JP2010000610A - Laminate of fluorine-containing polymer with vulcanized rubber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method which enables vulcanization adhesion of a composition containing fluorine resin with a nitrile- or epichlorohydrin-based rubber without an arrangement of an adhesive layer or a special surface treatment. <P>SOLUTION: A laminate is formed by vulcanization adhesion of the composition containing fluorine resin with an unvulcanized rubber composition. The composition containing fluorine resin is obtained by crosslinking an ethylene-tetrafluoroethylene(TFE) copolymer dynamically with at least one fluorine rubber under conditions of melting the copolymer and melt-kneading the resultant composition with a composition containing a fluorine polymer. The unvulcanized rubber composition is a nitrile-based rubber composition comprising an at least one adhesiveness-imparting agent selected from amine, quaternary ammonium salt and quaternary phosphonium salt-based adhesiveness-imparting agents, and a vulcanizing agent, or an epichlorohydrin-based rubber composition comprising at least one adhesiveness-imparting agent selected from the above, an acid-receiving agent and a vulcanizing agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a laminate of a fluoropolymer and a vulcanized rubber. More specifically, a composition containing a fluororesin and an unvulcanized rubber made of a nitrile rubber or an epihalohydrin rubber are directly added without an adhesive layer. The present invention relates to a laminated body and a laminated hose that are bonded with sulfur. Such a laminated body and laminated hose are used for, for example, an automobile fuel hose.

  Conventionally, hoses used for fuel oils such as gasoline, and chemical hoses used for acids, alkalis, organic solvents, etc. are layers made of fluorinated rubber vulcanizates that are highly resistant to chemicals and organic solvents. A multilayer hose in which a layer made of a vulcanized product of nitrile rubber or epihalohydrin rubber is disposed on a layer directly laminated thereon has been suitably used. In particular, in the case of automobile fuel hoses that require sour gasoline resistance and gasoline permeation resistance, a layer made of a fluorinated rubber vulcanizate is disposed as the innermost material, and the layer directly laminated on the hose is oil resistant. A multilayer hose having a layer made of a vulcanizate of nitrile rubber or epichlorohydrin rubber having excellent properties has been suitably used. However, due to fuel evaporation regulations that have been tightened year by year, a material with high gasoline permeability resistance has been required as a material for fuel oil hoses. Use is desired.

  In the case of a multilayer hose using rubber and resin, the adhesion between rubber and resin is the most important issue. It is known that fluororesin, nitrile rubber and epichlorohydrin rubber have poor adhesion even if they are vulcanized and bonded as they are. As a means for improving the adhesion between the fluororesin and the epichlorohydrin rubber, for example, epichlorohydrin rubber may be added to 1,8-diazabicyclo- (5,4,0) -undecene-7 (hereinafter referred to as DBU) or a derivative thereof. Means for blending various additives and vulcanizing and bonding have been proposed (see Patent Documents 1 and 2). On the other hand, various methods for improving the adhesion by treating the surface of the fluorine-based member have been tried. Known methods for treating fluorine-based members include mechanical surface roughening, chemical etching, and discharge treatment methods such as plasma and corona. Of these, the surface treatment by the plasma discharge treatment method is attracting attention as a surface treatment method for fluorine-based members because it is clean and has a high degree of freedom for surface modification, and the plasma-treated fluorine-based member and epichlorohydrin rubber are directly used. A method for vulcanization bonding has also been proposed (see Patent Documents 3 and 4).

JP-A-8-294998 JP-A-8-294999 JP 2006-272739 A JP 2006-272741 A

  However, in the method of adding vulcanization adhesion by adding an additive such as DBU or a derivative thereof to the epichlorohydrin rubber, the adhesive strength depends on the content of the vinylidene fluoride unit of the fluorine-based member. , Fluorine-based members with a reduced content of vinylidene fluoride units in order to increase fuel impermeability, and fluorine-based members that do not contain vinylidene fluoride units such as ethylene-tetrafluoroethylene copolymer significantly reduce the adhesive strength. There is a problem to do. In addition, in the method of bonding the surface of the fluorine-based member by plasma treatment, a large-scale processing apparatus must be introduced, and furthermore, the treatment surface of the fluorine-based member is likely to be altered, so that plasma treatment is vulcanized and bonded. There is a problem that the adhesive strength is lowered by the elapsed time until.

  The present invention has been made in view of the above circumstances, and a composition containing a fluororesin and a nitrile rubber or an epichlorohydrin rubber are directly vulcanized and bonded without using an adhesive layer or a special surface treatment. The object is to obtain a laminate.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have heretofore made a thermoplastic fluoropolymer and a nitrile rubber or an epihalohydrin rubber with a small amount of vinylidene fluoride units or no vinylidene fluoride units. It was difficult to vulcanize and bond directly. However, as a composition containing a fluororesin, at least one part obtained by dynamically cross-linking at least one fluororubber under the melting conditions of an ethylene-TFE copolymer composed of TFE (tetrafluoroethylene) and ethylene Attaching amine-based adhesives to nitrile rubber or epihalohydrin rubber compositions using a cross-linked fluororubber that has been cross-linked and a fluororesin composition obtained by melt-kneading a composition containing the fluororesin and a composition containing a fluoropolymer The vulcanization adhesion is made possible by including at least one adhesion-imparting agent selected from a quaternary ammonium salt-based adhesion imparting agent and a quaternary phosphonium salt-based adhesion imparting agent, thereby completing the present invention. It came to.

