JP5401954B2 - Laminated body comprising rubber layer and fluororesin layer and rubber composition for vulcanization - Google Patents

Description

  The present invention relates to a rubber layer formed from a vulcanized rubber composition containing an unvulcanized rubber, an amine compound, and, if necessary, an epoxy resin, and a fluororesin layer formed from a fluororesin having a reactive functional group. The present invention relates to a vulcanized and bonded laminate, and further to a rubber composition for vulcanization.

  Conventionally, due to the recent increase in environmental awareness, the development of laws to prevent fuel volatilization has progressed. Especially in the automobile industry, there is a significant tendency to suppress fuel volatilization, especially in the United States, and there is a great need for materials with excellent fuel barrier properties. It is becoming.

  In particular, in fuel transport rubber hoses, laminated hoses with fluororesin as a barrier layer (rubber other than the barrier layer) are used to improve fuel permeation resistance. Due to the recent strong demand for reducing environmental impact, The barrier layer requires one layer of low fuel permeability. Attempts have been made to secure low permeability by increasing the thickness of the barrier layer or by using a perfluoro fluororesin that is most excellent in low transmission. However, increasing the thickness of the barrier layer (fluorine resin) increases the weight of the hose and is also disadvantageous from the viewpoint of energy saving. Further, the bendability (flexibility) of the hose itself is impaired, and handling properties ( It is also disadvantageous from the viewpoint of assembly.

  In addition, when using a perfluoro-based fluororesin as a barrier layer, it is difficult to adhere to the rubber of the outer and inner layers, which is the counterpart material, and surface treatment of the resin to improve the adhesion, film or tape A process such as a wrapping method is required, which complicates the work process, significantly lowers productivity, and has a problem in practical use such as a significant increase in cost.

  In order to improve the adhesion between the perfluoro fluororesin and the rubber layer, for example, as disclosed in Patent Document 1, an epoxidized rubber or a blend of epoxidized rubber and rubber may be used as the rubber used in the rubber layer. Are known. Further, as in Patent Document 2, in order to directly bond rubber to the fluororesin, a thermoplastic fluororesin having a reactive functional group such as a carbonyl group is used as the fluororesin, and at least one of the thermoplastic fluororesin and the rubber layer is used. It is also known to incorporate a polyfunctional compound such as triallyl isocyanurate.

JP 7-266501 A Japanese Patent Laid-Open No. 2005-22403

  The present invention provides a vulcanized laminate in which a rubber layer and a fluororesin layer are firmly bonded without using an adhesive and without subjecting each of the rubber layer and the fluororesin layer to a surface treatment. With the goal.

  Another object of the present invention is to provide a rubber composition for vulcanization excellent in adhesiveness with a fluororesin layer.

The present invention provides a rubber layer (A) formed from a vulcanized rubber composition containing unvulcanized rubber (a1) and an amine compound (a2);
A fluororesin layer (B) formed of a fluororesin (b) having at least one reactive functional group selected from the group consisting of a carbonyl group and a hydroxyl group at the side chain and / or main chain end is adhered. It relates to a laminate.

  The rubber composition for vulcanization may further contain an epoxy resin (a3).

  In the laminate of the present invention, the rubber layer (A) and the fluororesin layer (B) are vulcanized and bonded.

  In the present invention, the unvulcanized rubber (a1) is preferably a non-fluorinated rubber, and particularly preferably acrylonitrile-butadiene rubber (NBR).

  The content of the amine compound (a2) in the rubber layer (A) is 1 to 25 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1), and when the epoxy resin (a3) is blended, the content thereof It is preferable that it is 1-25 mass parts with respect to 100 mass parts of unvulcanized rubber (a1).

  In the rubber composition for vulcanization, the unvulcanized rubber (a1) is NBR in which NBR or polyvinyl chloride (PVC) is blended, and further, a sulfur-based vulcanizing agent or a peroxide-based vulcanizing agent is used as the vulcanizing agent (a4). It is preferable to include a sulfurizing agent.

  The rubber composition for vulcanization preferably contains a 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) vulcanization accelerator as the vulcanization accelerator (a5).

