WO2013161800A1

WO2013161800A1 - Laminate

Info

Publication number: WO2013161800A1
Application number: PCT/JP2013/061879
Authority: WO
Inventors: 祐己桑嶋; 充宏大谷; 利昭増井; 剛志稲葉
Original assignee: ダイキン工業株式会社
Priority date: 2012-04-25
Filing date: 2013-04-23
Publication date: 2013-10-31
Also published as: JPWO2013161800A1; CN104245308A; KR20150003328A

Abstract

The purpose of the present invention is to provide a laminate wherein a non-fluorine rubber layer and a fluorine rubber layer are able to be firmly adhered to each other without using an adhesive and without subjecting the non-fluorine rubber layer and the fluorine rubber layer to a surface treatment. The present invention is a laminate which is provided with a fluorine rubber layer (B) and a non-fluorine rubber layer (A) that is laminated on the fluorine rubber layer (B). This laminate is characterized in that: the non-fluorine rubber layer (A) is formed from a non-fluorine rubber composition, and the non-fluorine rubber composition contains (a1) an unvulcanized non-fluorine rubber, (a2) at least one compound that is selected from the group consisting of 1,8-diazabicyclo(5.4.0)undecene-7 salts and 1,8-diazabicyclo(5.4.0)undecene-7, (a3) magnesium oxide and (a4) silica; and the fluorine rubber layer (B) is formed from a fluorine rubber composition that contains (b1) a fluorine rubber.

Description

Laminated body

The present invention relates to a laminate.

Fluororubber is widely used in various fields such as the automobile industry, semiconductor industry, chemical industry, etc. because it exhibits excellent chemical resistance, solvent resistance and heat resistance. It is used as hoses, sealing materials, etc. for devices, AT devices, fuel systems and peripheral devices.

Although fluororubber exhibits the above-mentioned excellent characteristics, its price is very expensive compared to ordinary rubber materials, and it is a problem in terms of cost to make materials such as hoses using only fluororubber. was there. In addition, acrylonitrile-butadiene copolymer rubber, which has been conventionally used as a fuel transportation hose, is inferior to fluororubber in terms of various properties such as heat resistance, oil resistance, and aging resistance, and its improvement is It was requested.

Under the background as described above, it has been proposed to use fluororubber and non-fluororubber together. For example, Patent Document 1 discloses hoses made of non-fluorinated rubber such as epichlorohydrin rubber as an outer layer using a thin fluororubber as an inner layer. However, the adhesiveness between the fluororubber layer and the non-fluororubber layer such as epichlorohydrin rubber is poor, causing a problem in practical use.

In order to improve the adhesion between the fluororubber layer and the non-fluororubber layer, 1,8-diazabicyclo (5.4.0) -7-undecene salt (DBU salt) is blended in the non-fluororubber layer as an adhesive compounding agent. A method of blending an epoxy resin with a non-fluororubber layer has also been studied. However, even if these methods are used, sufficient adhesion cannot be imparted.

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), The fluoropolymer layer (A) is formed of a fluoropolymer composition containing a fluoropolymer and a vulcanizing agent, and the non-fluororubber layer (B) is a non-fluorine rubber and an adhesive compounding agent. The adhesive compounding agent is formed from an orthophthalate, octylate, toluenesulfonate and phenol of 1,8-diazabicyclo (5.4.0) -7-undecene. A method for producing a fluoropolymer laminate, which is at least one selected from the group consisting of a salt and an imidazole having or not having a substituent There has been described.

By the way, for the purpose of providing a vulcanized laminate in which a rubber layer and a fluororesin layer are firmly bonded, Patent Document 3 discloses that a rubber layer (A) and a rubber layer (A) are laminated on each other. A fluororesin layer (B), wherein the rubber layer (A) is a layer formed from a rubber composition for vulcanization, and the rubber composition for vulcanization comprises unvulcanized rubber ( a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt, 1,5-diazabicyclo (4.3.0) -nonene-5 salt, 1,8-diazabicyclo (5.4.0) At least one compound (a2) selected from the group consisting of undecene-7 and 1,5-diazabicyclo (4.3.0) -nonene-5, magnesium oxide (a3), and silica (a4) The compound (a2) is contained in 100 parts by mass of the unvulcanized rubber (a1). The fluororesin layer (B) is a layer formed from a fluoropolymer composition, and the fluoropolymer composition is added to chlorotrifluoroethylene. A laminate comprising a fluoropolymer (b1) having a copolymerized unit derived therefrom is described.

International Publication No. 2006/082843 Pamphlet JP 2011-116004 A International Publication No. 2011/001756 Pamphlet

The present invention provides a laminate capable of firmly bonding a non-fluororubber layer and a fluororubber layer without using an adhesive and without subjecting the non-fluororubber layer and the fluororubber layer to surface treatment. The purpose is to provide.

The present invention is a laminate comprising a fluororubber layer (B) and a non-fluororubber layer (A) laminated on the fluororubber layer (B), wherein the non-fluororubber layer (A) A non-fluorinated rubber composition comprising an unvulcanized non-fluorinated rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt, and 1, Containing at least one compound (a2) selected from the group consisting of 8-diazabicyclo (5.4.0) undecene-7, magnesium oxide (a3), and silica (a4), and containing a fluororubber layer (B ) Relates to a laminate characterized by being a layer formed from a fluororubber composition containing fluororubber (b1).

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

The fluororubber (b1) is at least one fluororubber selected from the group consisting of vinylidene fluoride-hexafluoropropylene fluororubber and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluororubber. Is preferred.

