KR20150003328A

KR20150003328A - Laminate

Info

Publication number: KR20150003328A
Application number: KR1020147032002A
Authority: KR
Inventors: 유키 구와지마; 미츠히로 오타니; 도시아키 마스이; 다케시 이나바
Original assignee: 다이킨 고교 가부시키가이샤
Priority date: 2012-04-25
Filing date: 2013-04-23
Publication date: 2015-01-08
Also published as: JPWO2013161800A1; WO2013161800A1; CN104245308A

Abstract

An object of the present invention is to provide a laminate capable of firmly bonding a fluorine rubber layer and a fluorine rubber layer without using an adhesive and without applying a surface treatment to each layer of the fluorine rubber layer and the fluorine rubber layer. The present invention is a laminate comprising a fluororubber layer (B) and a fluororubber layer (A) laminated on the fluororubber layer (B), wherein the fluororubber layer (A) is a layer formed of a non- The non-fluorine rubber composition is a composition comprising an unvulcanized non-fluorine rubber (a1), a 1,8-diazabicyclo (5.4.0) undecene-7 salt, and a 1,8-diazabicyclo (5.4.0) undecene- (A2), magnesium oxide (a3) and silica (a4) selected from the group consisting of fluorine rubber (b1) and fluorine rubber (b1) .

Description

Laminate {LAMINATE}

The present invention relates to a laminate.

Fluorine rubber is widely used in various fields such as automobile industry, semiconductor industry, chemical industry and the like because it shows excellent chemical resistance, solvent resistance and heat resistance. For example, in the automobile industry, , Hoses such as fuel systems and peripheral devices, and sealing materials.

Although the fluororubber exhibits excellent properties as described above, its price is very high as compared with a usual rubber material, and production of a material such as a hose by using only the fluororubber has a problem in terms of cost. In addition, the acrylonitrile-butadiene copolymer rubber conventionally used as a hose for fuel transportation is inferior to the fluororubber in terms of properties such as heat resistance, oil resistance and aging resistance, and improvement thereof has been demanded.

Under the above circumstances, it has been proposed to use fluorine rubber and non-fluorine rubber in combination. For example, Patent Document 1 discloses a hose in which fluorine rubber is thinly used as an inner layer and non-fluorine rubber such as epichlorohydrin rubber is used as an outer layer. However, the adhesion between the fluorine rubber layer and the non-fluorine rubber layer such as the epichlorohydrin rubber is insufficient, which is problematic in practical use.

(5.4.0) -7-undecene salt (DBU salt) as an adhesive compounding agent to the non-fluorine rubber layer in order to improve the adhesion between the fluorine rubber layer and the non-fluorine rubber layer, A method of mixing an epoxy resin with a non-fluorine rubber layer has been studied. However, even when these methods are used, sufficient adhesion can not be given.

In order to solve the above problems, for example, Patent Document 2 discloses a method for producing a fluoropolymer laminate having a step of laminating a fluoropolymer layer (A) and a non-fluororubber layer (B), wherein the fluoropolymer layer A) is formed by a fluoropolymer composition comprising a fluoropolymer and a vulcanizing agent, and the non-fluorinated rubber layer (B) is formed by a non-fluorinated rubber composition comprising a non-fluorine rubber and an adhesive compounding agent, The adhesive compounding agent may be at least one selected from orthophthalic acid salts, octylic acid salts, toluenesulfonic acid salts and phenol salts of 1,8-diazabicyclo (5.4.0) -7-undecene, and imidazoles Wherein the fluoropolymer laminate is at least one selected from the group consisting of fluoropolymer and fluoropolymer.

Patent document 3 discloses a rubber composition comprising a rubber layer (A) and a fluororesin layer (B) laminated on the rubber layer (A) in order to provide a vulcanized laminate in which a rubber layer and a fluororesin layer are firmly adhered. Wherein the rubber layer (A) is a layer formed of a rubber composition for vulcanization, and the rubber composition for vulcanization includes an unvulcanized rubber (a1), a 1,8-diazabicyclo (5.4.0) undecene-7 salt Diazabicyclo (4.3.0) -nonene-5 salt, 1,8-diazabicyclo (5.4.0) undecene-7 and 1,5-diazabicyclo (4.3.0) (A2), magnesium oxide (a3) and silica (a4), wherein the compound (a2) contains 1.0 to 1.0 part by mass of the unvulcanized rubber (a1) (B) is a layer formed of a fluoropolymer composition, and the fluoropolymer composition is a fluoropolymer composition derived from chlorotrifluoroethylene In that it contains a fluoropolymer (b1) having polymerized units is described laminate according to claim.

International Publication No. 2006/082843 pamphlet Japanese Patent Application Laid-Open No. 11-116004 International Publication No. 2011/001756 brochure

An object of the present invention is to provide a laminate capable of firmly bonding a non-fluorine rubber layer and a fluorine rubber layer without using an adhesive and without applying a surface treatment to each layer of the fluorine rubber layer and the fluorine rubber layer .

The present invention is a laminate comprising a fluororubber layer (B) and a fluororubber layer (A) laminated on the fluororubber layer (B), wherein the fluororubber layer (A) is a layer formed of a non- The non-fluorine rubber composition is a composition comprising an unvulcanized non-fluorine rubber (a1), a 1,8-diazabicyclo (5.4.0) undecene-7 salt, and a 1,8-diazabicyclo (5.4.0) undecene- (A2), magnesium oxide (a3) and silica (a4) selected from the group consisting of fluorine rubber (b1) and fluorine rubber (b1) And the like.

The unvulcanized non-fluorine rubber (a1) is preferably an acrylonitrile-butadiene rubber (NBR) or a hydride thereof.

It is preferable that the fluorine rubber (b1) is at least one kind of fluorine rubber selected from the group consisting of vinylidene fluoride-hexafluoropropylene fluorine rubber and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluorine rubber.

In the non-fluorine rubber composition, it is preferable that the compounding amount of the compound (a2) is 0.7 to 5.0 parts by mass based on 100 parts by mass of the unvulcanized fluorine rubber (a1).

The non-fluorine rubber composition preferably further contains at least one vulcanizing agent (a5) selected from the group consisting of a sulfur vulcanizing vulcanizing agent and a peroxide vulcanizing vulcanizing agent.

