JP4731116B2 - Rubber laminate - Google Patents

Description

  The present invention relates to a laminate of fluororubber (I) and non-fluororubber (II), and vulcanization without using an intermediate or an adhesive in the adhesion between fluororubber (I) and non-fluororubber (II). The present invention relates to a rubber laminate that is more firmly adhered to and difficult to peel off even at high temperatures, a method for producing the same, and a use thereof.

  Fluoro rubber is excellent in heat resistance, oil resistance, chemical resistance, weather resistance and the like, and is useful in industrial materials and other fields. However, fluororubber is expensive, and economic efficiency cannot be ignored when used in general in these fields, so it cannot be expected that the amount used will increase dramatically while having excellent performance. is the current situation.

  Other than fluoro rubber, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acrylic rubber, acrylic ester-ethylene copolymer, acrylic ester-ethylene-vinyl acetate copolymer, and silicone rubber are heat resistant. It is relatively excellent in properties and is often used as a material for heat and oil resistant hoses such as oil hoses and air hoses.

  However, in recent years, the temperature in the engine room has been increased more and more for the purpose of improving performance and fuel efficiency in automobiles, and materials having improved heat resistance are required for conventional heat and oil resistant hoses. As a result, conventionally used acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acrylic rubber, acrylate ester-ethylene copolymer, acrylate ester-ethylene-vinyl acetate copolymer Then, heat resistance is becoming insufficient. Silicone rubber has heat resistance that is second only to that of fluororubber, but there are problems with oil swelling and oil permeation, and silicone rubber alone cannot be used. Thus, in order to satisfy the conflicting requirements of high performance and low price at the same time, it can be said that it has become difficult to cope with one kind of rubber material.

  Therefore, silicone rubber, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acrylic rubber, acrylate ester-ethylene copolymer, acrylate ester-ethylene-vinyl acetate copolymer are used to solve such problems. A method of laminating a polymer and fluororubber and thereby forming a heat and oil resistant hose has been studied (Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6). , Patent Document 7, Patent Document 8 and Patent Document 9, etc.), due to poor affinity between fluororubbers and other rubbers or different vulcanization methods. There is a problem that it is easy to do.

  In addition, even if a relatively high adhesive strength is obtained in a room temperature environment, interface peeling may occur at a temperature of 100 ° C. or higher, which is the use environment of heat and oil resistant hoses, and improvement from the viewpoint of durability is required. .

Japanese Patent Laid-Open No. 61-169243 JP-A 61-189934 JP-A-62-282929 JP 62-51439 A Japanese Unexamined Patent Publication No. 63-317339 Japanese Unexamined Patent Publication No. 1-152060 JP-A-1-159245 Japanese Patent No. 2526134 Japanese Patent Laid-Open No. 3-221442

  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 bonded by vulcanization and difficult to peel at 100 ° C. or higher.

  The present invention relates to a fluororubber (I) layer comprising a fluororubber compound (A) containing fluororubber (I) and a vulcanizing agent, and a rubber compound (B) containing non-fluororubber (II) and a vulcanizing agent. A rubber laminate in which a non-fluororubber (II) layer made of is directly vulcanized and bonded, wherein at least one of the blends (A) and (B) contains 4 metal oxides per 100 parts by weight of rubber. It relates to a rubber laminate in which -100 parts by weight are mixed.

  As the non-fluororubber (II), silicone rubber is preferable.

  Moreover, it is preferable that 4-100 weight part of metal oxides are mixed with 100 weight part of rubber | gum with both said compound (A) and (B).

  This rubber laminate can achieve an adhesive strength at 100 ° C. of 0.7 N / mm or more.