In the non-fluororubber composition, the compounding amount of the compound (a2) is preferably 0.7 to 5.0 parts by mass with respect to 100 parts by mass of the unvulcanized non-fluororubber (a1).

It is preferable that the non-fluororubber composition 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-fluororubber composition preferably further contains at least one metal salt (a6) selected from the group consisting of a carbamic acid metal salt and a thiazole 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-fluororubber layer (A1) and the vulcanized fluororubber layer (B1) are vulcanized and bonded. It is also a body.

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

The laminate of the present invention can firmly bond the non-fluororubber layer and the fluororubber layer without using an adhesive, and without subjecting the non-fluororubber layer and the fluororubber layer to surface treatment. it can.

The laminate of the present invention comprises a fluororubber layer (B) and a non-fluororubber layer (A) laminated on the fluororubber layer (B).

Hereinafter, each layer will be described.

(A) Non-fluorinated rubber layer The non-fluorinated rubber layer (A) is a layer formed from a non-fluorinated rubber composition.

The non-fluorinated rubber composition contains, as essential components, an unvulcanized non-fluorinated rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt, and 1,8-diazabicyclo (5.4.0). ) It contains at least one compound (a2) selected from the group consisting of undecene-7, magnesium oxide (a3), and silica (a4).
By using the compound (a2), magnesium oxide (a3) and silica (a4) in combination with the non-fluorine rubber composition, an adhesive can be used, or the non-fluorine rubber layer (A) and the fluororubber layer (B) Even if each layer is not subjected to surface treatment, the vulcanized laminate obtained from the laminate of the present invention is obtained by firmly bonding the vulcanized non-fluororubber layer and the vulcanized fluororubber layer.
Accordingly, when the non-fluororubber layer (A) and the fluororubber layer (B) are laminated, it is not necessary to use a particularly complicated process and can be easily molded at low cost. Furthermore, since it can be formed by an ordinary method such as extrusion, a thin film can be formed, and the flexibility is improved.

The non-fluororubber composition may further contain at least one of a vulcanizing agent (a5) and a metal salt (a6) as an optional component. In particular, when the non-fluorinated rubber composition contains the vulcanizing agent (a5) and the metal salt (a6), the vulcanized laminate obtained from the laminate of the present invention has a vulcanized non-fluorinated rubber layer and a vulcanized fluorine. The rubber layer is more firmly bonded. The vulcanizing agent (a5) and the metal salt (a6) will be described later.

Specific examples of the unvulcanized non-fluorinated rubber (a1) include, for example, acrylonitrile-butadiene rubber (NBR) or a hydride thereof (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), and butadiene rubber (BR). And diene rubbers such as natural rubber (NR) and isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, and acrylic rubber.

The unvulcanized non-fluorinated rubber (a1) is preferably a diene rubber, more preferably NBR or HNBR, from the viewpoint of good heat resistance, oil resistance, weather resistance and extrusion moldability.

The non-fluorine rubber composition comprises 1,8-diazabicyclo (5.4.0) undecene-7 salt (hereinafter also referred to as “DBU salt”) and 1,8-diazabicyclo (5.4.0) undecene- And at least one compound (a2) selected from the group consisting of 7 (hereinafter also referred to as “DBU”). The compound (a2) is preferably 0.7 to 5.0 parts by mass with respect to 100 parts by mass of the unvulcanized non-fluorinated rubber (a1). The compound (a2) is more preferably 1.0 part by mass or more with respect to 100 parts by mass of the unvulcanized non-fluorinated rubber (a1). If the amount of the compound (a2) is too small, sufficient adhesive strength may not be obtained. Further, the compound (a2) is more preferably 4.0 parts by mass or less, still more preferably 3.5 parts by mass or less, relative to 100 parts by mass of the unvulcanized non-fluorinated rubber (a1). The amount is particularly preferably 3.0 parts by mass or less. When there is too much compound (a2), there exists a possibility that vulcanization | cure may be inhibited.

Compound (a2) is at least one compound selected from the group consisting of a DBU salt and DBU.

DBU salts include DBU carbonate, long chain aliphatic carboxylate, aromatic carboxylate, orthophthalate, p-toluenesulfonate, phenol salt, phenol resin salt, naphthoate, octylate, Oleate, formate, phenol novolac resin salt, chloride salt (preferably 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride (DBU-B)) It is done.

From the viewpoint of improving adhesive strength, the compound (a2) is selected from the group consisting of DBU, DBU-B, DBU naphthoate, DBU phenol salt, DBU orthophthalate, and DBU formate. Preferably it is at least one compound. The compound (a2) is more preferably at least one compound selected from the group consisting of DBU, DBU-B, and orthophthalate of DBU, and DBU-B is more preferable.

The non-fluororubber composition may contain a quaternary ammonium salt other than the compound (a2). 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) -nonene. -5 (DBN) and the like.

DBN salts include DBN carbonate, long chain aliphatic carboxylate, aromatic carboxylate, orthophthalate, p-toluenesulfonate, phenol salt, phenol resin salt, naphthoate, octylate, Examples include oleate, formate, phenol novolac resin salt, and chloride salt.

The non-fluororubber composition contains magnesium oxide (a3). The blending amount of magnesium oxide (a3) is preferably 3 to 20 parts by mass, particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the unvulcanized non-fluorinated rubber (a1) from the viewpoints of adhesion and rubber properties. It is. Since the laminate having a specific structure of the present invention requires magnesium oxide (a3) as an essential component, the vulcanized laminate obtained from the laminate of the present invention comprises a vulcanized non-fluororubber layer, a vulcanized fluororubber layer, Is firmly bonded.