The non-fluorine rubber composition preferably further contains at least one metal salt (a6) selected from the group consisting of a carbamic acid metal salt and a thiazole-based metal salt.

The compound (a2) is preferably 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride.

The present invention is also a vulcanized laminate obtained by heat-treating the above laminate, wherein the vulcanized non-fluoro rubber layer (A1) and the vulcanized fluoro rubber layer (B1) are vulcanized and bonded.

It is preferable that the vulcanized laminate of the present invention is a hose or a tube, and the vulcanized fluoro rubber layer (B1) is laminated inside the vulcanized non-fluoro rubber layer (A1).

The laminate of the present invention can firmly adhere the fluorine rubber layer and the fluorine rubber layer without using an adhesive and without performing surface treatment on each layer of the fluorine rubber layer and the fluorine rubber layer.

The laminate of the present invention is characterized by comprising a fluororubber layer (B) and a non-fluororubber layer (A) laminated on the fluororubber layer (B).

Each layer will be described below.

(A) a non-fluorine rubber layer

The non-fluorine rubber layer (A) is a layer formed of a non-fluorine rubber composition.

The non-fluorine rubber composition comprises an unvulcanized non-fluorine rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt and 1,8-diazabicyclo (5.4.0) undecene (A2), magnesium oxide (a3) and silica (a4) selected from the group consisting of -7.

(A2), magnesium oxide (a3) and silica (a4) are used in combination in the non-fluorine rubber composition, or the surface of each layer of the non-fluorine rubber layer (A) and the fluorine rubber layer (B) The vulcanized laminate obtained from the laminate of the present invention is firmly bonded to the vulcanized fluororubber layer and the vulcanized fluororubber layer.

Therefore, when the non-fluorine rubber layer (A) and the fluorine rubber layer (B) are laminated, it is not necessary to undergo a particularly complicated process, and it is possible to easily mold at low cost. Further, since it can be molded by a usual method such as extrusion molding, it can be made thinner and it is also improved in flexibility.

The non-fluorine rubber composition may further comprise at least one of the vulcanizing agent (a5) and the metal salt (a6) as optional components. Particularly, when the non-fluorine rubber composition contains the vulcanizing agent (a5) and the metal salt (a6), the vulcanized laminate obtained from the laminate of the present invention is more firmly bonded to the vulcanized fluorine rubber layer and the vulcanized fluorine rubber layer. The vulcanizing agent (a5) and the metal salt (a6) will be described later.

Specific examples of the unvulcanized sulfuric fluorine rubber (a1) include acrylonitrile-butadiene rubber (NBR) or its hydride (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber ), Diene rubber such as natural rubber (NR) and isoprene rubber (IR), ethylene-propylene-tri-monomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber and acrylic rubber.

The unvulcanized sulfur-free fluorine rubber (a1) is preferably a diene-based rubber in view of heat resistance, oil resistance, weather resistance and extrusion moldability, and more preferably NBR or HNBR.

The non-fluorine rubber composition is prepared by mixing 1,8-diazabicyclo (5.4.0) undecene-7 salt (hereinafter also referred to as "DBU salt") and 1,8-diazabicyclo (5.4.0 undecene- (Hereinafter also referred to as " DBU "). The compound (a2) is preferably 0.7 to 5.0 parts by mass based on 100 parts by mass of the unvulcanized naphthalene rubber (a1). More preferably, the compound (a2) is 1.0 part by mass or more based on 100 parts by mass of the unvulcanized norbornene rubber (a1). If the amount of the compound (a2) is too small, there is a possibility that a sufficient adhesive force may not be obtained. The amount of the compound (a2) is more preferably 4.0 parts by mass or less, more preferably 3.5 parts by mass or less, and particularly preferably 3.0 parts by mass or less, based on 100 parts by mass of the unvulcanized norbornene rubber (a1). If the amount of the compound (a2) is too large, the vulcanization may be inhibited.

The compound (a2) is at least one compound selected from the group consisting of DBU salts and DBU.

Examples of DBU salts include salts of DBU, long chain aliphatic carboxylic acid salts, aromatic carboxylic acid salts, orthophthalic acid salts, p-toluene sulfonic acid salts, phenol salts, phenol resin salts, naphthoic acid salts, octylic acid salts, oleic acid salts, Novolac resin salts and chloride salts (preferably 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride (DBU-B)).

From the viewpoint of improving the bonding strength, the compound (a2) is at least one compound selected from the group consisting of DBU, DBU-B, DBU naphrate, DBU phenol, DBU orthophthalate and DBU formate Compound. The compound (a2) is more preferably at least one compound selected from the group consisting of DBU, DBU-B and orthophthalic acid of DBU, and DBU-B is more preferable.

The non-fluorine rubber composition may contain a quaternary ammonium salt other than the compound (a2). Examples of quaternary ammonium salts other than the compound (a2) include 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt), 1,5-diazabicyclo (4.3.0) DBN).

Examples of the DBN salt include a carbonate salt of DBN, a long chain aliphatic carboxylic acid salt, an aromatic carboxylic acid salt, an orthophthalic acid salt, a p-toluenesulfonic acid salt, a phenol salt, a phenol resin salt, a naphtate salt, an octylate salt, an oleate salt, Novolac resin salts, chloride salts and the like.

The non-fluorine rubber composition comprises magnesium oxide (a3). The blending amount of the magnesium oxide (a3) is preferably 3 to 20 parts by mass, particularly preferably 5 to 15 parts by mass, based on 100 parts by mass of the unvulcanized naphthalene rubber (a1) from the viewpoints of adhesiveness and rubber properties. Since the laminate having the specific structure of the present invention is made of magnesium oxide (a3), the vulcanized laminate obtained from the laminate of the present invention is firmly bonded to the vulcanized fluoro rubber layer and the vulcanized fluoro rubber layer.

The non-fluorine rubber composition comprises silica (a4). As the silica (a4), basic silica and acidic silica can be used, and from the viewpoint of adhesion, it is preferable to use basic silica. As the basic silica, Caplex 1120 (manufactured by DSL Japan Co., Ltd.) can be mentioned. The blending amount of the silica (a4) is preferably from 10 to 40 parts by mass, particularly preferably from 15 to 25 parts by mass, per 100 parts by mass of the unvulcanized naphthalene rubber (a1) from the viewpoints of adhesiveness and rubber properties . When the laminate having a specific structure of the present invention contains silica (a4) as an essential component, the vulcanized laminate obtained from the laminate of the present invention is obtained by firmly bonding the vulcanized fluororubber layer and the vulcanized fluororubber layer.