  An organic peroxide is preferable as the vulcanizing agent in the fluororubber compound (A), and an organic peroxide is also preferable as a 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 dispersing agent, or a coupling agent in order to improve dispersibility and water resistance, for example. As said metal oxide, the minimum of the particle diameter is 0.1 micrometer, 0.5 micrometer or more is preferable and 1.0 micrometer or more is more preferable. When the particle diameter is less than 0.1 μm, mixing with rubber becomes difficult, or the rubber becomes hard and elasticity tends to be impaired. The upper limit of the particle diameter is 500 μm, preferably 50 μm or less, and more preferably 10 μm or less. When the particle diameter exceeds 500 μm, the specific surface area of the particles tends to be small and the adhesive force tends to be low.

  Further, the fluororubber (I) is preferably a fluororubber having iodine, bromine and / or a double bond as a cross-linking point and having a cross-linking 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 comprising an inner layer and an outer layer, or the fluororubber ( On the inner layer composed of either one of I) and the non-fluorinated rubber (II), a rubber laminate composed of an inner layer and an outer layer is formed by extruding the other rubber as an outer layer using an extruder, Subsequently, the rubber laminate obtained can be produced by vulcanizing and bonding the layers.

  In addition, this manufacturing method can provide a heat-resistant / oil-resistant rubber hose that adheres firmly between layers and is difficult to peel even at 100 ° C or higher.

  According to the present invention, a fluororubber (I) layer and a non-fluororubber (II) layer are firmly bonded by vulcanization, and a rubber laminate that is difficult to peel off even at high temperatures is obtained. Further, according to the present invention, the fluororubber (I) layer and non-fluororubber (which are suitable as a heat- and oil-resistant rubber hose that retains the heat resistance, oil resistance, chemical resistance and weather resistance characteristic of the fluororubber ( II) A laminate with the layer can be obtained.

  Hereinafter, the present invention will be further described in detail.

  Examples of the fluororubber (I) in the present invention include vinylidene fluoride (VdF) / hexafluoropropylene (HFP) copolymer, VdF / tetrafluoroethylene (TFE) / HFP copolymer, VdF / TFE / perfluoro ( Alkyl vinyl ether) (PAVE) copolymer, VdF / perhaloolefin elastomer such as VdF / chlorotrifluoroethylene (CTFE) copolymer; TFE / propylene / VdF copolymer, HFP / ethylene / VdF copolymer, etc. Examples thereof include VdF / non-perhaloolefin elastomers; perfluoroelastomers such as TFE / PAVE copolymers; non-perfluoroelastomers such as TFE / propylene copolymers and HFP / ethylene copolymers; fluorosilicone rubbers and the like.

  The fluoro (alkyl vinyl ether) may contain a plurality of ether bonds. Further, the molecular weight of the fluororubber (I) is 20,000 to 300,000, preferably 50,000 to 200,000 in terms of number average molecular weight.

  Among these, VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / TFE / PAVE copolymer, TFE / propylene / VdF copolymer are used from the viewpoint of compatibility with the non-fluororubber (II) layer. Polymers, HFP / ethylene / VdF copolymers, TFE / propylene copolymers, HFP / ethylene copolymer elastomers are preferred, VdF / HFP copolymers, and VdF / TFE / HFP copolymer elastomers are particularly preferred. .

  Moreover, it is good also as a blend rubber with 2 or more types of blend rubbers of fluororubber (I), and 1 type, or 2 or more types of non-fluororubber (II).

  Of course, as the crosslinkable group-containing unit, a polyfunctional monomer having a plurality of vinyl groups or allyl groups, or an iodine or bromine-containing monomer may be copolymerized. Further, by performing heat treatment or the like, dehydrofluorination may be promoted to generate a double bond serving as a crosslinking point in the molecule. In particular, those containing iodine, bromine and / or double bonds are preferred, and among them, highly reactive iodine-containing fluororubber is more preferred.

  The content of crosslinking points 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%. If the crosslinking point is less than this, the sealing property and the adhesive strength are insufficient, and if it is more than this, rubber elasticity is lost such as elongation and flexibility are lowered.