The non-fluororubber composition contains silica (a4). As silica (a4), basic silica and acidic silica can be used, and from the viewpoint of adhesiveness, it is preferable to use basic silica. Examples of basic silica include Carplex 1120 (manufactured by DSL Japan Co., Ltd.). In addition, the blending amount of silica (a4) is preferably 10 to 40 parts by weight, particularly preferably 15 to 25 parts by weight, based on 100 parts by weight of the unvulcanized non-fluorinated rubber (a1), from the viewpoints of adhesiveness and rubber properties. Part. The vulcanized laminate obtained from the laminate of the present invention comprises a vulcanized non-fluororubber layer and a vulcanized fluororubber layer by making the laminate having a specific structure of the present invention essential silica (a4). It will be firmly bonded.

A conventionally well-known thing can be used for a vulcanizing agent (a5) according to the vulcanization system of a non-fluororubber composition. By vulcanizing the unvulcanized non-fluorinated rubber (a1), mechanical strength such as tensile strength of the obtained vulcanized non-fluorinated rubber layer is improved, and good elasticity can be obtained.

The vulcanization systems that can be used in the present invention include sulfur vulcanization systems, polyamine vulcanization systems, polyol vulcanization systems, peroxide vulcanization systems, imidazole vulcanization systems, triazine vulcanization systems, oxazole vulcanization systems, thiazole vulcanization systems. Any of the vulcanization systems can be used, but when the vulcanized rubber contains vulcanizable groups (cure sites), it can be selected as appropriate depending on the type of cure sites or the properties and applications to be applied to the vulcanized laminate. That's fine.

As the vulcanizing agent (a5), sulfur vulcanizing vulcanizing agent, polyamine vulcanizing vulcanizing agent, polyol vulcanizing vulcanizing agent, peroxide vulcanizing vulcanizing agent, imidazole vulcanizing agent can be used. Any of a vulcanizing vulcanizing agent, a triazine vulcanizing vulcanizing agent, an oxazole vulcanizing vulcanizing agent, and a thiazole vulcanizing vulcanizing agent may be employed, or they may be used alone or in combination.

For example, when the unvulcanized non-fluorinated rubber (a1) is a diene-based non-fluorinated rubber (NBR, SBR, BR, etc.), a sulfur vulcanized system and a peroxide vulcanized system are usually employed. Is preferably at least one vulcanizing agent selected from the group consisting of a sulfur vulcanizing agent and a peroxide vulcanizing agent. More preferred is a sulfur vulcanizing agent.

The addition amount of the vulcanizing agent (a5) is preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the unvulcanized non-fluorinated rubber (a1). The addition amount is more preferably 10.0 parts by mass or less, still more preferably 5.0 parts by mass or less, particularly preferably 3.0 parts by mass or less, and 1.0 part by mass. More preferably.

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

The compounding amount of the sulfur vulcanizing agent is preferably 1.0 to 10.0 parts by mass with respect to 100 parts by mass of the unvulcanized non-fluorinated rubber (a1). If the amount is too small, the adhesiveness is insufficient, and if the amount is too large, it tends to be too hard.

As the peroxide vulcanizing agent, an organic peroxide that easily generates a peroxy radical in the presence of heat or a redox system is preferable.

Examples of organic peroxides include 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, and di-t-butyl. Peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxide Oxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoyl) Peroxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and the like. Of these, preferred are dialkyl compounds. In general, the type and blending amount are selected from the amount of active —O—O—, decomposition temperature and the like. The amount is usually 0.1 to 15.0 parts by weight, preferably 0.3 to 5.0 parts by weight, based on 100 parts by weight of the unvulcanized non-fluorinated rubber (a1).

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

Examples of the carbamic acid metal salt include zinc salt of dimethyldithiocarbamate (ZnMDC), zinc salt of diethyldithiocarbamate (ZnEDC), zinc salt of dibutyldithiocarbamate (ZnBDC), iron salt of dimethyldithiocarbamate (FeMDC), Zinc salt of ethylphenyldithiocarbamate (ZnEPDC), zinc salt of N-pentamethylenedithiocarbamate, zinc salt of dibenzyldithiocarbamate, sodium salt of dimethyldithiocarbamate (NaMDC), sodium salt of diethyldithiocarbamate (NaEDC), dibutyl Examples include sodium salt of dithiocarbamate (NaBDC), copper salt of dimethyldithiocarbamate (CuMDC), tellurium salt of diethyldithiocarbamate (TeEDC), and the like. These may be used alone or in combination of two or more. Among these, ZnMDC, ZnEDC, or ZnBDC is preferably used in terms of adhesion and rubber properties.

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

The compounding 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 with respect to 100 parts by mass of the unvulcanized non-fluorinated rubber (a1). Particularly preferred is 0.05 to 0.3 parts by mass. When the blending amount of the metal salt (a6) is too small, the physical properties of the vulcanized rubber tend to deteriorate, and when it is too large, the unvulcanized physical properties tend to deteriorate.

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

Further, in the present invention, as necessary or necessary, conventional additives blended in a general non-fluorinated rubber composition, for example, fillers, processing aids, plasticizers, softeners, anti-aging agents, colorants, stability agents Agent, adhesion aid, mold release agent, conductivity imparting agent, thermal conductivity imparting agent, surface non-adhesive agent, tackifier, flexibility imparting agent, heat resistance improver, flame retardant, ultraviolet absorber, oil resistance improvement Various additives such as an agent, a foaming agent, a scorch inhibitor, a lubricant, and an epoxy resin can be blended. Moreover, you may mix | blend 1 type (s) or 2 or more types of the usual vulcanizing agent and vulcanization accelerator different from the above-mentioned thing. However, these additives are blended in amounts that do not impair the interlayer adhesion of the vulcanized laminate obtained from the laminate of the present invention, which is the object of the present invention.