As the vulcanizing agent (a5), conventionally known vulcanizing agents may be used in accordance with the vulcanization system of the non-fluorine rubber composition. Vulcanization of the unvulcanized sulfur-free fluorine rubber (a1) improves mechanical strength such as tensile strength of the resulting vulcanized fluorine rubber layer, and good elasticity can be obtained.

Examples of the vulcanizing system that can be used in the present invention include a sulfur vulcanizing system, a polyamine vulcanizing system, a polyol vulcanizing system, a peroxide vulcanizing system, an imidazole vulcanizing system, a triazine vulcanizing system, an oxazole vulcanizing system, However, when the vulcanizable rubber (cure site) is contained in the unvulcanized rubber, it may be suitably selected depending on the kind of cure site or the properties and applications given to the vulcanized laminate.

Examples of the vulcanizing agent (a5) include, for the vulcanization system, sulfur vulcanizing vulcanizing agents, polyamine vulcanizing vulcanizing agents, polyol vulcanizing vulcanizing agents, peroxide vulcanizing vulcanizing agents, imidazole vulcanizing vulcanizing agents, An oxazole vulcanizing vulcanizing agent, and a thiazole vulcanizing vulcanizing agent may be employed, and they may be used alone or in combination.

For example, when the unvulcanized sulfuric fluorine rubber (a1) is a dienic non-fluorine rubber (NBR, SBR, BR, etc.), a sulfur vulcanization system and a peroxide vulcanization system are usually employed. And at least one kind of a vulcanizing agent selected from the group consisting of a peroxide vulcanizing agent and a peroxide vulcanizing vulcanizing agent. More preferably, it is a sulfur vulcanizing vulcanizing agent.

The addition amount of the vulcanizing agent (a5) is preferably 0.5 to 15.0 parts by mass based on 100 parts by mass of the unvulcanized norbornene rubber (a1). The amount added is more preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, particularly preferably 3.0 parts by mass or less, and more preferably 1.0 part by mass or more.

Examples of the sulfur vulcanizing vulcanizing agent include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, sulfur chloride, sulfur dichloride, disulfide compounds and polysulfide compounds.

The blending amount of the sulfur vulcanizing vulcanizing agent is preferably 1.0 to 10.0 parts by mass based on 100 parts by mass of the unvulcanized norbornene rubber (a1). If it is too small, the adhesiveness becomes insufficient, and if it is too much, it tends to become excessively hard.

As the peroxide vulcanizing vulcanizing agent, an organic peroxide capable of easily generating a peroxy radical in the presence of heat or an oxidation-reduction system is preferable.

Examples of the organic peroxide include 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, butyl peroxide, t-butyl peroxide, dicumyl peroxide,?,? '-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, benzoylperoxide, t- butylperoxybenzene, 2,5- 5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropylcarbonate, and the like. Among them, preferred is a dialkyl compound. Generally, the kind and blending amount are selected from the amount of active -O-O-, the decomposition temperature, and the like. The blending amount is usually 0.1 to 15.0 parts by mass, preferably 0.3 to 5.0 parts by mass based on 100 parts by mass of the unvulcanized fluororubber (a1).

The metal salt (a6) is preferably at least one selected from the group consisting of a carbamic acid metal salt and a thiazole-based metal salt.

Examples of the carbamic acid metal salt include zinc salt (ZnMDC) of dimethyldithiocarbamate, zinc salt (ZnEDC) of diethyldithiocarbamate, zinc salt (ZnBDC) of dibutyldithiocarbamate, (FeMDC) of dimethyldithiocarbamate, zinc salt (ZnEPDC) of ethylphenyldithiocarbamate, zinc salt of N-pentamethylenedithiocarbamate, zinc salt of dibenzyldithiocarbamate, The sodium salt of dimethyldithiocarbamate (NaMDC), the sodium salt of diethyldithiocarbamate (NaEDC), the sodium salt of dibutyldithiocarbamate (NaBDC), the copper salt of dimethyldithiocarbamate (CuMDC), and tellurium salt of diethyldithiocarbamate (TeEDC). These may be used alone or in combination of two or more. Of these, ZnMDC, ZnEDC, or ZnBDC are suitably used in view of adhesiveness and rubber properties.

As the thiol-based metal salt, a zinc salt of mercaptobenzothiazole (ZnMBT) is suitably used.

The amount of the metal salt (a6) is preferably 0.01 to 3.0 parts by mass, more preferably 0.01 to 0.5 parts by mass, and particularly preferably 0.05 to 0.3 parts by mass with respect to 100 parts by mass of the unvulcanized naphthalene rubber (a1). When the amount of the metal salt (a6) is too small, the physical properties of the vulcanized rubber tend to deteriorate, while when it is too large, the unvulcanized properties tend to deteriorate.

The non-fluorine rubber composition may contain a resin in order to give properties to the non-fluorine rubber layer (A) different from the unvulcanized fluorine rubber (a1). As the resin, for example, PVC, chlorinated polystyrene, chlorosulfonated polystyrene ethylene, ethylene-vinyl acetate copolymer and the like can be given. For example, when the non-fluorine rubber composition contains NBR and PVC, ozone resistance can be improved. In this case, the blending amount of PVC is preferably 10 to 70 parts by mass relative to 100 parts by mass of NBR.

In the present invention, it is also possible to add, in accordance with the purpose or necessity, a conventional additive to be incorporated into a general non-fluorine rubber composition, for example, fillers, processing aids, plasticizers, softeners, antioxidants, colorants, stabilizers, Various additives such as an imparting agent, a thermal conductivity imparting agent, a surface non-sticking agent, a tackifier, a flexibility imparting agent, a heat resistance improving agent, a flame retardant, an ultraviolet absorber, an oil resistance improver, a foaming agent, a scorch inhibitor, a lubricant and an epoxy resin. In addition, one or two or more kinds of commercial vulcanizing agents and vulcanization accelerating agents different from those described above may be blended. However, these additives are compounded in such an amount as not to impair the interlaminar adhesive strength of the vulcanized laminate obtained from the laminate of the present invention for the purpose of the present invention.