  The vulcanization system of the fluororubber (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-fluororubber (II) in the present invention is, for example, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, natural rubber, polyisoprene, propylene-butadiene copolymer. Polymer, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, polychloroprene, chloroprene polymer, poly 1-chlorobutadiene, 1-chlorobutadiene-butadiene copolymer, chlorinated butyl rubber, chlorosulfonated Polyethylene, chlorinated polyethylene, chlorinated or brominated butyl rubber, acrylic rubber, silicone rubber, as well as copolymers of epichlorohydrin and other unsaturated epoxides, acrylates and vinyl compounds, olefin compounds, dieneization Things, alpha, and copolymers of such β- ethylenically unsaturated carboxylic acid.

  Among these, in terms of excellent heat resistance, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acrylic rubber, silicone rubber, acrylic acid ester and vinyl compound, olefin compound, diene compound, A copolymer with α, β-ethylenically unsaturated carboxylic acid or the like is preferable, and a silicone rubber having the best heat resistance is more preferable. Silicone rubbers include those that 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 in which an organic peroxide is mixed as a crosslinking agent is more preferable in order to sufficiently perform vulcanization adhesion with the fluororubber (I).

  In the present invention, preferred vulcanizing agents mixed with the fluororubber (I), for example, organic peroxides, polyamine compounds, polyhydroxy compounds, and polythiol compounds are listed below, but are not limited thereto.

  As the organic peroxide used for peroxide vulcanization, one that easily generates a peroxy radical in the presence of heat or a redox system is generally suitable. For example, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α ' -Bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexyne-3, benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl Peroxy maleic acid, and the like can be exemplified t- butylperoxy isopropyl carbonate. Of these, preferred are dialkyl compounds. In general, the type and amount used are selected from the amount of active —O═O—, decomposition temperature and the like. 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).

  Moreover, when using an organic peroxide, you may use a vulcanization adjuvant and a co-vulcanizing agent together. The vulcanization aid or co-vulcanizing agent is effective in principle as long as it has a reaction activity with respect to peroxy radicals and polymer radicals, and the type is not particularly limited. Preferable examples include triallyl cyanurate, triallyl isocyanurate, triacryl formal, triallyl trimellitate, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, bismaleimide and the like. The vulcanizing aid or co-vulcanizing agent is not necessarily used, but when used, 0.1 to 10 parts by weight is preferred, more preferably 0.3 to 100 parts by weight of the fluororubber (I). It is a ratio of ˜5 parts by weight.

The polyamine compound used for polyamine vulcanization is a primary amine or a secondary amine in which two or more basic nitrogen atoms are bonded in the molecule, and in many cases, these are converted into a salt form to suppress the reactivity. use. Specific examples include alkylene diamines such as ethylene diamine carbamate, hexamethylene diamine carbamate, and 4,4-diamine cyclohexyl methane carbamate; Schiff salts such as N, N′-dicinnamylidene-1,6-hexamethylene diamine, and the like. . In addition, an aromatic polyamine compound having poor basicity can be used as a vulcanizing agent when used in combination with other basic compounds. Other basic compounds include, for example, diphenylguanidine, di-O-triguanidine, diphenylthiourea, 2-mercaptoimidazoline, a vulcanization accelerator for synthetic rubber, and —NH ₃ and / or —NH in the molecule. A compound having-, a divalent metal hydroxide, and the like. The amount used is usually preferably 0.5 to 5 parts by weight per 100 parts by weight of fluororubber (I).

を有するポリヒドロキシ化合物、式：Ｒｆ（ＣＨ₂ＯＨ）₂（式中、Ｒｆは炭素数１〜２０のポリフルオロアルキレン基またはパークロロフルオロアルキレン基）で示されるジヒドロキシ化合物またはこれらのアルカリ金属塩、これらの混合物などが好適にあげられる。 Polyhydroxy compounds used for polyol vulcanization include phenolic hydroxyl groups,

A dihydroxy compound represented by the formula: Rf (CH ₂ OH) ₂ (wherein Rf is a polyfluoroalkylene group or perchlorofluoroalkylene group having 1 to 20 carbon atoms) or an alkali metal salt thereof, A mixture thereof is preferred.

