WO2003039858A1

WO2003039858A1 - Rubber laminate

Info

Publication number: WO2003039858A1
Application number: PCT/JP2002/011486
Authority: WO
Inventors: Kazuhisa Matsumoto; Katsusada Tokuhira
Original assignee: Daikin Industries, Ltd.
Priority date: 2001-11-05
Filing date: 2002-11-05
Publication date: 2003-05-15
Also published as: JP4731116B2; JPWO2003039858A1

Abstract

A rubber laminate which is formed by subjecting a fluororubber (I) layer comprising a fluororubber compound (A) containing a fluororubber (I) and a vulcanizing agent and a fluorine-free rubber layer (II) comprising a rubber compound (B) containing a fluorine-free rubber (I) and a vulcanizing agent to direct vulcanization bonding, wherein at least one of the compounds (A) and (B) contains 4 to 100 parts by weight of a metal oxide relative to 100 parts by weight of rubber.

Description

Akira Itoda Rubber laminate Technical field

TECHNICAL FIELD 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. However, 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.

Other than fluororubber, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acrylic rubber, acrylate-ethylene-ethylene copolymer, acrylate-ethylene-vinyl acetate copolymer, and silicone rubber are heat-resistant. It is 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 increasingly increased for the purpose of improving performance and fuel efficiency in automobiles, and materials for heat-resistant and oil-resistant hoses with higher heat resistance have been demanded. As a result, conventional acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acrylic rubber, acrylate The heat resistance of the tereethylene copolymer and the acrylate-ethylene-vinyl acetate copolymer has become insufficient. In addition, although silicone rubber has the second highest heat resistance than fluoro rubber, oil swelling and oil permeation are problematic, and silicone rubber alone cannot be used. It can be said that it has become difficult to use a single type of rubber material to simultaneously satisfy the conflicting demands of high performance and low price.

In order to solve such problems, 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. 61-169243, and JP-A-89-9334, JP-A-62-28-29-28, JP-A-62-514-39, JP-A-63-31 1739 JP, JP-A-1-1520620, JP-A-1-15992, JP-A No. 252613, JP-A-3-2-21445 No. 2, etc.), due to poor affinity between fluoro rubber and other rubbers and different vulcanization methods, etc. There is a problem that the adhesive strength is low and it is easy to peel off.

In addition, even if a relatively high adhesive strength is obtained in a room temperature environment, 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. . Disclosure of the invention

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. A rubber laminate in which a non-fluorinated rubber (II) layer made of rubber is directly vulcanized and bonded, and at least one of the compounds (A) and (B) contains 4 parts by weight of metal oxide per 100 parts by weight of rubber. To 100 parts by weight of a rubber laminate.

As the non-fluorine rubber (Π), silicone rubber is preferable.

In addition, it is preferable that 4 to 100 parts by weight of a metal oxide is mixed with 100 parts by weight of the rubber in both of the compounds (A) and (B).

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.

Further, by this manufacturing method, it is possible to provide a heat-resistant and oil-resistant rubber hose in which the layers are firmly adhered to each other and difficult to peel off even at 100 ° C or more. BEST MODE FOR CARRYING OUT THE INVENTION

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

Examples of the fluororubber (I) in the present invention 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. Further, 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.

Among these, 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.

It is also possible to use a blend rubber of two or more fluororubbers (I) or a blend rubber of one or more non-fluororubbers (II).

Of course, as the 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. In addition, 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. In particular, 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 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, 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-ethylenically unsaturated carboxylic acid Copolymer, and the like.

Among them, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, acryl rubber, silicone rubber, and acrylic acid ester and vinyl compound, olefin compound, Copolymers with compounds, β-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).

In the present invention, 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. . As the 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. For example, 1,1,1-bis (t-butylperoxy) 1,3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, G-t-butylperoxide, t— Butylcumylperoxide, dicumylperoxide, 0!,-Bis (t-butylperoxy) -1-p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5 —Dimethyl-2,5-di (t-butylperoxy) hexine— 3, benzoylperoxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, Examples thereof include t-butyl peroxymaleic acid, t-butyl peroxy isopropyl acid, and the like. Among them, preferred are dialkyl compounds. Generally, the type and amount used are selected from the amount of activity 0 = 0- and the decomposition temperature. 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).

When an organic peroxide is used, 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. Can be 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. Specific examples include alkylenediamines such as ethylenediaminecarbamate, hexamethylenediaminecarbamate and 4,4-diaminecyclohexylmethanecarbamate; N, N, 1-dicinnamylidene-1,6-hexamethylenediamine; And Schiff's salt. In addition, 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 ゴム, a vulcanization accelerator for synthetic rubber, and one NH ₃ and Z in the molecule. Or a compound having —NH—, a divalent metal hydroxide, or the like. Usually, the amount 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,

I

= 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) Alternatively, 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〇CH ₂ (CF ₂ ) ₃ CH ₂ OH, HOCH ₂ CF ₂ C FH (CF ₂ ) ₃ CFHCF ₂ CH ₂ OH, H〇CH ₂ CH ₂ CH ₂ (CF ₂ ) ₃ CH ₂ CH ₂ CH ₂ 〇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.