Examples of the filler include metal oxides such as calcium oxide, titanium oxide and aluminum oxide; Metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide; Carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate; Silicates such as magnesium silicate, calcium silicate, sodium silicate and aluminum silicate; Sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; Metal hydroxides such as synthetic hydrotalcite, molybdenum disulfide, iron sulfide and copper sulfide; (Barium sulfide), graphite, carbon black, fluorocarbon, calcium fluoride, coke, quartz powder, zincation, talc, mica powder, wollastonite, carbon fiber, aramid fiber, various whiskers , Glass fibers, organic reinforcing agents, and organic fillers.

Examples of the processing aid 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; Higher fatty acid esters such as ethyl oleate, higher aliphatic amines 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 vaseline and paraffin; Silicone oil, silicone polymer, low molecular weight polyethylene, phthalic acid esters, phosphoric acid esters, rosin, (dialkylated) dialkylamines, (dialkylated) dialkylsulfones, and surfactants.

Examples of the plasticizer include phthalic acid derivatives, adipic acid derivatives, sebacic acid derivatives and softening agents such as lubricating oil, process oil, coal tar, castor oil, calcium stearate and antioxidants such as phenylenediamines, Phosphates, quinolines, cresols, phenols, dithiocarbamate metal salts and the like.

The non-fluorine rubber composition comprises an unvulcanized fluorine rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt and 1,8-diazabicyclo (5.4.0) undecene-7 (A2), magnesium oxide (a3) and silica (a4), if necessary, and at least one vulcanizing agent (a5), a metal salt (a6) and other additives.

The kneading can be carried out using, for example, an open roll, a Banbury mixer, a pressurizing kneader or the like at a temperature of 100 DEG C or lower.

The non-fluorine rubber composition preferably has an optimum vulcanization time (T ₉₀ ) of 18 minutes or less. More preferably not more than 15 minutes, even more preferably not more than 13 minutes. The lower limit of T ₉₀ is not particularly limited, but is, for example, 1 minute. With the above-described non-fluorine rubber composition, the vulcanization time can be shortened and the productivity can be improved. T ₉₀ is a value obtained by measuring the maximum torque value (M _H ) and the minimum torque value (M _L ) at 160 ° C. and is a value obtained by {(M _H ) - (M _L )} × 0.9 + M _L. M _H and M _L are measured values in accordance with JIS K 6300-2.

Next, the fluorine rubber layer (B) in the laminate of the present invention will be described.

(B) fluorine rubber layer

The fluororubber layer (B) is a layer formed of a fluororubber composition. The fluorine rubber composition contains the fluorine rubber (b1).

The fluorine rubber (b1) may be an unvulcanized fluorine rubber or a vulcanized fluorine rubber.

Examples of the fluorine rubber (b1) include a peroxide-vulcanizable fluorine rubber, a polyol-vulcanizable fluorine rubber, and a polyamine vulcanizable fluorine rubber. The peroxide-vulcanizable fluorine-containing rubber is not particularly limited and may be a fluorine rubber having a peroxide-vulcanizable region. The peroxide-vulcanizable site is not particularly limited, and examples thereof include iodine atom and bromine atom.

The polyol vulcanizable fluoro rubber is not particularly limited and may be a fluoro rubber having a polyol vulcanizable region. The polyol vulcanizable region is not particularly limited, and examples thereof include sites having a vinylidene fluoride (VdF) unit. Examples of the method of introducing the vulcanization site include a method of copolymerizing a monomer that provides a vulcanization site at the time of polymerization of the fluorine rubber.

Examples of the fluorine rubber (b1) include fluorine rubber based on vinylidene fluoride (VdF) / hexafluoropropylene (HFP), fluorine rubber based on VdF / HFP / tetrafluoroethylene (TFE), fluorine rubber based on TFE / Fluorine rubber based on ethylene / HFP / VdF, fluorine rubber based on ethylene / HFP / TFE, fluorine rubber based on VdF / TFE / perfluoroalkyl vinyl ether (PAVE), fluorine rubber based on ethylene / VdF / CTFE based fluorine rubber, and the like.

The fluorine rubber (b1) is more preferably a fluorine rubber (VdF fluorine rubber) containing VdF units from the viewpoints of heat resistance, compression set, workability and cost, and more preferably VdF-HFP fluororubber and VdF- And at least one kind of fluorine rubber selected from the group consisting of TFE-based fluorine rubber is more preferable.

As the fluorine rubber (b1), there may be used not only one type of fluorine rubber as described above but also two or more kinds thereof, and they may be vulcanized.

The fluorine rubber (b1) used in the present invention is preferably a fluorine rubber having a fluorine content of 64 mass% or more, more preferably a fluorine rubber having a fluorine content of 66 mass% or more. The upper limit value of the fluorine content is not particularly limited, but is preferably 74% by mass or less. When the fluorine content is less than 64 mass%, the chemical resistance, fuel oil repellency and fuel permeability tend to deteriorate.

The fluorine rubber composition may comprise a fluorine rubber (b1) and a fluorine resin. The fluorine rubber (b1) may be obtained by dynamically vulcanizing the unvulcanized fluorine rubber under the molten condition in the presence of a fluorine resin and a vulcanizing agent It may be a vulcanized fluorine rubber. Thus, the fluorine rubber of unvulcanized sulfur is dynamically vulcanized to improve the flexibility of the fluorine rubber layer formed of the fluorine rubber composition.

Here, "dynamically vulcanizing" means dynamically vulcanizing the unvulcanized fluororubber at the same time as the melt-kneading by using a Banbury mixer, a pressurizing kneader, an extruder or the like. Of these, an extruder such as a biaxial extruder is preferable in that a high shear force can be applied. By the dynamic vulcanization treatment, the phase structure of the fluororesin and the vulcanized fluororubber can be controlled.

Further, the melting condition means that the temperature is higher than or equal to the melting temperature of the fluororesin. The suitable temperature range differs depending on the melting point of the fluororesin and the glass transition temperature of the unvulcanized fluororubber, but is preferably 120 to 330 ° C, more preferably 130 to 320 ° C. If the temperature is lower than 120 占 폚, the dispersion between the fluorine resin and the fluorine rubber tends to be coarsened, and if it exceeds 330 占 폚, the fluorine rubber tends to be thermally deteriorated.