The present invention provides a laminate comprising (A) a composition containing a fluororesin and (B) a vulcanized and bonded unvulcanized rubber composition.
(A) a composition containing a fluororesin,
At least one fluororubber is dynamically cross-linked under a melting condition of an ethylene-TFE copolymer composed of TFE and ethylene, and the resulting cross-linked cross-linked fluororubber and a composition containing the fluororesin And a fluororesin composition obtained by melt-kneading a composition containing a fluoropolymer,
The (B) unvulcanized rubber composition is
(B1) A nitrile rubber composition containing at least one kind of adhesion-imparting agent and vulcanizing agent selected from amine-based adhesion imparting agents, quaternary ammonium salt-based adhesion imparting agents, and quaternary phosphonium salt-based adhesion imparting agents, or B2) An epihalohydrin rubber composition containing at least one kind of adhesion-imparting agent selected from amine-based adhesion imparting agents, quaternary ammonium salt-based adhesion imparting agents, and quaternary phosphonium salt-based adhesion imparting agents, acid acceptors and vulcanizing agents. It is the laminated body characterized by these.

The present invention also relates to (A) a cross-linked fluororubber in which at least one fluororubber is dynamically cross-linked under the melting condition of an ethylene-TFE copolymer comprising TFE and ethylene, and at least a part of the obtained cross-linked fluororubber is obtained. And a fluororesin composition obtained by melt-kneading a composition containing the fluororesin and a composition containing a fluoropolymer, and (B1) an amine-based adhesion imparting agent, a quaternary ammonium salt-based adhesion imparting agent, and a quaternary phosphonium salt-based Nitrile-based rubber composition containing at least one adhesion-imparting agent selected from an adhesion-imparting agent and a vulcanizing agent, or (B2) amine-based adhesion imparting agent, quaternary ammonium salt-based adhesion imparting agent, quaternary phosphonium salt-based adhesion A laminate comprising a step of vulcanizing and bonding an epihalohydrin rubber composition containing at least one adhesion-imparting agent selected from an imparting agent, an acid acceptor and a vulcanizing agent It is a manufacturing method.

  In the laminate or the laminate manufacturing method of the present invention, the cost is reduced because there is no step of providing an adhesive layer, and it is not necessary to perform plasma treatment on the surface of the fluorine-based member. It is very preferable because it is not necessary to vulcanize and bond immediately after the plasma treatment.

The present invention is described in detail below.
First, a composition containing a fluororesin that forms a laminate that is vulcanized and bonded together with an unvulcanized rubber composition will be described.
The composition containing the fluororesin of the present invention is obtained by dynamically crosslinking at least one fluororubber under the melting condition of an ethylene-TFE copolymer composed of TFE and ethylene, and at least a part of the resulting composition is crosslinked. A fluororesin composition obtained by melt-kneading a composition containing a cross-linked fluororubber and the fluororesin and a composition containing a fluoropolymer. As a manufacturing method of said fluororesin composition, the method of Unexamined-Japanese-Patent No. 2007-277348 etc. are disclosed, for example.

  (A) A composition containing a fluororesin is a cross-linked fluororubber in which at least one fluororubber is dynamically cross-linked under the melting condition of an ethylene-TFE copolymer composed of TFE and ethylene, and at least partly cross-linked And a step of obtaining a composition containing the fluororesin (Step A) and at least one obtained by dynamically crosslinking at least one fluororubber under the melting condition of an ethylene-TFE copolymer comprising TFE and ethylene. It is produced in a process including at least a process (process B) of melt-kneading a composition containing a cross-linked fluororubber having a cross-linked part and the fluororesin and a composition containing a fluoropolymer to obtain a fluororesin composition. .

First, step A will be described.
The ethylene-TFE copolymer can be obtained by copolymerizing TFE and ethylene, and the production method is not particularly limited. The content molar ratio of the TFE unit to the ethylene unit is preferably 20:80 to 90:10. Moreover, there is no problem even if other components that can be copolymerized with TFE and ethylene are contained as components.

  When the laminate of the present invention is used as a member of a fuel hose for automobiles, from the viewpoints of low fuel permeability and flexibility, the structural units of the fluoropolymer are tetrafluoroethylene units, ethylene units, hexafluoropropylene. A copolymer having a unit as a main component is preferred.

Other components capable of copolymerization 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- (tri fluoromethyl) propene -1,2,3,3,4,4,5,5- heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 2 H) can be exemplified.

  Examples of the fluororubber include perfluorofluororubber, non-perfluorofluororubber, and fluorine-containing thermoplastic elastomer.

  Examples of the perfluorofluororubber include a TFE / perfluoro (alkyl vinyl ether) (hereinafter referred to as PAVE) copolymer, a TFE / hexafluoropropylene (HFP) / PAVE copolymer, and the like.

  Examples of the non-perfluorofluororubber include vinylidene fluoride (VdF) -based polymers and TFE / propylene-based copolymers, which are each independently or arbitrarily within a range not impairing the effects of the present invention. They can be used in combination.

  Moreover, what was illustrated as said perfluoro fluororubber or non-perfluoro fluororubber is the structure of a main monomer, and what copolymerized the monomer for crosslinking, a modified monomer, etc. can be used suitably. As the crosslinking monomer or the modifying monomer, a known crosslinking monomer such as an iodine atom, bromine atom, or one containing a double bond, a transfer agent, a modified monomer such as a known ethylenically unsaturated compound, or the like can be used. .

  Specific examples of the VdF polymer include a VdF / HFP copolymer, a VdF / TFE / HFP copolymer, a VdF / TFE / propylene copolymer, and a VdF / ethylene / HFP copolymer. VdF / TFE / PAVE copolymer, VdF / PAVE copolymer, VdF / chlorotrifluoroethylene (hereinafter referred to as CTFE) copolymer, and the like. More specifically, it is preferably a fluorine-containing copolymer composed of 25 to 85 mol% of VdF and 75 to 15 mol% of at least one other monomer copolymerizable with VdF, more preferably , A fluorine-containing copolymer comprising 50 to 80 mol% of VdF and 50 to 20 mol% of at least one other monomer copolymerizable with VdF.

  Here, as at least one other monomer copolymerizable with VdF, for example, TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetra Examples thereof include fluorine-containing monomers such as fluoroisobutene, PAVE and vinyl fluoride, and non-fluorine monomers such as ethylene, propylene and alkyl vinyl ether. These can be used alone or in any combination.