In addition, as 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. 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 is.

In the present invention, as 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. .

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, 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. When mixing metal oxides, especially these specific metal oxides, the fluororubber (I) layer and the non-fluororubber (II) The effect of improving the vulcanization adhesive strength with the layer is obtained. 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. When both are mixed with a metal oxide, 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.

Note that 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.

In the present invention, 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 In addition to inorganic fillers, such as organic fillers, organic fillers and the like. As described above, silicon oxides such as wet silica, dry silica, fine quartz powder, and glass fiber can also be used.

As a processing aid, 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. 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.

Examples of plasticizers include fluoric acid derivatives and sebacic acid derivatives. Examples of softening agents include lubricating oils, process oils, coal tar, castor oil, and calcium stearate. Examples of 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). 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. That is, 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 method of forming a laminate, and then vulcanizing the obtained rubber laminate to bond the layers together; or on the inner layer made of one of the fluororubber (I) and the non-fluororubber (II), After applying a fiber reinforcement layer as necessary, 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. And vulcanizing the rubber laminate to bond the layers (I) and (Π). The case where the above-mentioned fiber reinforcing layer is applied is suitable for use in a turbo air hose.

Of course, 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 fluororubber (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. For example, when a high temperature fluid flows on the inner surface of the hose, a highly heat-resistant rubber layer is placed on the inner layer. . Of course, 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. The same applies to 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. Further, even when the above-mentioned metal oxide is not blended in both the fluororubber (I) layer and the non-fluororubber (II) layer, the non-fluororubber (II) is made of silicone rubber and the vulcanization system is not used. When the peroxide vulcanization system is used, 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.

That is, (A) a fluororubber (I) layer composed of a fluororubber compound in which an organic peroxide vulcanizing agent is mixed with a fluororubber (I); and (B1) an organic peroxide vulcanizate on a silicone rubber. 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.

The 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.

Particularly preferred embodiments of the rubber laminate of the present invention include, for example, the following, but are not limited thereto. Rubber laminate (1)

Fluororubber (I) layer:

Fluororubber (I): VdF-based fluororubber (Iodine content: 0.05 mol% or more)

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 oxide: any

Rubber laminate (2)

Fluororubber (I) layer:

Fluororubber (I): VdF fluororubber (Iodine content 0.15 mol% or more)

Vulcanizing agent: Peroxide vulcanizing agent

Non-fluororubber (II) layer:

Non-fluorine rubber: Silicone rubber

Vulcanizing agent: Peroxide vulcanizing agent

Rubber laminate (3)

Fluororubber (I) layer:

Fluororubber (I): VdF-based fluororubber (iodine content 0.25 mol% that's all)

Vulcanizing agent: Peroxide vulcanizing agent

Metal oxide: magnesium oxide

Non-fluororubber (Π) layer:

Non-fluorine rubber: Silicone rubber

Vulcanizing agent: Peroxide vulcanizing agent

Metal oxide: magnesium oxide

Rubber laminate (4)

Fluororubber (I) layer:

Fluoro rubber (I): V d F type fluoro rubber (Iodine content 0.40 mol% or more)

Vulcanizing agent: peroxide vulcanizing agent

Metal oxide: magnesium oxide

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. For example, 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. Heat resistance * Oil resistance · Fuel oil resistance · LLC resistance · Gasket requiring steam resistance ゃ Non-contact type and contact type packings (self-sealing packing, piston ring, split ring type packing, mechanical seal) , Oil seal, etc.) Suitable for seals, bellows, diaphragms, hoses, tubes, wires, etc.

Specifically, it can be used for the applications listed below.

Engine body:

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.

Valve train:

Valve stem oil seals for engine valves, etc.

Lubrication · Cooling system:

Engine oil cooler hoses for engine oil coolers, oil cleaning hoses, seal gaskets, etc., Ota hoses around Laje night, vacuum pump oil hoses for vacuum pumps, etc.

Fuel system:

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. Fuel tube tube body and connector o-ring, etc., Injector cushion ring for injector, Injector seal ring, Injector eleven ring, Prescher regular Yuichi diaphragm, Check valve , Carburetor needle valve petals, acceleration pumps Valve seats and diaphragms for complex air control equipment (CAC) such as pistons, flange gaskets, and control hoses.

Intake and exhaust systems:

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.

Trans mission system:

Transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses, etc. AT transmission oil hoses, ATF hoses, 0-rings, packings, etc.

Steering system:

Power steering oil hose, etc.

Brake system:

Oil seals, packings, packings, brake oil hoses, etc., master back air valves, vacuum valves, diaphragms, etc. Master cylinder cylinder piston cups (rubber cups), etc. Carrier seals, boots, etc. Basic electrical components:

Wires (harness) insulators and sheaths, and tubes for harness exterior parts.