The obtained fluororubber composition may have a structure in which the fluororesin forms a continuous phase and a structure in which the vulcanized fluororubber forms a disperse phase or a structure in which the fluororesin and the vulcanized fluororubber form a coin. And the vulcanized fluorine rubber forms a dispersed phase.

The unvulcanized fluororubber becomes a vulcanized fluororubber and the melt viscosity increases so that the vulcanized fluororubber becomes a dispersed phase or the fluororubber of the fluororubber To form a structure of performance.

The fluororubber composition may contain a structure of a fluororesin and a vulcanized fluororubber in a co-fired state in a part of the structure in which the fluororesin forms a continuous phase and the vulcanized fluororubber forms a dispersed phase.

When such a structure is formed, the vulcanized laminate obtained from the laminate of the present invention shows superior fuel barrier properties, heat resistance, chemical resistance and oil resistance. The average dispersed particle diameter of the vulcanized fluororubber is preferably 0.01 to 30 占 퐉, more preferably 0.1 to 20 占 퐉, and even more preferably 0.1 to 10 占 퐉. When the average dispersed particle diameter is less than 0.01 탆, the fluidity tends to decrease. When the average dispersed particle diameter exceeds 30 탆, the strength of the molded product tends to decrease.

The mass ratio of the fluorine rubber (b1) to the fluorine resin in the fluorine rubber composition is preferably 3/97 to 80/20 (fluorine rubber (b1) / fluorine resin). When the mass ratio of the fluororesin is smaller than 80/20 (fluororubber (b1) / fluororesin), the effect of improving the fuel permeability and resistance to low temperature resistance at low temperatures is reduced. On the other hand, If it is large, the inherent elasticity of the rubber is remarkably impaired, and the permanent compression set remarkably deteriorates or the hardness becomes remarkably high, which is not preferable. (Fluorine rubber (b1) / fluorine resin) is more preferably 5/95 to 70/30, and more preferably 10/90 to 50/60, in view of enhancing balance of fuel permeability, low temperature embrittlement resistance and rubber elasticity. 50 is more preferable.

The fluororesin is not particularly limited, but a fluororesin containing at least one fluorine-containing ethylenic polymer is preferable in terms of good compatibility with the VdF fluororubber. The fluorine-containing ethylenic polymer is not particularly limited, and for example, it is preferable to have a structural unit derived from at least one fluorine-containing ethylenic monomer. Examples of the fluorine-containing ethylenic monomer include tetrafluoroethylene (TFE), the formula (2):

(Wherein Rf ² represents -CF ₃ or -ORf ³ (Rf ³ represents a perfluoroalkyl group having 1 to 5 carbon atoms)), perfluoroolefin such as perfluoroethylenically unsaturated compound, Trifluoroethylene, hexafluoroisobutene, vinylidene fluoride (VdF), vinyl fluoride, the formula (3):

(Wherein X ³ represents a hydrogen atom or a fluorine atom, X ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 1 to 10).

The fluorine-containing ethylenic polymer may have a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer, and examples of such a monomer include a fluoroolefin, a nonfluorine ethylenic monomer other than the perfluoroolefin, . The non-fluorine ethylenic monomer is not particularly limited, and examples thereof include ethylene, propylene, alkyl vinyl ethers and the like. Here, the alkyl vinyl ether refers to an alkyl vinyl ether having an alkyl group having 1 to 5 carbon atoms.

Among these, the following fluorine-containing ethylenic polymers are preferable in that the vulcanized laminate obtained from the laminate of the present invention has good fuel permeability and cold resistance.

(1) Ethylene / TFE copolymer (ETFE) containing TFE and ethylene

(2) a TFE-perfluoro (alkyl vinyl ether) copolymer (PFA) or a TFE / HFP-based copolymer (FEP) containing a perfluoroethylenically unsaturated compound represented by the formula (2)

(3) a TFE / VdF / perfluoro (alkyl vinyl ether) copolymer containing a perfluoroethylenically unsaturated compound represented by TFE, VdF and formula (2), or a TFE / HFP / VdF copolymer

(4) Polyvinylidene fluoride (PVdF)

(5) a CTFE-TFE copolymer or a CTFE / TFE / perfluoroethylenically unsaturated compound-based copolymer comprising a CTFE, TFE and a perfluoroethylenically unsaturated compound represented by formula (2)

Among them, fluorine-containing ethylenic polymers represented by (1), (2) and (5) are more preferable.

Next, preferred fluorine-containing ethylenic polymers (1), (2) and (5) will be described.

(1) ETFE

ETFE is preferable in that it exhibits excellent fuel permeability. The molar ratio of the TFE unit to the ethylene unit is preferably 20:80 to 90:10, more preferably 37:63 to 85:15, and particularly preferably 38:62 to 80:20. It may contain a third component, and the third component is not limited as long as it is copolymerizable with TFE and ethylene. The third component is usually a compound represented by the following formula:

_{^{CH 2 = CX 5 Rf 4,}} CF 2 = CFRf 4, CF 2 = CFORf 4, CH 2 = C (Rf 4) 2 ( wherein, X ⁵ is a hydrogen atom or fluorine atom, Rf ⁴ is an ether-bonding oxygen atom A fluorine-containing vinyl monomer represented by CH ₂ CX ⁵ Rf ⁴ is more preferable, and a fluorine-containing vinyl monomer represented by Rf ⁴ having a carbon number of 1 to 8 Is particularly preferable.

Specific examples of the fluorine-containing vinyl monomers represented by the above formulas include 1,1-dihydroperfluoro-olefin-1, 1,1-dihydro perfluoro-butene-1,1,1,5-trihydro- 1,1, 7-tetrahydroperfluoroheptene-1, 1,1,2-trihydroperfluorohexene-1, 1,1,2-trihydroperfluorooctene-1 , 2,2,3,3,4,4,5,5-octafluoropentyl vinyl ether, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), hexafluoropropene, perfluoro Butene-1, 3,3,3-trifluoro-2- (trifluoromethyl) propene-1, 2,3,3,4,4,5,5-heptafluoro-1-pentene ( CH ₂ = CFCF ₂ CF ₂ CF ₂ H).