  The fluorine-containing thermoplastic elastomer is not particularly limited, but may be a fluorine-containing multi-segmented polymer in which an elastomeric polymer segment and a non-elastomeric polymer segment are bonded in the form of a block or graft in one molecule. Preferably, the fluorinated thermoplastic elastomer is composed of a triblock polymer composed of one elastomeric polymer segment and two non-elastomeric polymer segments, at least one of which is a fluorinated polymer segment.

  In the present invention, at least one type of fluororubber is dynamically cross-linked under the melting condition of an ethylene-TFE copolymer composed of TFE and ethylene to obtain a cross-linked fluororubber at least partially crosslinked. Dynamically crosslinking means that the fluororubber is dynamically crosslinked simultaneously with melt kneading using a Banbury mixer, a pressure kneader, an extruder, or the like. Among these, it is preferable to use an extruder such as a twin screw extruder because a high shear force can be applied. In this step, a composition in which the cross-linked fluororubber is uniformly dispersed in the fluororesin can be obtained by dynamically performing a cross-linking treatment under the melting condition of the fluororesin.

  Further, the melting condition means a temperature at which the ethylene-TFE copolymer and the fluororubber are melted. The melting point of the ethylene-TFE copolymer is preferably 150 to 310 ° C, more preferably 150 to 290 ° C, and further preferably 170 to 250 ° C. When the melting point of the ethylene-TFE copolymer is less than 150 ° C., the heat resistance of the resulting composition containing the fluororesin tends to decrease. In the case of dynamically crosslinking, it is necessary to set the melting temperature to be equal to or higher than the melting point of the ethylene-TFE copolymer.

The weight ratio of the ethylene-TFE copolymer to the fluororubber or fluorine-containing thermoplastic elastomer added to the ethylene-TFE copolymer is preferably in the range of 10/90 to 95/5, more Preferably it is in the range of 20/80 to 80/20. The weight ratio of fluororubber or fluorine-containing thermoplastic elastomer added to the fluororesin is 5% by weight.
If the amount is less than 90% by weight, the flexibility of the resulting fluororesin composition tends to decrease, and if it exceeds 90% by weight, the fluidity of the resulting fluororesin composition tends to deteriorate and the moldability tends to decrease. .

  It is preferable to use a crosslinking agent when dynamically crosslinking treatment, but the type of the crosslinking agent is not particularly limited, and may be appropriately selected depending on the type of fluororubber to be crosslinked and the melt-kneading conditions. it can.

  The cross-linking system used in the present invention may be appropriately selected depending on the type of the cure site or the use of the molded product obtained when the fluororubber contains a cross-linkable group (cure site). As the crosslinking system, any of a polyol crosslinking system, an organic peroxide crosslinking system, and a polyamine crosslinking system can be employed.

As the polyol crosslinking agent, a compound conventionally known as a crosslinking agent for fluororubber can be used, and a polyhydroxy compound, particularly a polyhydroxy aromatic compound is preferably used.
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) Trafluorodichloropropane, 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.

  Examples of the polyamine crosslinking agent include polyamine compounds such as hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, and 4,4′-bis (aminocyclohexyl) methanecarbamate. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.

  The organic peroxide cross-linking agent may be an organic peroxide that can easily generate a peroxy radical in the presence of heat or a redox system. Specifically, for example, 1,1-bis (T-Butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, 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, benzoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t-butylperoxyiso Examples thereof include propyl carbonate. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is preferable.

  Among these, a polyhydroxy compound is preferable from the viewpoint of small compression set such as a molded article to be obtained and excellent moldability, a polyhydroxy aromatic compound is more preferable because of excellent heat resistance, and bisphenol AF is preferable. Further preferred.

  In the polyol crosslinking system, a crosslinking accelerator is usually used in combination with the polyol crosslinking agent. When a crosslinking accelerator is used, the crosslinking reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.

  An onium compound is generally used as a crosslinking accelerator for a polyol crosslinking system. The onium compound is not particularly limited, and examples thereof include ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and monofunctional amine compounds. Of these, quaternary ammonium salts and quaternary phosphonium salts are preferred.

  The quaternary ammonium salt is not particularly limited. For example, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5, 4,0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5 , 4,0] -7-Undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5,4,0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 , 4,0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [ , 4,0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [5]. , 4,0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8-benzyl- 1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8- (3 -Phenylpropyl) -1,8-diazabicyclo [5,4,0] -7-undecenium chloride and the like. Among these, DBU-B is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

  The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl. Examples thereof include -2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and among these, benzyltriphenylphosphonium chloride (BTPPC) is preferable from the viewpoint of crosslinkability and physical properties of the crosslinked product.

Examples of organic peroxide crosslinking accelerators include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N′-m-phenylenebismaleimide, and dipropargyl. Terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3, 5-triazine-2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N,
N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N, N, N ′, N′-tetraallylphthalamide, N, N, N ′, N′-tetraallylmalonamide, Examples thereof include trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl phosphite and the like. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

  The addition amount of the crosslinking agent and the crosslinking accelerator is preferably an amount adjusted so that the 90% completion time T90 at the temperature when dynamically crosslinking is performed is 2 to 6 minutes. More preferably, the amount is adjusted so that the 90% completion time T90 is 3 to 5 minutes. If the optimum vulcanization time T90 is less than 2 minutes, the dispersion of the crosslinked fluororubber tends to be uneven and coarse, and if it exceeds 6 minutes, it takes a long time for the fluororubber to crosslink. And there is a tendency to not completely crosslink.

  Here, the 90% completion time T90 is obtained by obtaining a vulcanization curve at the temperature during dynamic vulcanization using JSR type curlastometer type II and V type at the time of primary press vulcanization of fluoro rubber. The time to reach 90% of the maximum torque value is the 90% vulcanization completion time (T90).