Specific examples include 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, HOCH ₂ (CF ₂ ) ₃ CH ₂ OH, HOCH ₂ CF ₂ CFH (CF ₂ ) ₃ CFHCF ₂ CH ₂ OH, HOCH ₂ CH ₂ CH ₂ (CF ₂ ) ₃ CH ₂ CH ₂ CH ₂ OH, HOCH ₂ CF ₂ CH ₂ (CF ₂ ) ₃ CH ₂ CF ₂ CH ₂ OH, or an alkali metal salt thereof.

  Examples of the polythiol compound include dimercaptodimethylether, dimercaptomethylsulfide, 1,6-hexanedithiol, ethylenebismercaptoacetate, 1,5-naphthalenedithiol, 4,4′-dimercaptodiphenyl, 2-anilino-4,6. -Dithiol-S-triazine, 2-dibutylamino-4,6-dithiol-S-triazine, or alkali metal salts thereof.

  In addition, as vulcanization aids and vulcanization accelerators, tertiary amines, tri-substituted amidines, penta-substituted guanidines or organic or inorganic acid salts, quaternary ammonium salts, quaternary phosphonium salts or nitrogen-containing compounds of these compounds. Cyclic polyethers can be used as needed. These 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 you have.

  In the present invention, as the vulcanizing agent and the vulcanization aid mixed with the non-fluororubber (II), those commonly used, including those used for the fluororubber (I), can be used.

  In the present invention, 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, 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 from the viewpoint of higher surface activity. The metal oxide may be surface-treated with a surface treatment agent such as a wetting agent, a dispersing agent, or a coupling agent in order to improve dispersibility and water resistance, for example. When mixing metal oxides, especially these specific metal oxides, the effect of improving the vulcanized adhesive strength between the fluororubber (I) layer and the non-fluororubber (II) layer can be obtained. As said metal oxide, the minimum of the particle diameter is 0.1 micrometer, 0.5 micrometer or more is preferable and 1.0 micrometer or more is more preferable. When the particle diameter is less than 0.1 μm, mixing with rubber becomes difficult, or the rubber becomes hard and elasticity tends to be impaired. The upper limit of the particle diameter is 500 μm, preferably 50 μm or less, and more preferably 10 μm or less. When the particle diameter exceeds 500 μm, the specific surface area of the particles tends to be small and the adhesive force tends to be low.

  The amount of the metal oxide mixed is preferably 4 to 100 parts by weight, more preferably 5 to 50 parts by weight, and particularly preferably 8 to 40 parts by weight with respect to 100 parts by weight of the fluororubber (I) or non-fluororubber (II). If the mixing amount is small, sufficient adhesive strength between the fluororubber (I) and the non-fluororubber (II) cannot be obtained, and if it is too large, the molded product becomes too hard and the flexibility is lost.

  The metal oxide may be mixed with only one of fluororubber (I) or non-fluororubber (II), or may be mixed with both. In particular, it is desirable to mix both of them because the adhesive strength is further increased. When the metal oxide is mixed in both, the amount of the metal oxide in each rubber compound is 4 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 8 to 100 parts by weight with respect to 100 parts by weight of the rubber. 40 parts by weight.

  Note that silicon oxide and the like, which are sometimes classified as metal oxides, have a small effect of improving the vulcanized adhesive strength, and are not included in the metal oxide in the present invention. However, as will be described later, mixing as a filler in addition to the metal oxide is not excluded.

  In this invention, you may mix | blend a filler with fluororubber (I) and non-fluororubber (II). Fillers include metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide; carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate, barium carbonate; magnesium silicate, calcium silicate, sodium silicate, aluminum silicate, etc. Silicates of aluminum; sulfates such as aluminum sulfate, calcium sulfate, barium sulfate; metal sulfides such as synthetic hydrotalcite, molybdenum disulfide, iron sulfide, copper sulfide; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), In addition to inorganic fillers such as graphite, carbon black, carbon fluoride, calcium fluoride, coke, talc, mica powder, wollastonite, carbon fiber, aramid fiber, various whiskers, organic reinforcing agents, organic fillers, etc. It is done. Further, as described above, silicon oxides such as wet silica, dry silica, quartz fine powder, and glass fiber can also be used.