Control system electrical components:

Coating materials for various sensors. Car air conditioner ring, packing, cooler hose, etc. For vehicles other than automobiles, for example, oil, chemical, heat, steam, or weather-resistant packing, air-rings, hoses, other sealing materials, diaphragms, valves, etc. Similar packing in brands, o-rings, seals, diaphragms, valves, hoses, rolls, tubes, chemical resistant coatings, linings, similar packing in food plant equipment and food equipment (including household goods) , E-rings, hoses, seals, belts, diaphragms, valves, rolls, tubes, similar packing in nuclear plant equipment, O-rings, hoses, seals, diaphragms, valves, tubes, general industrial parts Packing, Pi ring Hoses, sealing materials, die Yafuramu, valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, is suitable for application to such mouth one Rupuredo of PPC copying machine.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1

The fluororubber (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.

The abbreviations and components in Tables 1 and 2 are as follows. Fluororubber (I)

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 related

Silicone rubber: Silicone rubber compound manufactured by Shin-Etsu Chemical Co., Ltd.

(Product name: KE 551-U)

Vulcanizing agents

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)

Vulcanization aid

TAI C: Triaryl isocyanurate manufactured by Nippon Kasei Co., Ltd.

Metal oxide related

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)

Others (fillers, etc.)

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)

Treatment (weight parts)

Fluoro rubber Fluoro rubber (I) Metal oxide ί | Of course Other Compound FKM Vulcanizing agent 1 Vulcanizing aid

7ηΓ) ΜΤ Iron hydroxide hydroxide Cruel ship ^ AI2D 3 2

1 2 3 4 Calcium Calcium Formulation a 100 1.5 ― ― ― ― 4 20 ― Formulation b 100 1.5 10 ― ― ― ― '4 10

Formulation c 100 1.5 8 — — — — 4 10

Formulation d 100 1.5 10 — — — —. — 4 10

Formulation e ― 100 ― 1.5 8 4 10

Formulation f 100 1.5 10 ― ― ― ― 4 10 ― Formulation g 100 1.5 8 4 10

Formulation h 100 1.5 40 4 0

1 Compound I 100 1 5 10 4 10

Formulation j 100 1.5 10 4 10

Formulation k 100 1.5 10 4 10

Formulation 1 100 1.5 10 4 10

Formulation m 100 1.5 10 4 10

Formulation n 100 1.5 10 4 10

Polio Polio

Formulation o 100 vulcanized 3 vulcanized 206 6 * Auxiliary *

*: Combined with F KM 4

Table 2

Table 3

*: Cohesive failure Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, 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 (Π) layer can be obtained.

Claims

Scope of Word

1. From a fluororubber (I) layer consisting of a fluororubber (I) and a fluororubber compound (A) containing a vulcanizing agent, and from a rubber compound (B) containing a nonfluorinated rubber (II) and a vulcanizing agent A rubber laminate directly vulcanized and bonded to a non-fluorinated rubber (II) layer, wherein at least one of the compounds (A) and (B) contains metal oxide per 100 parts by weight of rubber. A rubber laminate mixed with 4 to 100 parts by weight.

2. The rubber laminate according to claim 1, wherein the non-fluorinated rubber (II) is a silicone rubber.

3. Claims 1 or 2 wherein both said compounds (A) and (B) are mixed with 4 to 100 parts by weight of metal oxide per 100 parts by weight of rubber. The rubber laminate as described in the above.

4. The rubber laminate according to claim 1, wherein the adhesive strength at 100 ° C. is 0.7 NZmm or more.

5. The rubber laminate according to claim 1, 2 or 3, wherein the vulcanizing agent in the fluororubber compound (A) is an organic peroxide.

6. The rubber laminate according to claim 1, 2 or 3, wherein the vulcanizing agent in the non-fluorinated rubber compound (B) is an organic peroxide. .

7. The claim 1 or 2, 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. 7. The rubber laminate according to any one of items 3, 3, 4, 5, and 6.

8. The rubber laminate according to any one of claims 1, 2, 3, 4, 5, 6, and 7, wherein the metal oxide is magnesium oxide.

9. The above fluororubber (I) crosslinks iodine, bromine and Z or double bond Claims 1, 2, 3, 4, 5, and 6 which are fluororubbers having a crosslinking point content of 0.05 to 5 mol%. 9. The rubber laminate according to item 7, or 8.

10. A rubber laminate composed of an inner layer and an outer layer is formed by simultaneously extruding the fluororubber (I) and the non-fluororubber (II) by an extruder, or is combined with the fluororubber (I). 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 any one of the above non-fluororubbers (II) by an extruder, and then obtained. Claims 1, 2, 3, 4, 5, 5, 6, 7, 8, or 9 to vulcanize the rubber laminate and bond the layers A method for producing the rubber laminate according to the above.

11. A heat- and oil-resistant rubber hose made of a rubber laminate obtained by the production method according to claim 10.