Fillers include metal oxides such as calcium oxide, titanium oxide, and aluminum oxide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; magnesium carbonate, aluminum carbonate, calcium carbonate, barium carbonate, etc. Carbonates; silicates such as magnesium silicate, calcium silicate, sodium silicate, and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate, and barium sulfate; synthetic hydrotalcite, molybdenum disulfide, iron sulfide, sulfide Metal sulfides such as copper; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, quartz fine powder, zinc white, talc, mica powder, wax Lastite, carbon fiber, aramid fiber Various whiskers, glass fiber, organic reinforcing agents, organic fillers and the like.

As processing aids, 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; oleic acid Higher fatty acid esters such as ethyl, 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 petroleum jelly and paraffin; Silicone oil, silicone polymer, low molecular weight polyethylene, phthalates, phosphates, rosin, (halogenated) dialkylamine, (halogenated) dialkylsulfone, surfactant And the like.

Examples of plasticizers include phthalic acid derivatives, adipic acid derivatives and sebacic acid derivatives, softeners such as lubricating oil, process oil, coal tar, castor oil, calcium stearate, and antiaging agents such as phenylenediamines, Examples thereof include phosphates, quinolines, cresols, phenols, and dithiocarbamate metal salts.

The non-fluorinated rubber composition comprises unvulcanized non-fluorinated rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt, and 1,8-diazabicyclo (5.4.0) undecene- At least one compound (a2) selected from the group consisting of 7, magnesium oxide (a3), and silica (a4), and if necessary, a vulcanizing agent (a5), a metal salt (a6), and other additions It is prepared by kneading the agent.

The kneading can be performed using, for example, an open roll, a Banbury mixer, a pressure kneader, or the like at a temperature of 100 ° C. or lower.

The non-fluororubber composition preferably has an optimal vulcanization time (T ₉₀ ) of 18 minutes or less. More preferably, it is 15 minutes or less, More preferably, it is 13 minutes or less. The lower limit of T ₉₀ is not particularly limited, for example, 1 minute. The said non-fluororubber composition can shorten vulcanization time and can improve productivity by being the said structure. 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 {(M _H ) − (M _L )} × 0.9 + M _L This is the value obtained by. M _H and _{M L} is the value measured according to JIS K 6300-2.

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

(B) Fluoro rubber layer The fluoro rubber layer (B) is a layer formed from a fluoro rubber composition. The fluororubber composition contains fluororubber (b1).

The fluororubber (b1) may be unvulcanized fluororubber or vulcanized fluororubber.

Examples of the fluororubber (b1) include peroxide vulcanizable fluororubber, polyol vulcanizable fluororubber, polyamine vulcanizable fluororubber, and the like. The peroxide vulcanizable fluoro rubber is not particularly limited as long as it is a fluoro rubber having a peroxide vulcanizable site. The peroxide vulcanizable site is not particularly limited, and examples thereof include an iodine atom and a bromine atom.
The polyol vulcanizable fluoro rubber is not particularly limited as long as it is a fluoro rubber having a polyol vulcanizable part. The polyol vulcanizable part is not particularly limited, and examples thereof include a part having a vinylidene fluoride (VdF) unit. Examples of the method for introducing the vulcanization site include a method of copolymerizing a monomer that gives a vulcanization site during the polymerization of the fluororubber.

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

The fluororubber (b1) is more preferably a fluororubber containing a VdF unit (VdF fluoropolymer) from the viewpoints of heat resistance, compression set, workability, and cost. VdF-HFP fluororubber and VdF- More preferred is at least one fluororubber selected from the group consisting of HFP-TFE fluororubbers.
As said fluororubber (b1), what was demonstrated above is not restricted to 1 type, You may use 2 or more types, You may vulcanize these.

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

The fluororubber composition may contain a fluororubber (b1) and a fluororesin, and the fluororubber (b1) melts an unvulcanized fluororubber in the presence of a fluororesin and a vulcanizing agent. It may be a vulcanized fluoro rubber that is dynamically vulcanized under conditions. As described above, it is preferable to dynamically vulcanize the unvulcanized fluororubber because flexibility of the fluororubber layer formed from the fluororubber composition is improved.

Here, dynamically vulcanizing means to vulcanize dynamically unvulcanized fluoro rubber simultaneously with melt kneading using a Banbury mixer, a pressure kneader, an extruder or the like. Among these, an extruder such as a twin screw extruder is preferable because a high shear force can be applied. By dynamically vulcanizing, the phase structure of the fluororesin and the vulcanized fluoro rubber can be controlled.

In addition, the melting condition means that the temperature is equal to or higher than the temperature at which the fluororesin melts. The suitable temperature range varies 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. When the temperature is less than 120 ° C., the dispersion between the fluororesin and the fluoro rubber tends to be coarsened, and when it exceeds 330 ° C., the fluoro rubber tends to be thermally deteriorated.

The obtained fluororubber composition has a structure in which the fluororesin forms a continuous phase and the vulcanized fluororubber forms a dispersed phase, or the fluororesin and the vulcanized fluororubber form a co-continuity. Among them, it is preferable that the fluororesin has a structure in which a continuous phase is formed and the vulcanized fluoro rubber forms a dispersed phase.

Even when unvulcanized fluororubber initially forms a matrix, as the vulcanization reaction proceeds, the unvulcanized fluororubber becomes vulcanized fluororubber, which increases the melt viscosity and vulcanizes. The fluororubber becomes a dispersed phase or forms a co-continuous structure with the fluororesin.