  As a specific method for determining the addition amount of the crosslinking agent and the crosslinking accelerator, the vulcanization 90% completion time T90 at 170 ° C. is 2 to 6 minutes, preferably 3 to 5 minutes with respect to 100 parts by weight of the fluororubber. First, X parts by weight of the crosslinking agent and Y parts by weight of the crosslinking accelerator are determined.

Next, based on the amount of X and Y,
(I) Amount of cross-linking agent: X weight, Amount of cross-linking accelerator: 0.2Y-0.5Y part by weight, preferably 0.3Y-0.4Y part by weight, or (ii) Amount of cross-linking agent: 2X- 5X parts by weight, amount of crosslinking accelerator: 0.4Y to 2.5Y parts by weight are the preferred addition amounts of the crosslinking agent and crosslinking accelerator in the present invention.

  When the cross-linking accelerator is less than 0.2 Y parts by weight, the cross-linking of the fluororubber does not proceed sufficiently, and the heat resistance and oil resistance of the resulting fluororesin composition tend to be reduced. When it exceeds, there exists a tendency for the mechanical strength of the fluororesin composition obtained to fall.

  The obtained composition can have a structure in which the fluororesin forms a continuous phase and the cross-linked fluororubber forms a dispersed phase, or a structure in which the fluororesin and the cross-linked rubber form a co-continuity.

  Even when the rubber initially formed a matrix, as the cross-linking reaction proceeds, the rubber becomes a cross-linked fluororubber, so that the melt viscosity increases and the cross-linked fluoro rubber becomes a dispersed phase, or with the fluororesin. It forms a co-continuous phase.

  In addition, when fluororubber is added in step B, it is more difficult for the rubber of the finally obtained fluororesin composition to form a continuous phase when the fluororubber is completely cross-linked by dynamic cross-linking in step A. Therefore, it is preferable. Here, the term “crosslinking is completed” refers to a state of kneading for a time longer than T90 described above.

Next, step B will be described.
The dispersibility of the crosslinked fluororubber in the composition can be further improved by further melt-kneading the composition obtained in step A with a fluoropolymer. In addition, when the cross-linked fluororubber in the composition obtained in step A has a structure that forms a co-continuity, the cross-linked fluororubber becomes a structure that forms a dispersed phase by being melt-kneaded in step B. It is.

  Examples of the fluoropolymer used in Step B include an ethylene-TFE copolymer or fluororubber. The fluoropolymer in step B may be the same as or different from the ethylene-TFE copolymer or fluororubber used in step A, but is compatible with the composition obtained in step A. From this point, it is preferably the same as the ethylene-TFE copolymer or fluororubber used in Step A. The amount of the fluoropolymer added to the composition obtained in Step A in Step B is not particularly limited.

  For the melt kneading of the composition obtained in Step A and the ethylene-TFE copolymer, a Banbury mixer, a pressure kneader, an extruder, or the like can be used. The melting temperature is preferably 150 to 310 ° C, and more preferably 170 to 250 ° C. If the temperature is less than 150 ° C., the fluororesin does not sufficiently melt and the resin phase tends to be non-uniform, and if it exceeds 310 ° C., the fluororubber tends to thermally deteriorate.

  When the fluoropolymer is fluororubber, examples of the fluororubber include the above-described fluororubber. The fluororesin composition obtained is that the step B is a step of dynamically cross-linking the fluororubber in the presence of the composition obtained in the step A to obtain a cross-linked fluororubber at least a part of which is cross-linked It is preferable from the viewpoint of improving the mechanical properties. As dynamic crosslinking conditions, the same conditions as described above can be employed.

  Further, when the fluoropolymer is fluororubber and the crosslinking is dynamically performed, it is preferable to use a crosslinking agent and, if necessary, a crosslinking accelerator. The types and addition amounts of the crosslinking agent and crosslinking accelerator are preferably the types and addition amounts described above.

  The obtained fluororesin composition can have a structure in which the fluororesin forms a continuous phase and the cross-linked fluororubber forms a dispersed phase, or a structure in which the fluororesin and the cross-linked fluororubber form a co-continuity. Among these, it is preferable that the fluororesin has a structure in which a continuous phase is formed and the crosslinked fluororubber forms a dispersed phase.

  In addition, the fluororesin composition of the present invention has a preferred form in which a fluororesin forms a continuous phase and a cross-linked fluororubber forms a disperse phase. It may contain a continuous structure.

  A fluoropolymer may be further added to the obtained fluororesin composition and melt kneaded.

Secondly, an unvulcanized rubber composition that forms a laminate that is vulcanized and bonded together with a composition containing a fluororesin will be described.
Examples of the unvulcanized rubber composition of the present invention include a nitrile rubber composition comprising a nitrile rubber as a rubber component and an epihalohydrin rubber composition comprising an epihalohydrin rubber as a rubber component. More specifically, a nitrile rubber composition containing at least one kind of adhesion-imparting agent selected from an amine-based adhesion imparting agent, a quaternary ammonium salt-based adhesion imparting agent, and a quaternary phosphonium salt-based adhesion imparting agent, and a vulcanizing agent, Or an epihalohydrin-based rubber composition containing at least one kind of adhesion-imparting agent selected from amine-based adhesion imparting agents, quaternary ammonium salt-based adhesion imparting agents, and quaternary phosphonium salt-based adhesion imparting agents, acid acceptors and vulcanizing agents. is there.

  First, the adhesion imparting agent contained in common in the nitrile rubber composition or epihalohydrin rubber composition used in the present invention will be described in detail. In the present invention, at least one kind of adhesion imparting agent selected from an amine-based adhesion imparting agent, a quaternary ammonium salt-based adhesion imparting agent, and a quaternary phosphonium salt-based adhesion imparting agent is included in the rubber component to enhance the adhesive force. Preferred adhesion promoters include weak acid salts of 1,8-diazabicyclo- (5,4,0) -undecene-7 or weak acid salts of 1,5-diazabicyclo- (4,3,0) -nonene-5. Can do. The addition amount of these adhesion-imparting agents is within the range of 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, with respect to 100 parts by weight of the rubber component of the nitrile rubber composition or epihalohydrin rubber composition. is there.