The content of the third component is preferably 0.1 to 10 mol%, more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol% based on the fluorine-containing ethylenic polymer.

(2) PFA or FEP

In the case of PFA or FEP, particularly excellent heat resistance is obtained, and excellent fuel permeability is exhibited. PFA or FEP is not particularly limited but is preferably a copolymer containing 70 to 99 mol% of TFE units and 1 to 30 mol% of perfluoroethylenically unsaturated compound units represented by formula (2) And more preferably from 3 to 20 mol% of a perfluoroethylenically unsaturated compound unit represented by the formula (2). When the TFE unit is less than 70 mol%, the mechanical properties tend to decrease. When the TFE unit is more than 99 mol%, the melting point tends to be excessively high and the moldability tends to decrease. The fluorine-containing ethylenic polymer containing TFE and the perfluoroethylenically unsaturated compound represented by the formula (2) may contain a third component, and as the third component, TFE and the purple represented by the formula (2) And the kind thereof is not limited as long as it is copolymerizable with the ethylenically unsaturated compound.

(5) a CTFE-TFE copolymer or a CTFE / TFE / perfluoroethylenically unsaturated compound-based copolymer

In the case of the CTFE-TFE copolymer, the molar ratio of the CTFE unit to the TFE unit is preferably in the range of CTFE: TFE = 2: 98 to 98: 2, more preferably 5:95 to 90:10. If the CTFE unit is less than 2 mol%, the fuel permeability tends to deteriorate and the melt processing tends to be difficult. When the CTFE unit is more than 98 mol%, the heat resistance and chemical resistance at the time of molding may deteriorate. The perfluoroethylenically unsaturated compound is preferably copolymerized with the perfluoroethylenically unsaturated compound in an amount of 0.1 to 10 mol% based on the total of the CTFE unit and the TFE unit, and the total of the CTFE unit and the TFE unit And preferably 90 to 99.9 mol%. When the content of the perfluoroethylenically unsaturated compound is less than 0.1 mol%, the moldability, the environmental stress cracking resistance and the crack resistance are liable to be deteriorated. When the content is more than 10 mol%, the fuel permeability, heat resistance, It tends to deteriorate. Examples of the CTFE / TFE / perfluoroethylenically unsaturated compound copolymer include a perfluoroethylenically unsaturated compound such as CTFE / TFE / perfluoro (alkyl (meth) acrylate) which is a perfluoroethylenically unsaturated compound represented by the formula Vinyl ether) copolymer is more preferable.

Of these, ETFE is preferred because it is particularly excellent in compatibility with the VdF-based fluororubber used preferably as the fluorine rubber.

The melting point of the fluorine-containing ethylenic polymer is preferably 120 to 340 ° C, more preferably 150 to 330 ° C, and even more preferably 170 to 320 ° C. If the melting point of the fluorine-containing ethylenic polymer is less than 120 占 폚, the fluorinated rubber layer (B) tends to bleed out during vulcanization, and if it is more than 340 占 폚, mixing with the VdF fluororubber tends to be difficult.

In the vulcanized laminate obtained from the laminate of the present invention, since the vulcanized fluorine rubber layer and the vulcanized fluorine rubber layer are more firmly adhered to each other, at least one polyfunctional compound may be added to the fluorine rubber composition. The polyfunctional compound is a compound having two or more functional groups of the same or different structure in one molecule.

The functional group of the polyfunctional compound may be any functional group known to have generally reactivity, such as a carbonyl group, a carboxyl group, a haloformyl group, an amide group, an olefin group, an amino group, an isocyanate group, a hydroxyl group or an epoxy group. The compounds having these functional groups are expected not only to have high affinity with the fluorine rubber but also to react with the functional groups of the fluorine resin to further improve the adhesiveness.

It is preferable that the fluorine rubber composition further comprises a vulcanizing agent. The vulcanizing agent can be appropriately selected depending on the vulcanization system of the fluororubber to be blended. Specifically, a peroxide-based vulcanizing agent, a polyol-based vulcanizing agent, and the like can be selected depending on the purpose. The peroxide-based vulcanizing agent is not particularly limited, and examples thereof include organic peroxides. As the organic peroxide, it is preferable that a peroxy radical is easily generated in the presence of heat or an oxidation-reduction system, and for example, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane , 2,5-dimethylhexane-2,5-dihydroxyperoxide, di-t-butylperoxide, t-butylcumylperoxide, dicumylperoxide, Butyl peroxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne- 3, benzoylperoxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t- butylperoxymaleic acid, t- butylperoxyisopropylcarbonate, etc. Can be exemplified. Among them, a dialkyl compound is preferable. Generally, the amount to be used is appropriately selected from the amount of active -O-O-, decomposition temperature and the like. The amount to be used is generally 0.1 to 15 parts by mass, preferably 0.3 to 5 parts by mass based on 100 parts by mass of the fluororubber.

When an organic peroxide is used as the vulcanizing agent, a vulcanization auxiliary agent or a co-vulcanizing agent may be used in combination. The vulcanization auxiliary agent or co-vulcanizing agent is not particularly restricted but includes, for example, the above-mentioned vulcanization auxiliary agent and co-vulcanizing agent. Among these, triallyl isocyanurate (TAIC) is preferable in view of vulcanizability and physical properties of the vulcanized product.

The blending amount of the vulcanization auxiliary agent and the co-vulcanizing agent is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 6 parts by mass, further preferably 1 to 5 parts by mass, per 100 parts by mass of the fluororubber. When the vulcanization agent is less than 0.2 parts by mass, the vulcanization density is lowered and the compression set distortion tends to become larger. When the vulcanization agent is more than 10 parts by mass, the vulcanization density becomes excessively high.

The polyol vulcanizing agent is not particularly limited, and for example, a polyhydroxy compound, in particular, a polyhydroxy aromatic compound is suitably used in view of excellent heat resistance. The polyhydroxy aromatic compound is not particularly limited, and examples thereof include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) Perfluoropropane (hereinafter referred to as bisphenol AF), resorcin, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) Butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane, 4,4'-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ', 5,5'-tetrachlorobisphenol A, 3,3' '- tetrabromobisphenol A and the like. These polyhydroxy aromatic compounds may be alkali metal salts, alkaline earth metal salts or the like, but when the copolymer is coagulated with an acid, it is preferable not to use the metal salt.