Further, the fluororubber composition includes a co-continuous structure of the fluororesin and the vulcanized fluororubber in a part of the structure in which the fluororesin forms a continuous phase and the vulcanized fluororubber forms a dispersed phase. Also good.

When such a structure is formed, the vulcanized laminate obtained from the laminate of the present invention exhibits more excellent fuel barrier properties, heat resistance, chemical resistance and oil resistance. The average dispersed particle size of the vulcanized fluoro rubber is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm, and still more preferably 0.1 to 10 μm. If the average dispersed particle size is less than 0.01 μm, the fluidity tends to decrease, and if it exceeds 30 μm, the strength of the molded product tends to decrease.

The mass ratio of the fluororubber (b1) to the fluororesin in the fluororubber composition is preferably 3/97 to 80/20 (fluororubber (b1) / fluororesin). When the mass ratio of the fluororesin is smaller than 80/20 (fluororubber (b1) / fluororesin), the effect of improving the low fuel permeability and low temperature embrittlement resistance is reduced, while the mass ratio of the fluororesin is 3 If it exceeds / 97, the original rubber elasticity is remarkably impaired, the compression set is significantly deteriorated, and the hardness is remarkably increased. From the viewpoint of improving the low fuel permeability, low temperature embrittlement resistance and rubber elasticity in a well-balanced manner, the mass ratio (fluororubber (b1) / fluororesin) is more preferably 5/95 to 70/30. More preferred is ˜50 / 50.

The fluororesin is not particularly limited, but a fluororesin containing at least one fluorine-containing ethylenic polymer is preferable from the viewpoint of good compatibility with the VdF-based fluororubber. The fluorine-containing ethylenic polymer is not particularly limited, and for example, a polymer having a structural unit derived from at least one fluorine-containing ethylenic monomer is preferable. Examples of the fluorine-containing ethylenic monomer include tetrafluoroethylene (TFE) and formula (2):
CF ₂ = CF-Rf ² (2)
(Wherein Rf ² represents —CF ₃ or —ORf ³ (Rf ³ represents a perfluoroalkyl group having 1 to 5 carbon atoms)) and a perfluoroolefin such as a perfluoroethylenically unsaturated compound , Chlorotrifluoroethylene (CTFE), trifluoroethylene, hexafluoroisobutene, vinylidene fluoride (VdF), vinyl fluoride, formula (3):
_{^{_{_{CH 2 = CX 3 (CF 2}}}} ) n X 4 (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. Mention may be made of non-fluorine ethylenic monomers other than fluoroolefins. The non-fluorine ethylenic monomer is not particularly limited, and examples thereof include ethylene, propylene, and alkyl vinyl ethers. 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 polymer is preferable from the viewpoint of good fuel low permeability and cold resistance of the vulcanized laminate obtained from the laminate of the present invention.
(1) Ethylene / TFE copolymer (ETFE) consisting of TFE and ethylene
(2) TFE-perfluoro (alkyl vinyl ether) copolymer (PFA) or TFE / HFP copolymer (FEP) composed of TFE and a perfluoroethylenically unsaturated compound represented by formula (2)
(3) TFE / VdF / perfluoro (alkyl vinyl ether) copolymer comprising TFE, VdF and a perfluoroethylenically unsaturated compound represented by formula (2), or TFE / HFP / VdF copolymer (4 ) Polyvinylidene fluoride (PVdF)
(5) CTFE-TFE copolymer, or CTFE / TFE / perfluoroethylenically unsaturated compound copolymer composed of CTFE, TFE and a perfluoroethylenically unsaturated compound represented by formula (2), The fluorine-containing ethylenic polymer represented by (1), (2), or (5) is more preferable.

Next, preferred fluorine-containing ethylenic polymers (1), (2) and (5) will be described.
(1) ETFE
In the case of ETFE, it is preferable in that excellent low fuel permeability is exhibited. 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. Moreover, the 3rd component may be contained and the kind will not be limited if it can copolymerize with TFE and ethylene as a 3rd component. As the third component, usually 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 a fluorine atom, Rf ⁴ is an etheric oxygen atom) Among these, a fluorine-containing vinyl monomer represented by CH ₂ ═CX ⁵ Rf ⁴ is more preferred, and the carbon number of Rf ⁴ is 1 to The monomer of 8 is particularly preferred.

Specific examples of the fluorine-containing vinyl monomer represented by the above formula include 1,1-dihydroperfluoropropene-1, 1,1-dihydroperfluorobutene-1, 1,1,5-trihydroperfluoropentene-1. 1,1,7-trihydroperfluoroheptene-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, perfluorobutene-1, 3,3,3-trifluoro-2- (trifluoromethyl) propene -1,2,3,3,4,4,5,5- heptafluoro-1-pentene _(CH 2 = CFC _{_₂} CF ₂ CF ₂ H), and the like.

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

(2) PFA or FEP
In the case of PFA or FEP, heat resistance is particularly excellent, and it is preferable in that excellent low fuel permeability is exhibited. PFA or FEP is not particularly limited, but is preferably a copolymer comprising 70 to 99 mol% of TFE units and 1 to 30 mol% of a perfluoroethylenically unsaturated compound unit represented by the formula (2). More preferred is a copolymer comprising 80 to 97 mol% of TFE units and 3 to 20 mol% of a perfluoroethylenically unsaturated compound unit represented by the formula (2). If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease. Moreover, the fluorine-containing ethylenic polymer which consists of a perfluoroethylenically unsaturated compound represented by TFE and Formula (2) may contain the 3rd component, and TFE and Formula (2) are contained as a 3rd component. The kind is not limited as long as it can be copolymerized with the perfluoroethylenically unsaturated compound represented by ().