  Examples of amine-based adhesion-imparting agents include 1,8-diazabicyclo- (5,4,0) -undecene-7, 1,5-diazabicyclo- (4,3,0) -nonene-5, or weak acids thereof Mention may be made of salts. These weak acid salts are preferred, and organic acids in the case of weak acid salts include phenol, octylic acid, p-toluenesulfonic acid, formic acid, acetic acid, orthophthalic acid, isophthalic acid, terephthalic acid, phenol novolac resin, hydroxynaphthoic acid. An acid etc. can be illustrated.

  The quaternary ammonium salt-based adhesion imparting agent is a quaternary ammonium salt compound represented by the following general formula (I). Examples thereof include benzyltriethylammonium chloride, tetrabutylammonium bromide, trimethyloctylammonium chloride, and triethylbenzyl. Examples include ammonium chloride.

（但し、Ｒはそれぞれ同一でも異なっていても良いアルキル基、アルケニル基を示し、Ｘは１価のアニオンを示す。） Formula (I)

(However, R represents the same or different alkyl and alkenyl groups, and X represents a monovalent anion.)

  The quaternary phosphonium salt-based adhesion imparting agent is a quaternary phosphonium salt compound represented by the following general formula (II), and examples thereof include tetrabutylphosphonium benzotriazolate.

（但し、Ｒはそれぞれ同一でも異なっていても良いアルキル基、アルケニル基を示し、Ｘは１価のアニオンを示す。） Formula (II)

(However, R represents the same or different alkyl and alkenyl groups, and X represents a monovalent anion.)

  Furthermore, in the present invention, the adhesive strength can be further improved by adding an epoxy compound to the unvulcanized rubber composition in addition to the adhesion-imparting agent. Examples of the epoxy compound include bisphenol A type epoxy, bisphenol F type epoxy, phenol novolac type epoxy, o-cresol novolac type epoxy, amine type epoxy, hydrogenated bisphenol A type epoxy, epoxidized soybean oil and the like. . The blending ratio of these epoxy compounds is in the range of 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the rubber component.

Next, the nitrile rubber composition used in the present invention will be described in detail.
The nitrile rubber is not particularly limited, but acrylonitrile-butadiene copolymer, modified nitrile rubber such as carboxyl-modified nitrile rubber obtained by copolymerizing the copolymer with a small amount of a copolymer component, and acrylonitrile-butadiene copolymer. Examples thereof include hydrogenated nitrile rubber in which some or all of the unsaturated bonds therein are hydrogenated. In the present invention, a nitrile rubber having a nitrile content in the range of 10 to 50% is preferably used from the viewpoint of low temperature flexibility and oil resistance.

  When applying a nitrile rubber to the laminated rubber component of the present invention, a known vulcanizing agent usually used for vulcanizing a nitrile rubber can be selected as the vulcanizing agent. Specific examples of the vulcanizing agent include sulfur, morpholine disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N′-dimethyl-N, N′-diphenylthiuram disulfide, dipentanemethylenethiuram. Sulfur-based vulcanizing agents such as tetrasulfide, dipentamethylene thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tert-butyl hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, tert-butyl peroxide, 1 , 3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, benzoyl peroxide, tert-butyl Organic peroxide vulcanizing agents such as peroxybenzoates, resin vulcanizing agents such as alkylphenol formaldehyde resins, quinone dioxime vulcanizing agents such as p-quinonedioxime and pp'-dibenzoylquinonedioxime Etc. The blending ratio of these vulcanizing agents is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the nitrile rubber component. If the vulcanizing agent is less than 0.1 parts by weight, the crosslinking effect is insufficient. On the other hand, if the vulcanizing agent exceeds 10 parts by weight, the vulcanized rubber molded product becomes too rigid to obtain practical rubber physical properties. .

  In addition to these vulcanizing agents, known vulcanization accelerators, vulcanization retarders, vulcanization accelerating agents, crosslinking auxiliaries, etc., which are usually used for vulcanizing nitrile rubbers, depending on the required performance. The addition is optional. Examples of these known additives include aldehyde ammonia accelerators, aldehyde amine accelerators, thiourea accelerators, guanidine accelerators, thiazole accelerators, sulfenamide accelerators, thiuram accelerators, dithiocarbamic acid. Various accelerators such as salt accelerators, xanthogen sun salt accelerators, retarders such as N-nitrosodiphenylamine, phthalic anhydride, N-cyclohexylthiophthalimide, zinc white, stearic acid, zinc stearate, etc. Vulcanization acceleration aids, quinonedioxime crosslinking aids, methacrylate crosslinking aids, allyl crosslinking aids, maleimide crosslinking aids and the like.

Next, the epihalohydrin rubber composition used in the present invention will be described in detail.
The epihalohydrin rubber is not particularly limited, but is epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-allyl glycidyl ether copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, epichlorohydrin-propylene Examples thereof include an oxide copolymer, an epichlorohydrin-propylene oxide-allyl glycidyl ether terpolymer, and an epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymer. Particularly preferred are epichlorohydrin homopolymers, epichlorohydrin-ethylene oxide copolymers, epichlorohydrin-allyl glycidyl ether copolymers, and epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymers. These can be used alone or in admixture of two or more. In the present invention, an epichlorohydrin rubber having a chlorine content of 20% or more is preferably used from the viewpoint of heat resistance and oil resistance.

  When an epihalohydrin rubber composition is applied as a rubber component constituting the laminate of the present invention, it is necessary to add an acid acceptor in addition to the adhesion-imparting agent, unlike the nitrile rubber composition.

Examples of acid acceptors include periodic table group (II) metal oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, periodic table group (IV). Metal oxides, basic carbonates, basic carboxylates, basic phosphites, basic sulfites, etc., and synthetic hydrotalcites represented by the following general formula (III), and general formula (IV) Li-Al-based inclusion compound represented by

_{Mg x Zn y Al z (OH} ) 2 (x + y) + 3z-2 CO 3 · wH 2 O (III)

(X and y are real numbers of 0 to 10, where x + y = 1 to 10, z is a real number of 1 to 5, and w is a real number of 0 to 10.)