  Processing aids include 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; ethyl oleate Higher fatty acid esters such as stearylamine and oleylamine; petroleum waxes such as carnauba wax and ceresin wax; polyglycols such as ethylene glycol, glycerin and diethylene glycol; aliphatic hydrocarbons such as petroleum jelly and paraffin; silicone Oils, silicone polymers, low molecular weight polyethylene, phthalates, phosphates, rosin, (halogenated) dialkylamine, (halogenated) dialkylsulfone, surfactants, etc. It is below.

  Examples of plasticizers include phthalic acid derivatives and sebacic acid derivatives, softening agents such as lubricating oil, process oil, coal tar, castor oil, calcium stearate, and antiaging agents such as phenylenediamines and phosphates. Quinolines, cresols, phenols, dithiocarbamate metal salts, etc., as well as acid acceptors, colorants, UV absorbers, flame retardants, oil resistance improvers, foaming agents, scorch prevention agents, tackifiers, A lubricant or the like can be arbitrarily added.

  For the production of molded products, a method of heat-compressing with a mold, a method of press-fitting the composition into a heated mold, a method of extruding steam with an extruder, a fluoro rubber (I) and a non-fluoro rubber (II) After separating with a calender or the like, it can be carried out by 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 and crosslinking with steam. Moreover, you may perform the secondary vulcanization by heat-processing a molded article for a characteristic improvement.

  Moreover, the rubber laminated body of this invention can be manufactured by the method illustrated next.

That is, a rubber laminate comprising an inner layer and an outer layer by simultaneously extruding the fluororubber (I) and non-fluororubber (II) kneaded by a mixer such as a cooling roll, a Banbury mixer, an intermixer, etc. Forming a body, and then vulcanizing the resulting rubber laminate to bond the layers together;
Alternatively, after applying a fiber reinforcing layer as necessary on the inner layer composed of either one of the fluororubber (I) and the non-fluororubber (II), the other rubber is extruded as an outer layer by an extruder. There is a method of forming a rubber laminate comprising a layer, and if necessary, a fiber reinforced layer and an outer layer, and then vulcanizing the obtained rubber laminate to bond the layers (I) and (II). When the fiber reinforcing layer is applied, it is suitable for a turbo air hose application.

  Of course, a fiber reinforcing layer may be applied to the inner layer and the outer layer of the rubber laminate of the present invention as necessary, or another rubber layer may be formed.

  The fluororubber (I) layer and the non-fluororubber (II) layer may be any layer structure such as an inner layer or an outer layer of a rubber laminate depending on the application. For example, when a high-temperature fluid flows on the inner surface of the hose, the rubber layer with high heat resistance is set as the inner layer, and when a high-temperature object or high-temperature fluid contacts or is close to the outer surface of the hose, the rubber layer with high heat resistance is set as the outer layer . Of course, a rubber layer having high heat resistance can be arranged in the inner layer and the outer layer, and a rubber layer having low heat resistance can be arranged in the middle, and vice versa. The same applies to the 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 a bond strength at 100 ° C. (strength at interfacial peeling or cohesive failure) of 0.7 N / mm or more, and even a high adhesive strength even at a high temperature of 1.5 N / mm or more. Can be provided. Furthermore, a rubber laminate having an adhesive strength of 0.4 N / mm or higher even at a high temperature of 140 ° C., or 1.0 N / mm or higher, and an adhesive strength of 0.3 N / mm or higher or 180 N / mm or higher at 180 ° C. is provided. it can. Of course, the upper limit of the adhesive strength is cohesive failure.