The polyol vulcanizing agent is preferably a polyhydroxy compound in view of small compression set distortion of the vulcanized fluororubber and excellent moldability and is more preferably a polyhydroxy aromatic compound because of excellent heat resistance, AF is more preferable.

The blending amount of the polyol vulcanizing agent is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 6 parts by mass, and further preferably 1 to 3 parts by mass with respect to 100 parts by mass of the fluororubber. If the blending amount is less than 0.2 parts by mass, the vulcanization density tends to be low and the permanent compression set tends to increase. When the blending amount exceeds 10 parts by mass, the vulcanization density becomes excessively high.

In addition, a vulcanization accelerator may be used in combination with a polyol vulcanizing agent. When the vulcanization accelerator is used, the vulcanization reaction can be promoted by promoting the formation of intramolecular double bonds in the dehydrofluorination reaction of the fluorine rubber main chain.

The fluororubber composition may contain conventional additives to be incorporated into the fluororubber composition, for example, fillers, processing aids, plasticizers, colorants, stabilizers, adhesion aids, acid acceptors, release agents, A vulcanizing accelerator, a vulcanizing accelerator, a vulcanizing accelerator, a vulcanizing accelerator, a vulcanizing accelerator, a vulcanizing accelerator, a vulcanizing accelerator, a vulcanizing accelerator, a vulcanizing accelerator, and the like.

The fluororubber composition can be obtained by kneading a fluororubber and other additives such as a vulcanizing agent, a vulcanization assistant, a co-vulcanizing agent, a vulcanization accelerator and a filler, if necessary, by using a rubber kneading apparatus generally used. As the rubber kneading apparatus, a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used.

The laminate of the present invention is a two-layer laminate including only the fluororubber layer (B) and the non-fluororubber layer (A) in that it can have low temperature, chemical resistance and flexibility, desirable.

The laminate of the present invention is a laminate of a polymer layer (A) different from the fluororubber layer (A) and the fluororubber layer (B) on one surface (surface on which the non-fluororubber layer (A) The fluororesin layer A and the fluororubber layer B may be laminated on one surface of the non-fluororubber layer A (the surface on which the fluororubber layer B is not laminated) May be a laminate of three or more layers in which different polymer layers (C) are laminated.

The laminate may be a laminate of three or more layers in which the fluororubber layer (A) is laminated on both sides of the fluororubber layer (B), or a laminate of three or more layers in which the fluororubber layer (B) is laminated on both sides of the non- Or

The polymer layer (C) is not particularly limited and may be suitably determined in accordance with the use of the vulcanized laminate obtained from the laminate of the present invention.

The vulcanized laminate of the present invention is obtained by subjecting a laminate comprising a fluororubber layer (B) and a fluororubber layer (A) laminated on a fluororubber layer (B) And the vulcanized fluoro rubber layer (B1) are vulcanized and bonded.

The laminate of the present invention comprising the fluororubber layer (B) and the non-fluororubber layer (A) laminated on the fluororubber layer (B) is subjected to heat treatment so that the vulcanized fluororubber layer (A1) A vulcanized and laminated vulcanized laminate can be obtained.

The vulcanized non-fluoro rubber layer (A1) is obtained by vulcanizing the non-fluoro rubber layer (A) by the above heat treatment.

The vulcanized fluororubber layer (B1) is obtained by heat-treating the fluororubber layer (B). When the heat treatment is performed on the unvulcanized fluororubber layer (B), the vulcanized fluororubber layer (B1) is obtained by vulcanizing the fluororubber (b1) in the fluororubber layer (B) by the above heat treatment.

By the heat treatment, the non-fluorine rubber layer (A) is vulcanized, and the vulcanized laminated product in which the vulcanized fluoro rubber layer (A1) and the vulcanized fluoro rubber layer (B1) are vulcanized and bonded is obtained.

The heat treatment can be performed by superimposing an unvulcanized fluororubber layer (A) and a vulcanized or unvulcanized fluororubber layer (B), followed by heat treatment. By heating treatment, the non-fluorine rubber layer (A) can be vulcanized. When the fluorine rubber layer (B) is unvulcanized, the fluorine rubber layer (B) can also be vulcanized.

The heat treatment is carried out under the condition of vulcanizing at least the non-fluorine rubber layer (A). When the fluorine rubber layer (B) is uncrosslinked, the non-fluorine rubber layer (A) and the fluorine rubber layer (B) are vulcanized.

Specific conditions for the heat treatment may be appropriately determined depending on the kind of the vulcanizing agent and the like to be used, but are usually carried out by heating at a temperature of 150 to 300 DEG C for 1 minute to 24 hours.

As a method of heat treatment, a method capable of vulcanizing at least the non-fluorine rubber layer (A) is used. When the fluorine rubber layer (B) is uncrosslinked, a method capable of vulcanizing the non-fluorine rubber layer (A) and the fluorine rubber layer (B) is used.

As a method of heat treatment, a vulcanization method for heating can be employed, and it may be a vulcanization method under atmospheric pressure, pressure or reduced pressure as well as a commonly used method such as steam vulcanization, or may be a vulcanization method in air .

The vulcanized laminate of the present invention can be produced by, for example, extruding a fluorine rubber composition and a non-fluorine rubber composition by an extruder, respectively, to prepare an unvulcanized fluorine rubber sheet and an unvulcanized fluorine rubber sheet, And a fluorine rubber sheet of unvulcanized sulfur are superimposed on each other and then inserted into a heated mold to be vulcanized and bonded.

The vulcanized laminate of the present invention can be obtained by simultaneously extruding the fluororubber composition and the non-fluororubber composition into two or more layers by an extruder or by extruding the two layers or two or more extruders over the inner layer Extruding the laminate of unvulcanized materials including the inner layer and the outer layer by extruding the outer layer, extruding the laminate by an extruder, integrating the laminate and vulcanizing and adhering by heating.

The vulcanized laminate of the present invention can be obtained by, for example, superimposing an unvulcanized fluororubber sheet on a sheet containing a vulcanized fluororubber obtained by the above-mentioned dynamically vulcanization and a fluororesin, inserting it into a heated mold, It may be obtained by bonding.