[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (IV)

(In the formula, X is an inorganic or organic anion, n is the valence of the anion X, and m is a number of 3 or less.)

  Specific examples of the acid acceptor include magnesium oxide, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, zinc oxide, Examples thereof include calcium phthalate, calcium phosphite, tin oxide, and basic tin phosphite.

Furthermore, examples of the synthetic hydrotalcite represented by the general formula (III) include Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ .wH ₂ O. Moreover, the following general formula (V) contained in general formula (III) may be sufficient.

_{Mg x Al y (OH) 2x} + 3y-2 CO 3 · wH 2 O (V)

(However, x represents 1 to 10, y represents 1 to 10, and w represents a positive fruit.)
More specifically, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ , Mg ₄ Al ₂ (OH) ₁₂ CO _{3 · 3.5H 2 O, Mg 6 Al} 2 (OH) 16 CO 3 · 4H 2 O, Mg 3 Al 2 (OH) may be mentioned ₁₀ CO ₃ · 1.7H ₂ O and the like.

Moreover, the for general formula Li-Al-based inclusion compound represented by (II), it includes _[Al 2 Li _{(OH) 6] 2} CO ₃ · _{H 2} O or the like.

  The anion species of the Li-Al clathrate compound include carbonic acid, sulfuric acid, perchloric acid, phosphoric acid oxyacid, acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, maleic acid, Examples include fumaric acid, succinic acid, p-oxybenzoic acid, salicylic acid, and picric acid. These acid acceptors can be used alone or in admixture of two or more.

  Among the acid acceptors, from the viewpoint of the heat resistance of the epihalohydrin rubber, the acid acceptor preferably used is a metal oxide, a metal hydroxide, or an inorganic microporous crystal, and its blending amount is 100 parts by weight of the rubber component. It is preferable that it is 0.5-15 weight part with respect to it, More preferably, it is 1-10 weight part. If the acid acceptor is less than 0.5 parts by weight, the crosslinking effect is insufficient, while if it exceeds 15 parts by weight, the vulcanized rubber molded article is insufficiently stretched.

  In the present invention, the vulcanizing agent used when applying an epihalohydrin rubber to the laminated rubber component is a known vulcanizing agent utilizing the reactivity of chlorine atoms, such as polyamines, thioureas, thiadiazoles, Examples include mercaptotriazines, pyrazines, mercaptoquinoxalines, bisphenols and the like. In addition, when applying a polymer having a double bond such as an epichlorohydrin-allyl glycidyl ether copolymer, an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer as an epihalohydrin rubber to the present invention, a nitrile rubber and Similar vulcanizing agents, vulcanization accelerators, vulcanization retarders, vulcanization acceleration aids, and crosslinking aids can be used. These vulcanizing agents can be used alone or in admixture of two or more.

  Examples of known vulcanizing agents utilizing the reactivity of the chlorine atom include polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, cumenediamine, N, Examples thereof include N′-dicinnamylidene-1,6-hexanediamine, ethylenediamine carbamate, and hexamethylenediamine carbamate.

  Examples of the thioureas include ethylene thiourea, 1,3-diethylthiourea, 1,3-dibutylthiourea, and trimethylthiourea.

  Examples of the thiadiazoles include 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole-5-thiobenzoate and the like.

  Examples of the mercaptotriazines include 2,4,6-trimercapto-1,3,5-triazine, 1-methoxy-3,5-dimercaptotriazine, 1-hexylamino-3,5-dimercaptotriazine, 1 -Diethylamino-3,5-dimercaptotriazine, 1-cyclohexaneamino-3,5-dimercaptotriazine, 1-dibutylamino-3,5-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine, 1 -Phenylamino-3,5-dimercaptotriazine and the like.

  Examples of the pyrazines include 2,3-dimercaptopyrazine derivatives, and examples of 2,3-dimercaptopyrazine derivatives include pyrazine-2,3-dithiocarbonate, 5-methyl-2,3-dimercapto. Examples include pyrazine, 5-ethylpyrazine-2,3-dithiocarbonate, 5,6-dimethyl-2,3-dimercaptopyrazine, 5,6-dimethylpyrazine-2,3-dithiocarbonate, and the like.

  Examples of the mercaptoquinoxalines include 2,3-dimercaptoquinoxaline derivatives. Examples of 2,3-dimercaptoquinoxaline derivatives include quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3- Examples include dithiocarbonate, 6-ethyl-2,3-dimercaptoquinoxaline, 6-isopropylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithiocarbonate, and the like.

  Examples of the bisphenols include 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone (bisphenol S), 1,1-cyclohexylidene-bis (4-hydroxybenzene), 2-chloro-1, 4-cyclohexylene-bis (4-hydroxybenzene), 2,2-isopropylidene-bis (4-hydroxybenzene) (bisphenol A), hexafluoroisopropylidene-bis (4-hydroxybenzene) (bisphenol AF) and 2 -Fluoro-1,4-phenylene-bis (4-hydroxybenzene) and the like.

  Among these vulcanizing agents, vulcanizing agents that are preferably used from the viewpoint of heat resistance of the epihalohydrin rubber component and adhesion to the thermoplastic fluoropolymer are thiourea vulcanizing agents, quinoxaline vulcanizing agents, bisphenol vulcanizing agents. A vulcanizing agent, particularly preferably a quinoxaline vulcanizing agent.

  The blending ratio of the epihalohydrin rubber vulcanizing agent used in the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component. is there. If the vulcanizing agent is less than 0.1 parts by weight, the crosslinking effect is insufficient. On the other hand, if the vulcanizing agent exceeds 10 parts by weight, the vulcanized rubber molded product becomes too rigid to obtain practical rubber physical properties. .

