouc (1) et un agent de vulcanisation ; et une couche de caoutchouc sans fluor (2) comprenant un composé de caoutchouc (B) contenant un caoutchouc sans fluor (1) et un agent de vulcanisation, l'un des composés (A) et (B) au moins contenant de 4 à 100 parties en poids d'un oxyde métallique pour 100 parties en poids de caoutchouc.
PCT/JP2002/011486 2001-11-05 2002-11-05 Caoutchouc lamine Ceased WO2003039858A1 (fr)

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JP2003541727A JP4731116B2 (ja) 2001-11-05 2002-11-05 ゴム積層体

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JP2001-339216 2001-11-05
JP2001339216 2001-11-05

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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JP2007284604A (ja) * 2006-04-19 2007-11-01 Nok Corp フッ素ゴム組成物
WO2007148759A1 (fr) * 2006-06-23 2007-12-27 Daikin Industries, Ltd. Composition de caoutchouc fluoré en vue d'une réticulation par un peroxyde et procédé de fabrication d'un stratifié de caoutchouc
JP2008189788A (ja) * 2007-02-05 2008-08-21 Asahi Kasei Chemicals Corp 磁性粉含有フッ素ゴム組成物
WO2008139967A1 (fr) * 2007-05-07 2008-11-20 Daikin Industries, Ltd. Stratifié composé de caoutchouc fluoré et de caoutchouc non fluoré, et procédé pour fabriquer le susdit
JP2010116542A (ja) * 2008-10-17 2010-05-27 Shin-Etsu Chemical Co Ltd フルオロシリコーンゴム組成物およびその硬化物
KR100972530B1 (ko) * 2008-10-17 2010-07-28 평화오일씰공업주식회사 자동 차고 유지장치용 고무 조성물
EP2639055A4 (fr) * 2011-03-11 2014-09-03 Tokai Rubber Ind Ltd Tuyau résistant à la chaleur monté sur un véhicule
WO2017115812A1 (fr) * 2015-12-28 2017-07-06 旭硝子株式会社 Composition de fluoroélastomère et procédé de production d'un produit réticulé
WO2017150612A1 (fr) 2016-03-04 2017-09-08 三井化学株式会社 Stratifié et son application
WO2018151104A1 (fr) 2017-02-20 2018-08-23 三井化学株式会社 Stratifié
WO2018151103A1 (fr) 2017-02-20 2018-08-23 三井化学株式会社 Stratifié
WO2018180140A1 (fr) 2017-03-30 2018-10-04 三井化学株式会社 Stratifié
JPWO2017122700A1 (ja) * 2016-01-14 2018-11-22 Ａｇｃ株式会社 水性分散液、その製造方法、水性塗料および塗装物品
WO2019098062A1 (fr) 2017-11-17 2019-05-23 ダイキン工業株式会社 Élément pour système de gestion d'air, et composition de caoutchouc fluoré
WO2019176767A1 (fr) 2018-03-14 2019-09-19 三井化学株式会社 Stratifié, et application de celui-ci

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JP2007284604A (ja) * 2006-04-19 2007-11-01 Nok Corp フッ素ゴム組成物
WO2007119834A1 (fr) * 2006-04-19 2007-10-25 Asahi Glass Company, Limited Composition de fluoro-élastomère et article de fluoro-caoutchouc moulé
JP5239857B2 (ja) * 2006-06-23 2013-07-17 ダイキン工業株式会社 パーオキサイド架橋用フッ素ゴム組成物およびゴム積層体の製造方法
WO2007148759A1 (fr) * 2006-06-23 2007-12-27 Daikin Industries, Ltd. Composition de caoutchouc fluoré en vue d'une réticulation par un peroxyde et procédé de fabrication d'un stratifié de caoutchouc
JP2008189788A (ja) * 2007-02-05 2008-08-21 Asahi Kasei Chemicals Corp 磁性粉含有フッ素ゴム組成物
JP5304645B2 (ja) * 2007-05-07 2013-10-02 ダイキン工業株式会社 フッ素ゴム層および非フッ素ゴム層からなる積層体およびその製造方法
JPWO2008139967A1 (ja) * 2007-05-07 2010-08-05 ダイキン工業株式会社 フッ素ゴム層および非フッ素ゴム層からなる積層体およびその製造方法
WO2008139967A1 (fr) * 2007-05-07 2008-11-20 Daikin Industries, Ltd. Stratifié composé de caoutchouc fluoré et de caoutchouc non fluoré, et procédé pour fabriquer le susdit
KR100972530B1 (ko) * 2008-10-17 2010-07-28 평화오일씰공업주식회사 자동 차고 유지장치용 고무 조성물
JP2010116542A (ja) * 2008-10-17 2010-05-27 Shin-Etsu Chemical Co Ltd フルオロシリコーンゴム組成物およびその硬化物
EP2639055A4 (fr) * 2011-03-11 2014-09-03 Tokai Rubber Ind Ltd Tuyau résistant à la chaleur monté sur un véhicule
JPWO2017115812A1 (ja) * 2015-12-28 2018-10-18 Ａｇｃ株式会社 フルオロエラストマー組成物および架橋物の製造方法
WO2017115812A1 (fr) * 2015-12-28 2017-07-06 旭硝子株式会社 Composition de fluoroélastomère et procédé de production d'un produit réticulé
JPWO2017122700A1 (ja) * 2016-01-14 2018-11-22 Ａｇｃ株式会社 水性分散液、その製造方法、水性塗料および塗装物品
KR20180113205A (ko) 2016-03-04 2018-10-15 미쓰이 가가쿠 가부시키가이샤 적층체 및 그의 용도
WO2017150612A1 (fr) 2016-03-04 2017-09-08 三井化学株式会社 Stratifié et son application
WO2018151103A1 (fr) 2017-02-20 2018-08-23 三井化学株式会社 Stratifié
WO2018151104A1 (fr) 2017-02-20 2018-08-23 三井化学株式会社 Stratifié
KR20190104613A (ko) 2017-02-20 2019-09-10 미쓰이 가가쿠 가부시키가이샤 적층체
KR20190110573A (ko) 2017-02-20 2019-09-30 미쓰이 가가쿠 가부시키가이샤 적층체
US11964447B2 (en) 2017-02-20 2024-04-23 Mitsui Chemicals, Inc. Laminate
WO2018180140A1 (fr) 2017-03-30 2018-10-04 三井化学株式会社 Stratifié
KR20190119084A (ko) 2017-03-30 2019-10-21 미쓰이 가가쿠 가부시키가이샤 적층체
WO2019098062A1 (fr) 2017-11-17 2019-05-23 ダイキン工業株式会社 Élément pour système de gestion d'air, et composition de caoutchouc fluoré
WO2019176767A1 (fr) 2018-03-14 2019-09-19 三井化学株式会社 Stratifié, et application de celui-ci
KR20200123192A (ko) 2018-03-14 2020-10-28 미쓰이 가가쿠 가부시키가이샤 적층체 및 그의 용도

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