(5) In the case of CTFE-TFE copolymer or CTFE / TFE / perfluoroethylenically unsaturated compound copolymer CTFE-TFE copolymer, the molar ratio of CTFE units to TFE units is CTFE: TFE. = 2: 98 to 98: 2 is preferable, and 5:95 to 90:10 is more preferable. If the CTFE unit is less than 2 mol%, the low fuel permeability tends to deteriorate and the melt processing tends to be difficult, and if it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate. Further, it is preferable to copolymerize a perfluoroethylenically unsaturated compound, and the perfluoroethylenically unsaturated compound unit is 0.1 to 10 mol% based on the total of the CTFE unit and the TFE unit, and the CTFE unit and The total of TFE units is preferably 90 to 99.9 mol%. If the perfluoroethylenically unsaturated compound unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, fuel low permeability, heat resistance, It tends to be inferior in mechanical properties and productivity. Further, as the CTFE / TFE / perfluoroethylenically unsaturated compound copolymer, CTFE / TFE / perfluoro, where the perfluoroethylenically unsaturated compound is a perfluoroethylenically unsaturated compound represented by the formula (2), A (alkyl vinyl ether) copolymer is more preferred.

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

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

In the vulcanized laminate obtained from the laminate of the present invention, the vulcanized non-fluororubber layer and the vulcanized fluororubber layer are more firmly bonded, and therefore the fluororubber composition contains at least one kind. A polyfunctional compound may be added. The polyfunctional compound is a compound having two or more functional groups having the same or different structures in one molecule.

The functional group possessed by the polyfunctional compound is generally known to have 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 hydroxy group, and an epoxy group. Any functional group can be used. These functional group-containing compounds are expected not only to have high affinity with fluororubber, but also to react with the functional group of the fluororesin to further improve the adhesion.

The fluororubber composition preferably further contains a vulcanizing agent. The vulcanizing agent can be appropriately selected depending on the vulcanization system of the fluororubber to be blended. Specifically, a peroxide vulcanizing agent, a polyol vulcanizing agent and the like can be selected according to the purpose. It does not specifically limit as said peroxide type | system | group vulcanizing agent, For example, an organic peroxide can be mentioned. The organic peroxide is preferably one that easily generates a peroxy radical in the presence of heat or a redox system. For example, 1,1-bis (t-butylperoxy) -3,5,5-trimethyl Cyclohexane, 2,5-dimethylhexane-2,5-dihydroxy peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxy) -P-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, benzoylper Oxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t -Butyl peroxyisopropyl carbonate and the like can be exemplified. Of these, dialkyl compounds are preferred. In general, the amount used is appropriately selected from the amount of active —O—O—, the decomposition temperature, and the like. The amount used is usually from 0.1 to 15 parts by weight, preferably from 0.3 to 5 parts by weight, based on 100 parts by weight of the fluororubber.

When using an organic peroxide as a vulcanizing agent, a vulcanization aid or a co-vulcanizing agent may be used in combination. The vulcanization aid or co-vulcanization agent is not particularly limited, and examples thereof include the above-described vulcanization aid and co-vulcanization agent. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of vulcanizability and physical properties of the vulcanizate.

The blending amount of the vulcanizing aid and co-vulcanizing agent is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 6 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of fluororubber. Part is more preferred. If the vulcanizing agent is less than 0.2 parts by mass, the vulcanization density tends to be low and the compression set tends to be large. If the vulcanizing agent exceeds 10 parts by mass, the vulcanization density becomes too high and cracks occur during compression. It tends to be easier.

The polyol vulcanizing agent is not particularly limited, and for example, a polyhydroxy compound, particularly a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance. The polyhydroxy aromatic compound is not particularly limited. For example, 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-dihydroxynaphthalene, 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) te Lafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 Examples include ', 5,5'-tetrabromobisphenol A. These polyhydroxy aromatic compounds may be an alkali metal salt, an alkaline earth metal salt, or the like, but when the copolymer is coagulated using an acid, it is preferable not to use the metal salt.

As the polyol-based vulcanizing agent, a polyhydroxy compound is preferable because the compression set of the fluorinated rubber after vulcanization is small and the moldability is excellent, and a polyhydroxy aromatic compound is preferable because of excellent heat resistance. More preferred is bisphenol AF.

The polyol vulcanizing agent is preferably added in an amount of 0.2 to 10 parts by weight, more preferably 0.5 to 6 parts by weight, based on 100 parts by weight of fluororubber. More preferably, it is part by mass. If the blending amount is less than 0.2 parts by mass, the vulcanization density tends to be low and the compression set tends to be large, and if it exceeds 10 parts by mass, the vulcanization density becomes too high and cracks during compression. It tends to be easier.

Further, a vulcanization accelerator may be used in combination with a polyol vulcanizing agent. When a vulcanization accelerator is used, the vulcanization reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.

The fluororubber composition is prepared by adding usual additives, for example, fillers, processing aids, plasticizers, colorants, stabilizers, adhesion aids, acid acceptors, release agents, as necessary. Various additives such as molds, conductivity-imparting agents, thermal conductivity-imparting agents, surface non-adhesives, flexibility-imparting agents, heat resistance improvers, flame retardants, etc. can be blended, and are different from those mentioned above One or more of these vulcanizing agents and vulcanization accelerators may be blended.