  Further, even when the metal oxide is not blended in either the fluororubber (I) layer or the non-fluororubber (II) layer, the non-fluororubber (II) is a silicone rubber and the vulcanization system is a peroxide. It was also surprisingly found that when a vulcanization system is used, a rubber laminate having a relatively large interlayer adhesion strength of, for example, 0.4 N / mm or more at 100 ° C., or even 0.6 N / mm or more can be obtained. .

  That is, (A) a fluororubber (I) layer comprising a fluororubber compound in which an organic peroxide vulcanizing agent is mixed with fluororubber (I), and (B1) an organic peroxide vulcanizing agent on silicone rubber A rubber laminate in which a silicone rubber layer made of a silicone rubber compound mixed with is directly bonded by peroxide vulcanization is also useful when used at a relatively low temperature.

  The composition and materials of the fluororubber compound (A) are the same as those described above, and the silicone rubber compound (B1) is the same as the composition and materials in the non-fluororubber compound except that silicone rubber is used as the non-fluorine rubber. It is. In addition, the same conditions and treatments as described above are employed for the method of manufacturing the rubber laminate, except that the vulcanization system is a peroxide vulcanization system.

  Examples of particularly preferred embodiments of the rubber laminate of the present invention include, but are not limited to, the following.

Rubber laminate (1)
Fluoro rubber (I) layer:
Fluoro rubber (I): VdF-based fluoro rubber (iodine content 0.05 mol% or more)
Vulcanizing agent: Peroxide-based vulcanizing agent Metal oxide: Magnesium oxide, zinc oxide, iron oxide, calcium oxide, titanium oxide, aluminum oxide non-fluorine rubber (II) layer:
Non-fluorinated rubber: Silicone rubber Vulcanizing agent: Peroxide-based vulcanizing agent Metal oxide: Arbitrary

Rubber laminate (2)
Fluoro rubber (I) layer:
Fluoro rubber (I): VdF-based fluoro rubber (iodine content 0.15 mol% or more)
Vulcanizing agent: Peroxide-based vulcanizing agent Metal oxide: Magnesium oxide, zinc oxide, iron oxide, calcium oxide, titanium oxide, aluminum oxide non-fluorine rubber (II) layer:
Non-fluorinated rubber: Silicone rubber Vulcanizing agent: Peroxide-based vulcanizing agent Metal oxide: Magnesium oxide, zinc oxide, iron oxide, calcium oxide, titanium oxide, aluminum oxide

Rubber laminate (3)
Fluoro rubber (I) layer:
Fluoro rubber (I): VdF-based fluoro rubber (iodine content 0.25 mol% or more)
Vulcanizing agent: Peroxide-based vulcanizing agent Metal oxide: Magnesium oxide non-fluorine rubber (II) layer:
Non-fluorinated rubber: Silicone rubber Vulcanizing agent: Peroxide-based vulcanizing agent Metal oxide: Magnesium oxide

Rubber laminate (4)
Fluoro rubber (I) layer:
Fluoro rubber (I): VdF-based fluoro rubber (iodine content of 0.40 mol% or more)
Vulcanizing agent: Peroxide-based vulcanizing agent Metal oxide: Magnesium oxide non-fluorine rubber (II) layer:
Non-fluorinated rubber: Silicone rubber Vulcanizing agent: Peroxide-based vulcanizing agent Metal oxide: Magnesium oxide

  The rubber laminate of the present invention can sufficiently withstand use under severe conditions and has various uses, for example, an engine body of an automobile engine, a main motion system, a valve system, a lubrication / cooling system, Heat resistance, oil resistance, and resistance such as fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, etc. Seals and bellows such as gaskets that require fuel oil resistance, LLC resistance, and steam resistance, and non-contact type and contact type packings (self-seal packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.) It has suitable characteristics as a diaphragm, a hose, a tube, and an electric wire.