  Also, known vulcanization accelerators and retarders can be used as they are in the present invention together with the vulcanizing agent. Examples of vulcanization accelerators used in combination with known vulcanizing agents that utilize the reactivity of chlorine atoms include basic silica, primary, secondary, tertiary amines, organic acid salts of these amines or their adducts, and guanidine. System accelerators, thiuram accelerators, dithiocarbamic acid accelerators, and the like. Examples of the retarder include N-cyclohexanethiophthalimide, acidic silica, and zinc salts of dithiocarbamic acids.

  As examples of the vulcanization accelerator, primary, secondary, and tertiary amines are preferably primary, secondary, or tertiary amines of aliphatic or cyclic fatty acids having 5 to 20 carbon atoms. Representative examples of such amines are n-hexylamine, octylamine, dibutylamine, tributylamine, hexamethylenediamine and the like.

  Examples of the organic acid that forms a salt with the amine include carboxylic acid, carbamic acid, 2-mercaptobenzothiazole, and dithiophosphoric acid. Examples of the substance that forms an adduct with the amine include alcohols and oximes. Specific examples of the organic acid salt or adduct of amine include n-butylamine / acetate, hexamethylenediamine / carbamate, dicyclohexylamine salt of 2-mercaptobenzothiazole, and the like.

  Examples of the guanidine accelerator include diphenyl guanidine and ditolyl guanidine.

  Specific examples of the thiuram vulcanization accelerator include tetramethyl thiuram disulfide, tetramethyl thiuram monosulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide and the like.

  Examples of the dithiocarbamic acid accelerator include pentamethylenedithiocarbamic acid piperidine salt.

  The blending amount of the vulcanization accelerator or retarder used in combination with the known vulcanizing agent utilizing the reactivity of the chlorine atom is preferably 0 to 10 parts by weight with respect to 100 parts by weight of the rubber component. Preferably it is 0.1-5 weight part.

  As a compounding method of the rubber component used in the present invention, any means conventionally used in the field of polymer processing, for example, a mixing roll, a Banbury mixer, various kneaders, and the like can be used.

  In addition, other additives usually used in the technical field, such as lubricants, anti-aging agents, fillers, reinforcing agents, plasticizers, processing aids, pigments, foaming agents, etc. are arbitrarily added to the rubber component used in the present invention. Can be blended.

  Furthermore, it is possible to perform blending with a resin or the like that is usually performed in the technical field as long as the characteristics of the present invention are not lost. Examples of resins used in the present invention include polymethyl methacrylate (PMMA) resin, polystyrene (PS) resin, polyurethane (PUR) resin, polyvinyl chloride (PVC) resin, ethylene / vinyl acetate (EVA) resin, styrene. / Acrylonitrile (AS) resin, polyethylene (PE) resin and the like.

  The laminate of the present invention can be obtained by overlaying the composition containing the fluororesin according to the present invention and an unvulcanized rubber composition of nitrile rubber or epihalohydrin and usually vulcanizing and bonding at 100 to 250 ° C. Although the vulcanization time varies depending on the temperature, it is generally performed between 0.5 and 300 minutes. As the molding method, compression molding, injection molding, multilayer extrusion molding or the like can be applied, and as the heating method, any method such as heating by a steam can, an air bath, infrared rays, or microwaves can be used. it can.

  Hereinafter, examples and the like specifically showing the configuration and effects of the present invention will be described, but the present invention is not limited to such examples.

  Various rubber compositions were prepared at the ratios shown in Table 1. The rubbers and compounding agents used are as follows.

Fluorine-containing polymer: ethylene-tetrafluoroethylene copolymer, NEOFRON ETFE EP-610 manufactured by Daikin Industries, Ltd.
Composition containing fluororesin: 25 parts by weight of the above-mentioned EP-610, 100 parts by weight of ternary fluororubber consisting of VdF, TFE and HEP at a temperature of 260 ° C., melted and kneaded with a lab plast mill. A composition containing a fluororesin obtained by melting and kneading again 100 parts by weight of a composition containing the composition and 14.3 parts by weight of a ternary fluororubber composed of VdF, TFE and HEP at a temperature of 260 ° C. . The composition is composed of 70 parts by weight of fluororesin and 30 parts by weight of fluororubber.
NBR: Nitrile rubber, JSR N-230S
ECO: Epichlorohydrin-ethylene oxide copolymer rubber, manufactured by Daiso Corporation, Epichromer C
Ester plasticizer: Adeka Sizer RS-107 manufactured by Asahi Denka Kogyo Co., Ltd.
Lubricant: Splendor R-300 manufactured by Kao Corporation
Anti-aging agent OD: alkylated diphenylamine anti-aging agent NBC: nickel dibutyl dithiocarbamate synthetic hydrotalcite: DHT-4A manufactured by Kyowa Chemical Co., Ltd.
Adhesion imparting agent 1: Weak acid salt of 1,8-diazabicyclo- (5,4,0) -undecene-7 Daiso P-152
Adhesion imparting agent 2: quaternary ammonium salt-based triethylbenzylammonium chloride adhesion imparting agent 3: quaternary phosphonium salt-based Dynamer FX-5166
Epoxy compound: Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.
Delay agent: N-cyclohexylthiophthalimide accelerator CZ: Cyclohexylbenzothiazylsulfenamide accelerator TT: Tetramethylthiuram disulfide quinoxaline vulcanizing agent: 6-methylquinoxaline-2,3-dithiocarbonate thiourea vulcanizing agent: Ethylenethiourea bisphenol vulcanizing agent: Dynamer FC-5157 manufactured by Dyneon

[Example 1]
100 parts by weight of nitrile rubber was masticated in a 1 liter kneader set at 120 ° C. for 1 minute, and then the A kneading compound shown in Table 1 was added in the compounding amount shown in Table 1. These were kneaded for 4 minutes, then taken out from the kneader and formed into a sheet with a 7-inch roll set at 70 ° C. to prepare a rubber sheet (hereinafter referred to as “A kneaded sheet”).