The fluororubber composition is a rubber that is generally used with fluororubbers and, if necessary, other additives such as vulcanizing agents, vulcanizing aids, co-vulcanizing agents, vulcanization accelerators, and fillers. It can be obtained by kneading using a kneading apparatus. 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 has a simple structure and can be provided with low temperature, chemical resistance, and flexibility despite its low cost, and therefore only from the fluororubber layer (B) and the non-fluororubber layer (A). It is preferable that it is the laminated body of 2 layers which becomes.
In the laminate of the present invention, the non-fluororubber layer (A) and the fluororubber layer (B) are provided on one side of the fluororubber layer (B) (the side on which the non-fluorine rubber layer (A) is not laminated). It may be a laminate of three or more layers in which different polymer layers (C) are laminated, or non-fluorine rubber layer (A) on one side (the side on which no fluororubber layer (B) is laminated). It may be a laminate of three or more layers in which polymer layers (C) different from the fluororubber layer (A) and the fluororubber layer (B) are laminated.
Moreover, the laminated body of 3 or more layers by which the non-fluororubber layer (A) is laminated | stacked on both sides of the fluororubber layer (B) may be sufficient, and a fluororubber layer ( It may be a laminate of three or more layers in which B) is laminated.
It does not specifically limit as said polymer layer (C), What is necessary is just to determine suitably according to the use etc. of the vulcanized laminated body obtained from the laminated body of this invention.

The vulcanized laminate of the present invention is obtained by heat-treating a laminate comprising a fluororubber layer (B) and a non-fluororubber layer (A) laminated on the fluororubber layer (B), The vulcanized non-fluororubber layer (A1) and the vulcanized fluororubber layer (B1) are bonded by vulcanization.

By subjecting the laminate of the present invention comprising the fluororubber layer (B) and the non-fluororubber layer (A) laminated on the fluororubber layer (B), the vulcanized non-fluororubber layer (A1) ) And a vulcanized fluoro rubber layer (B1) can be obtained.

The vulcanized non-fluorinated rubber layer (A1) is obtained by vulcanizing the non-fluorinated rubber layer (A) by the heat treatment.
The vulcanized fluoro rubber layer (B1) is obtained by heat-treating the fluoro rubber layer (B). When the heat treatment is performed on the unvulcanized fluororubber layer (B), the vulcanized fluororubber layer (B1) is the same as the fluororubber (b1) in the fluororubber layer (B). It is vulcanized by.
By the heat treatment, a vulcanized laminate in which the non-fluorinated rubber layer (A) is vulcanized and the vulcanized non-fluorinated rubber layer (A1) and the vulcanized fluororubber layer (B1) are vulcanized and bonded is obtained.

The heat treatment can be carried out by stacking the unvulcanized non-fluorinated rubber layer (A) and the vulcanized or unvulcanized fluororubber layer (B) and heat-treating them. By performing the heat treatment, the non-fluorinated rubber layer (A) can be vulcanized. Moreover, when the fluororubber layer (B) is unvulcanized, the fluororubber layer (B) can also be vulcanized.

As the heat treatment conditions, at least the non-fluorinated rubber layer (A) is vulcanized. When the fluororubber layer (B) is uncrosslinked, it is carried out under conditions for vulcanizing the non-fluororubber layer (A) and the fluororubber layer (B).
The specific conditions for the heat treatment may be appropriately determined depending on the type of the vulcanizing agent to be used, but it is usually performed by heating at a temperature of 150 to 300 ° C. for 1 minute to 24 hours.

As a heat treatment method, at least a method capable of vulcanizing the non-fluorinated rubber layer (A) is used. When the fluororubber layer (B) is uncrosslinked, a method capable of vulcanizing the non-fluororubber layer (A) and the fluororubber layer (B) is used.
As a heat treatment method, a vulcanization method for heating can be adopted, and not only a method usually used such as steam vulcanization but also a vulcanization method under normal pressure, pressure, and reduced pressure, Moreover, the vulcanization method in the air may be used.

The vulcanized laminate of the present invention is prepared by, for example, extruding a fluororubber composition and a non-fluororubber composition with an extruder to produce an unvulcanized non-fluororubber sheet and an unvulcanized fluororubber sheet, respectively. The unvulcanized non-fluorinated rubber sheet and the unvulcanized fluororubber sheet can be overlapped and inserted into a heated mold for vulcanization and adhesion.

In addition, the vulcanized laminate of the present invention comprises a fluororubber composition and a non-fluororubber composition that are co-extruded in two layers or two or more layers with an extruder, or inside with two or two or more extruders. It is also possible to obtain an unvulcanized laminate composed of an inner layer and an outer layer by extruding the outer layer on the layer and extruding them with an extruder and then vulcanizing and bonding them by heating.

Furthermore, the vulcanized laminate of the present invention comprises, for example, a laminate of a vulcanized fluororubber and a fluororesin obtained by the above-described dynamic vulcanization treatment and an unvulcanized non-fluororubber sheet. In addition, it can be obtained by vulcanization adhesion by inserting it into a heated mold.

The vulcanized laminate of the present invention is a laminate having low fuel permeability, low temperature embrittlement resistance, chemical resistance, oil resistance, and heat resistance, and is useful as a hose, tube, container, sealing material, etc. around the fuel. In particular, it is useful as a fuel transport hose or tube for automobile engines and peripheral devices, AT devices, fuel systems and peripheral devices.

The vulcanized laminate of the present invention is a hose or tube, and it is preferable that the vulcanized fluoro rubber layer (B1) is laminated inside the vulcanized non-fluoro rubber layer (A1).
For example, a fuel transport hose or tube has a laminated structure in which a vulcanized fluororubber layer (A1) is disposed in the innermost layer of the hose or tube, and a vulcanized non-fluororubber layer (B1) is disposed in the outer layer thereof. It is preferable.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Hereinafter, it describes about the fluororesin used in an Example and a comparative example, and its measuring method.