Specifically, it can be used for the applications listed below.
Engine body:
Gaskets such as cylinder head gasket, cylinder head cover gasket, oil pan packing, general gasket, seals such as O-ring, packing, timing belt cover gasket, hoses such as control hose, vibration-proof rubber for engine mount, etc.
Main motor system:
Shaft seals such as crankshaft seals and camshaft seals.
Valve system:
Valve stem oil seal for engine valves.
Lubrication / cooling system:
Engine oil cooler hose, oil return hose, seal gasket, water hose around the radiator, vacuum pump oil hose for vacuum pump, etc.
Fuel system:
Fuel pump oil seal, diaphragm, valve, etc. Filler (neck) hose, fuel supply hose, fuel return hose, fuel hose such as vapor (evaporation) hose, fuel tank in-tank hose, filler seal, tank packing, in-tank Fuel pump mount, fuel tube body and connector O-ring, etc. Fuel injector injector cushion ring, injector seal ring, injector O-ring, pressure regulator diaphragm, check valves, carburetor needle valve petals, acceleration Pump seats, diaphragm gaskets, control hoses, etc. Valve seats, diaphragms, etc. for complex air control devices (CAC).
Intake and exhaust system:
Manifold intake manifold packing, exhaust manifold packing, EGR (exhaust circulation) diaphragm, control hose, emission control hose, BPT diaphragm, AB valve afterburn prevention valve seat, throttle valve body packing, turbo Charger turbo oil hose (supply), turbo oil hose (return), turbo air hose, intercooler hose, turbine shaft seal, etc.
Transmission system:
Transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses, AT mission oil hoses, ATF hoses, O-rings, packings, etc.
Steering system:
Power steering oil hose etc.
Brake system:
Oil seals, O-rings, packings, brake oil hoses, etc. Master back atmospheric valves, vacuum valves, diaphragms, etc. Master cylinder piston cups (rubber cups), caliper seals, boots, etc.
Basic electrical components:
Tubes for harness exterior parts such as electric wire (harness) insulators and sheaths.
Control system electrical components:
Coating materials for various sensor wires.
Equipment equipped:
Car air conditioner O-ring, packing, cooler hose, etc.

  In addition to automobiles, for example, oil, chemical, heat, steam, or weather resistant packings, O-rings, hoses, other sealing materials, diaphragms, valves, chemical plants, etc. Similar packings, O-rings, sealing materials, diaphragms, valves, hoses, rolls, tubes, chemical coatings, linings, and similar packings, O-rings in food plant equipment and food equipment (including household products) , Hose, sealing material, belt, diaphragm, valve, roll, tube, similar packing in nuclear power plant equipment, O-ring, hose, sealing material, diaphragm, valve, tube, similar packing in general industrial parts, O -Rings, hoses, sealing materials, diaphragms Is suitable valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, the application to a roll blade PPC copying machine.

  EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1
Fluororubber (I) shown in Table 1 and non-fluorinated rubber (II) (silicone rubber) shown in Table 2 are respectively blended according to the formulations in Tables 1 and 2, kneaded on a 40 ° C. roll, and each unvulcanized. A rubber sheet (1.2 mm thick) was produced. These sheets were brought into contact with each other in the combinations shown in Table 3, press vulcanized at 170 ° C. for 10 minutes, cut to a width of 25 mm, and subjected to a T-type peel test in accordance with JIS K6256-1993. The results are shown in Table 3.

  Each abbreviation and each component in Table 1 and Table 2 are respectively shown below.

Fluororubber (I) -related FKM1: A 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 (ML1 + 10, 100 ° C)
FKM2: VdF / TFE / HFP (50/20/30 mol%) copolymer fluororubber containing about 0.36 mol% of iodine manufactured by Daikin Industries, Ltd. Mooney viscosity is 61 (ML1 + 10, 100 ° C)
FKM3: VdF / TFE / HFP (50/20/30 mol%) copolymer fluororubber containing about 0.53 mol% iodine manufactured by Daikin Industries, Ltd. Mooney viscosity is 76 (ML1 + 10, 100 ° C)
FKM4: VdF / HFP (78/22 mol%) copolymer fluororubber containing no iodine, manufactured by Daikin Industries, Ltd. Contains polyol vulcanizing agent and vulcanization aid. Mooney viscosity is 50 (ML1 + 10, 100 ° C)

Silicone rubber related Silicone rubber: Silicone rubber compound (trade name: KE551-U) manufactured by Shin-Etsu Chemical Co., Ltd.