  Next, using a 7-inch roll set at a temperature of 70 ° C., the B kneading compounding agent having the blending ratio shown in Table 1 was added to the A kneading sheet, and kneaded for about 5 minutes, whereby a rubber sheet (hereinafter referred to as “B A kneaded sheet ").

  The obtained B-kneaded sheet and the composition containing the fluororesin listed in Table 1 and a fluoropolymer sheet (0.2 mm thickness) were superposed and heated under a press set at 170 ° C. under pressure. Vulcanization adhesion was performed for 15 minutes to obtain a laminate having a vulcanized rubber component thickness of about 2 mm and a fluoropolymer component thickness of about 0.2 mm, and the laminate was cut into a 1 cm width to obtain a test piece for measuring adhesive strength. Obtained.

For [Examples 2 to 12] and [Comparative Examples 1 to 4], rubber sheets were produced in the same manner as in [Example 1], according to the formulations in Tables 1, 3 and 5.
In Table 1, Table 3, and Table 5, ◯ indicates a composition containing the fluoropolymer or fluororesin used in the laminate.

[Adhesive strength test]
The measurement was performed according to JIS K 6330-6. However, a 1 cm wide strip-shaped test piece was used as the test piece. The peeling speed was 50 mm / min. The test results are shown in Table 2, Table 4, and Table 6.

  In Comparative Example 1 and Comparative Example 3, it was confirmed that neither the nitrile rubber nor the epihalohydrin rubber could be bonded because the fluoropolymer did not have a reactive functional group.

  In Comparative Example 2 and Comparative Example 4, it was confirmed that neither the nitrile rubber nor the epihalohydrin rubber could be bonded because the adhesion-imparting agent that is an essential component of the present invention was not included.

  In Example 4 and Example 8, it was confirmed that the adhesive strength could be further improved by adding an epoxy compound.

  The laminate of the present invention is obtained by vulcanizing and bonding a fluorine-containing polymer excellent in fuel impermeability and a nitrile rubber or epihalohydrin rubber. It can be widely applied to uses such as chemical hoses used in alkalis, organic solvents, and the like.

Claims (9)

In the laminate comprising (A) a composition containing a fluororesin and (B) an unvulcanized rubber composition vulcanized and bonded,
(A) a composition containing a fluororesin,
At least one kind of fluororubber is dynamically cross-linked under the melting condition of an ethylene-TFE copolymer comprising TFE and ethylene, and the resulting cross-linked cross-linked fluororubber and a composition containing the fluororesin And a fluororesin composition obtained by melt-kneading a composition containing a fluoropolymer,
The (B) unvulcanized rubber composition is
(B1) A nitrile rubber composition containing at least one kind of adhesion imparting agent and a vulcanizing agent selected from an amine based adhesion imparting agent, a quaternary ammonium salt based adhesive imparting agent, and a quaternary phosphonium salt based adhesive imparting agent, or ( B2) An epihalohydrin rubber composition containing at least one kind of adhesion-imparting agent selected from amine-based adhesion imparting agents, quaternary ammonium salt-based adhesion imparting agents, and quaternary phosphonium salt-based adhesion imparting agents, acid acceptors and vulcanizing agents. The laminated body characterized by the above-mentioned.   The amine-based adhesion promoter is a weak acid salt of 1,8-diazabicyclo- (5,4,0) -undecene-7 or a weak acid salt of 1,5-diazabicyclo- (4,3,0) -nonene-5 The laminate according to claim 1.   (B) The laminate according to claim 1 or 2, wherein the nitrile rubber composition (B1) or the epihalohydrin rubber composition (B2) which is an unvulcanized rubber composition further contains an epoxy compound. The acid acceptor of the epihalohydrin rubber (B2) is a metal oxide, a metal hydroxide, a synthetic hydrotalcite represented by the general formula (III), or a Li-Al based clathrate represented by the general formula (IV) The laminate according to any one of claims 1 to 3, which is at least one selected from the group consisting of:
_{Mg x Zn y Al z (OH} ) 2 (x + y) + 3z-2 CO 3 · wH 2 O (III)

(X and y are real numbers of 0 to 10, where x + y = 1 to 10, z is a real number of 1 to 5, and w is a real number of 0 to 10.)

[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (IV)

(In the formula, X is an inorganic or organic anion, n is the valence of the anion X, and m is a number of 3 or less.)   The vulcanizing agent of the epihalohydrin rubber (B2) is one selected from the group consisting of a thiourea vulcanizing agent, a quinoxaline vulcanizing agent, and a bisphenol vulcanizing agent. Laminated body.   The laminate according to any one of claims 1 to 5, wherein the vulcanizing agent of the epihalohydrin rubber (B2) is a quinoxaline vulcanizing agent.   The laminate according to any one of claims 1 to 5, wherein the vulcanizing agent of the epihalohydrin rubber (B2) is a bisphenol vulcanizing agent.   The hose for motor vehicles using the laminated body in any one of Claims 1-7. (A) At least one kind of fluororubber is dynamically cross-linked under the melting condition of an ethylene-TFE copolymer composed of TFE and ethylene, and the obtained cross-linked fluororubber and the fluororesin are cross-linked at least partially. A fluororesin composition obtained by melt-kneading a composition containing a fluoropolymer and a composition containing a fluoropolymer; and (B1) an amine-based adhesion imparting agent, a quaternary ammonium salt-based adhesion imparting agent, and a quaternary phosphonium salt-based adhesion imparting agent. A nitrile rubber composition containing at least one kind of adhesion-imparting agent and vulcanizing agent, or (B2) an amine-based adhesion imparting agent, a quaternary ammonium salt-based adhesion imparting agent, and a quaternary phosphonium salt-based adhesion imparting agent. A method for producing a laminate comprising a step of vulcanizing and bonding an epihalohydrin rubber composition containing at least one kind of adhesion-imparting agent, acid acceptor and vulcanizing agent.