(Vulcanization characteristics)
With respect to the obtained non-fluororubber composition, a maximum torque value (M _H ) and a minimum torque value (M) at 160 ° C. using a curast meter type II (model number: JSR Clast Meter, manufactured by JSR). _L ) was measured, and the induction time (T ₁₀ ) and the optimum vulcanization time (T ₉₀ ) were determined. The measurement results are shown in Table 2. _{Incidentally, T 10} _is - a _{{(M H) (M L} )} × 0.1 + M L become _{time, T 90} _is - a _{{(M H) (M L} )} × 0.9 + M L is time, _{M H} and _{M L} is the value measured according to JIS K 6300-2.

(Adhesive strength)
The obtained laminate was cut into strips each having a width of 10 mm, a length of 40 mm, and a set of 3 pieces, and a release film was peeled off to prepare a test piece that was grasped. About this test piece, using an autograph (AGS-J 5 kN, manufactured by Shimadzu Corporation), in accordance with the method described in JIS K 6256 (adhesion test method for cross-linked rubber), at 25 ° C., 50 mm / min. A peel test was performed at a tensile speed. The adhesiveness was evaluated according to the following criteria by observing the peeling mode. The obtained results are shown in Table 2.

Example 1
(Preparation of fluororubber composition and production of fluororubber sheet)
The materials shown in Table 1 below were kneaded using an 8 inch open roll adjusted to 25 ° C. to obtain a sheet-like fluororubber composition (fluororubber sheet) having a thickness of about 3 mm.

(Preparation of non-fluorinated rubber composition and production of unvulcanized non-fluorinated rubber sheet)
The materials shown in Table 2 below were kneaded using an 8-inch open roll whose temperature was adjusted to 25 ° C. to obtain a sheet-like non-fluororubber composition (non-fluororubber sheet) having a thickness of about 3 mm.

(Production of laminate)
The fluoro rubber composition (fluoro rubber sheet) having a thickness of about 3 mm and the non-fluoro rubber composition (non-fluoro rubber sheet) having a thickness of about 3 mm are overlapped, and a width of about 10 to 15 mm is provided at one end. After a resin film (10 μm thick release film) is sandwiched between both sheets, the resulting sheet is inserted into a mold with a metal spacer so that the thickness is 2 mm, and pressed at 160 ° C. for 45 minutes. Thus, a sheet-like laminate was obtained.

(Examples 2 to 9 and Comparative Examples 1 to 3)
A non-fluorinated rubber composition was prepared and vulcanized in the same manner as in Example 1 except that the type and addition amount of the non-fluorinated rubber composition (non-fluorinated rubber sheet) were changed as shown in Table 2. Characteristics were evaluated. Moreover, the laminated body was produced like Example 1 and the adhesiveness of the laminated body was evaluated. The results are shown in Table 2.

(Adhesion evaluation)
◯: The non-fluorinated rubber sheet or the fluorinated rubber sheet after vulcanization at the interface of the laminate failed to peel off at the interface.
X: Peeled relatively easily at the interface of the laminate.

The laminate of the present invention is useful as a hose, a tube, a container, a sealing material and the like around a fuel, and in particular, a hose or a tube for transporting a fuel such as an automobile engine and a peripheral device, an AT device, a fuel system and a peripheral device. As useful as.

Claims

A laminate comprising a fluororubber layer (B) and a non-fluororubber layer (A) laminated on the fluororubber layer (B),
The non-fluorine rubber layer (A) is a layer formed from a non-fluorine rubber composition,
The non-fluorinated rubber composition comprises an unvulcanized non-fluorinated rubber (a1),
1,8-diazabicyclo (5.4.0) undecene-7 salt and at least one compound (a2) selected from the group consisting of 1,8-diazabicyclo (5.4.0) undecene-7,
Magnesium oxide (a3), and
Containing silica (a4),
The laminate, wherein the fluororubber layer (B) is a layer formed from a fluororubber composition containing the fluororubber (b1).
The laminate according to claim 1, wherein the unvulcanized non-fluorinated rubber (a1) is acrylonitrile-butadiene rubber (NBR) or a hydride thereof.
The fluororubber (b1) is at least one fluororubber selected from the group consisting of vinylidene fluoride-hexafluoropropylene fluororubber and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluororubber. Item 3. A laminate according to item 1 or 2.
4. The non-fluorine rubber composition, wherein the compounding amount of the compound (a2) is 0.7 to 5.0 parts by mass with respect to 100 parts by mass of the unvulcanized non-fluorine rubber (a1). Laminated body.
The non-fluorine rubber composition further includes
The laminate according to claim 1, 2, 3, or 4, comprising at least one vulcanizing agent (a5) selected from the group consisting of a sulfur vulcanizing agent and a peroxide vulcanizing agent.
The non-fluorine rubber composition further includes
The laminate according to claim 1, 2, 3, 4, or 5, comprising at least one metal salt (a6) selected from the group consisting of a carbamic acid metal salt and a thiazole metal salt.
The laminate according to claim 1, 2, 3, 4, 5 or 6, wherein the compound (a2) is 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride.
Obtained by heat-treating the laminate according to claim 1, 2, 3, 4, 5, 6 or 7,
A vulcanized laminate in which a vulcanized non-fluorinated rubber layer (A1) and a vulcanized fluororubber layer (B1) are bonded by vulcanization.
Hose or tube,
The vulcanized laminate according to claim 8, wherein the vulcanized fluoro rubber layer (B1) is laminated inside the vulcanized non-fluoro rubber layer (A1).