Vulcanizing agent Vulcanizing agent 1: Perhexa 25B (trade name: peroxide (2,5-dimethyl-2,5-di (t-butylperoxy) hexane) manufactured by Nippon Oil & Fats Co., Ltd.)
Vulcanizing agent 2: C-3 manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: containing about 20% dicumyl peroxide)

Vulcanizing aid TAIC: triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.

Metal oxide related Magnesium oxide: Kyowa Mug 150 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.
Zinc oxide: Special name for zinc oxide (trade name) manufactured by Sakai Chemical Industry Co., Ltd.
Iron oxide: Tensho-in valve handle (trade name) manufactured by Nippon Valve Industry Co., Ltd.
Lead oxide: Resurge (product name) manufactured by Lead City Chemical Industry Co., Ltd.
Calcium oxide: CML # 35 (trade name) manufactured by Omi Chemical Industry Co., Ltd.
Aluminum oxide: Alumina AL-45-1 (trade name) manufactured by Showa Denko KK
Titanium oxide: R-650 (trade name) manufactured by Sakai Chemical Industry Co., Ltd.

Other (fillers, etc.)
MT Carbon: Carbon black ThermaxN-990 (trade name) manufactured by Cancarb
Calcium hydroxide: Caldic 2000 (trade name) manufactured by Omi Chemical Industry Co., Ltd.
Colorant: KE-ColorBR manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: containing 50% iron oxide)

Claims (10)

Fluororubber (I) layer comprising a fluororubber compound (A) containing a fluororubber (I) and a vulcanizing agent, and a non-fluorine comprising a rubber compound (B) containing a non-fluororubber (II) and a vulcanizing agent A rubber laminate in which a rubber (II) layer is directly vulcanized and bonded, wherein 4 to 100 parts by weight of metal oxide is added to 100 parts by weight of rubber in at least one of the blends (A) and (B) A rubber laminate in which the non-fluorinated rubber (II) is a silicone rubber, which is a mixed rubber laminate . Both of the above formulations (A) and (B), the rubber laminate according to claim 1 Symbol mounting metal oxide is mixed 4-100 parts by weight per 100 parts by weight of rubber. The rubber laminate according to claim 1 or 2, wherein the adhesive strength at 100 ° C is 0.7 N / mm or more. The rubber laminate according to any one of claims 1 to 3, wherein the vulcanizing agent in the fluororubber compound (A) is an organic peroxide. The rubber laminate according to any one of claims 1 to 4, wherein the vulcanizing agent in the non-fluororubber compound (B) is an organic peroxide. The rubber according to any one of claims 1 to 5 , wherein the metal oxide is at least one selected from the group consisting of magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, iron oxide, zinc oxide, and lead oxide. Laminated body. The rubber laminate according to any one of claims 1 to 6 , wherein the metal oxide is magnesium oxide. The said fluororubber (I) is a fluororubber which makes iodine, bromine, and / or a double bond a crosslinking point, The crosslinking point content is 0.05-5 mol% in any one of Claims 1-7 The rubber laminate as described. The fluororubber (I) and the non-fluororubber (II) are simultaneously extruded by an extruder to form a rubber laminate composed of an inner layer and an outer layer, or the fluororubber (I) and the non-fluorine A rubber laminate composed of an inner layer and an outer layer is formed by extruding the other rubber as an outer layer with an extruder on the inner layer made of either rubber (II), and then the obtained rubber laminate The method for producing a rubber laminate according to any one of claims 1 to 8, wherein the body is vulcanized and the layers are bonded together. A heat and oil resistant rubber hose comprising a rubber laminate obtained by the production method according to claim 9 .