The vulcanized laminate according to the present invention is a laminate having both low permeability to fuel, low-temperature embrittlement resistance, chemical resistance, oil resistance and heat resistance and is useful as a hose, tube, container, sealant or the like around fuel, And hoses or tubes for transporting fuel, such as peripherals, AT devices, fuel systems and peripherals.

It is preferable that the vulcanized laminate of the present invention is a hose or a tube and the vulcanized fluoro rubber layer (B1) is laminated inside the vulcanized non-fluoro rubber layer (A1).

For example, it is preferable that the hose or tube for fuel transportation has a laminated structure in which the vulcanized fluoro rubber layer (A1) is disposed on the innermost layer of the hose or tube and the vulcanized fluoro rubber layer (B1) is disposed on the outer layer.

Example

The following examples illustrate the invention, but the invention is not limited to these examples.

Hereinafter, the fluororesin used in Examples and Comparative Examples and the measuring method thereof will be described.

(Vulcanization characteristics)

A maximum torque value (M _H ) and a minimum torque value (M _L ) were measured at 160 ° C using a Curastometer Model II (model number: JSR Kyurastometer, manufactured by JSR Corporation) The induction time (T ₁₀ ) and the optimum vulcanization time (T ₉₀ ) were obtained. The measurement results are shown in Table 2. In addition, T ₁₀ is _{{(M H) - (M} L)} and the time is in × 0.1 + M _L, T ₉₀ is _{{(M H) - (M} L)} and the time is in × 0.9 + M _L, M _H and M _L are measured values in accordance with JIS K 6300-2.

(Adhesive strength)

The resulting laminate was cut into a rectangle having a width of 10 mm and a length of 40 mm x 3 sets, and a release film was peeled off to prepare a test piece having a holding margin. This test piece was subjected to a test at a rate of 50 mm / min at 25 占 폚 in accordance with the method described in JIS K 6256 (Adhesion Test Method of Crosslinked Rubber) using Autograph (AGS-J 5kN, Shimadzu Seisakusho Co., min. With respect to the evaluation of the adhesiveness, the peeling mode was observed and evaluated according to the following criteria. The obtained results are shown in Table 2.

(Example 1)

(Production of fluorine rubber composition and production of fluorine rubber sheet)

The materials shown in Table 1 below were kneaded using an 8-inch open roll controlled at 25 캜 to obtain a sheet-like fluororubber composition (fluororubber sheet) having a thickness of about 3 mm.

(Production of non-fluorine rubber composition and production of unvulcanized fluorine rubber sheet)

The materials shown in Table 2 below were kneaded using an 8-inch open roll whose temperature was adjusted to 25 캜 to obtain a sheet-like non-fluorine rubber composition (non-fluorine rubber sheet) having a thickness of about 3 mm.

(Preparation of laminate)

The fluorine rubber composition (fluorine rubber sheet) having a thickness of about 3 mm and the non-fluorine rubber composition (non-fluorine rubber sheet) having a thickness of about 3 mm were laminated and a resin film having a width of about 10 to 15 mm A release film of 10 mu m) was sandwiched between the both sheets, the resultant sheet was inserted into a metal mold having a metal spacer so as to have a thickness of 2 mm and pressed at 160 DEG C for 45 minutes to obtain a sheet-like laminate.

(Examples 2 to 9 and Comparative Examples 1 to 3)

A non-fluorine rubber composition was prepared in the same manner as in Example 1 except that the type and amount of the compounding agent of the non-fluorine rubber composition (non-fluorine rubber sheet) were changed as shown in Table 2, and the vulcanization characteristics were evaluated. A laminate was prepared in the same manner as in Example 1, and the adhesiveness of the laminate was evaluated. The results are shown in Table 2.

(Evaluation of adhesion)

○ ... The vulcanized non-fluorine rubber sheet or the fluorine rubber sheet breaks the material at the interface of the laminate, and it is impossible to peel off from the interface.

× ... And was relatively easily peeled from the interface of the laminate.

The laminate of the present invention is useful as a hose, a tube, a container, a sealing material, etc. around a fuel, and particularly useful as a hose or a tube for fuel transportation such as automobile engines and peripheral devices, AT devices, fuel systems and peripheral devices .

Claims

A laminate comprising a fluorine rubber layer (B) and a non-fluorine rubber layer (A) laminated on the fluorine rubber layer (B)
The non-fluorine rubber layer (A) is a layer formed of a non-fluorine rubber composition,
The non-fluorine rubber composition includes unvulcanized non-fluorine rubber (a1),
At least one compound (a2) selected from the group consisting of 1,8-diazabicyclo (5.4.0) undecene-7 salt and 1,8-diazabicyclo (5.4.0) undecene-
Magnesium oxide (a3), and
Silica (a4)
Wherein the fluorine rubber layer (B) is a layer formed of a fluorine rubber composition containing a fluorine rubber (b1).

The method according to claim 1,
Wherein the unvulcanized non-fluorine rubber (a1) is an acrylonitrile-butadiene rubber (NBR) or a hydride thereof.

3. The method according to claim 1 or 2,
Wherein the fluorine rubber (b1) is at least one fluorine rubber selected from the group consisting of vinylidene fluoride-hexafluoropropylene fluorine rubber and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluorine rubber.

4. The method according to any one of claims 1 to 3,
Wherein the non-fluorine rubber composition is a laminate in which the compounding amount of the compound (a2) is 0.7 to 5.0 parts by mass based on 100 parts by mass of the unvulcanized fluorine rubber (a1).

5. The method according to any one of claims 1 to 4,
The non-fluorine rubber composition,
At least one vulcanizing agent (a5) selected from the group consisting of a sulfur vulcanizing vulcanizing agent and a peroxide vulcanizing vulcanizing agent.

6. The method according to any one of claims 1 to 5,
The non-fluorine rubber composition,
At least one metal salt (a6) selected from the group consisting of carbamic acid metal salts and thiazole-based metal salts.

7. The method according to any one of claims 1 to 6,
Wherein the compound (a2) is 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride.

A laminated body obtained by heat-treating the laminate according to any one of claims 1 to 7,
Wherein the vulcanized non-fluoro rubber layer (A1) and the vulcanized fluoro rubber layer (B1) are vulcanized and bonded.

9. The method of claim 8,
Hose or tube,
Wherein the vulcanized fluoro rubber layer (B1) is laminated on the inner side of the vulcanized non-fluoro rubber layer (A1).