  The fluororesin (b) includes chlorotrifluoroethylene (CTFE) -tetrafluoroethylene (CTFE) -tetrafluoroethylene (CTFE) having at least one reactive functional group selected from the group consisting of a carbonyl group and a hydroxyl group at the side chain and / or main chain terminal. TFE) -perfluoro (alkyl vinyl ether) (PAVE) copolymer is preferred.

  Moreover, it is preferable that the rubber layer (A) is laminated | stacked on both sides of the fluororesin layer (B) from the point which improves a sealing performance, and both sides of a rubber layer (A) are preferable from the point which improves chemical resistance. It is preferable that the fluororesin layer (B) is laminated on.

  Further, a polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B) may be laminated.

  The present invention also relates to a vulcanized laminate in which the rubber layer (A1) obtained by vulcanizing the laminate and the fluororesin layer (B) are vulcanized and bonded.

  The present invention also provides a rubber composition for vulcanization comprising an unvulcanized rubber (a1), an amine compound (a2) and a vulcanizing agent (a4) and, if necessary, an epoxy resin (a3). The present invention also relates to a rubber composition for vulcanization in which the vulcanized rubber (a1) is NBR in which NBR or PVC is blended, and the vulcanizing agent (a4) is a sulfur vulcanizing agent or a peroxide vulcanizing agent.

  The rubber composition for vulcanization is 1 to 25 parts by mass of the amine compound (a2) and 1 to 10 parts by mass of the vulcanizing agent (a4) with respect to 100 parts by mass of the unvulcanized rubber (a1). When mix | blending (a3), it is preferable to contain 1-25 mass parts.

  Furthermore, it is preferable that a DBU vulcanization accelerator is included as the vulcanization accelerator (a5). The content of the DBU vulcanization accelerator is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the unvulcanized rubber.

  The laminated body of the present invention does not require a special process for bonding because it can provide a chemically strong bond during rubber vulcanization without particularly complicated processes when laminating a fluororesin layer and a rubber layer. Yes, it can be molded at low cost, and molding is also easy. Moreover, since it can shape | mold by a normal method like extrusion molding, thin film formation is also possible and the softness | flexibility point is also improved.

  The laminate of the present invention comprises a rubber layer (A) formed from a specific rubber composition for vulcanization and a fluororesin layer (B) formed from a fluororesin (b) having a specific reactive functional group. It is characterized by being bonded.

  Hereinafter, each layer will be described.

(A) Rubber layer The rubber layer (A) is formed from a vulcanized rubber composition containing an unvulcanized rubber (a1) and an amine compound (a2) and, if necessary, an epoxy resin (a3).

  The unvulcanized rubber (a1) may be fluororubber, but non-fluororubber is preferred because of its good cold resistance and cost.

  Specific examples of the non-fluorine rubber include, for example, acrylonitrile-butadiene rubber (NBR) or a hydride thereof (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), and natural rubber (NR). And diene rubber such as isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, acrylic rubber and the like. Among these, it is preferable that the unvulcanized rubber contains NBR from the viewpoint of good heat resistance, oil resistance, weather resistance, and extrusion moldability.

  Moreover, in order to provide the rubber layer (A) with characteristics different from those of the unvulcanized rubber, the unvulcanized rubber may be a blend of resins. Examples of the resin include PVC, chlorinated polystyrene, chlorosulfonated polyethylene, and ethylene-vinyl acetate copolymer. For example, when PVC is blended with NBR, 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.

  The amine compound (a2) and the epoxy resin (a3) react with the reactive functional group (carbonyl group and / or hydroxyl group) of the fluororesin (b) to form a chemical bond with the fluororesin (b). This function improves the adhesion between the layers.

  Examples of the amine compound include hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-bis (aminocyclohexyl) methanecarbamate, and the like. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.

  Content of an amine compound (a2) is 1 mass part or more with respect to 100 mass parts of unvulcanized rubber (a1) from the point which improves the adhesive force with a fluororesin (b), and 2 mass parts The above is preferable, 3 parts by mass or more is more preferable, and 5 parts by mass or more is particularly preferable. Moreover, 25 mass parts or less are preferable with respect to 100 mass parts of unvulcanized rubber from the point that the vulcanization characteristic of unvulcanized rubber (a1) is not impaired, 20 mass parts or less are more preferable, and 10 mass parts The following are particularly preferred:

で表わされるエポキシ樹脂が特に好ましくあげられる。ここで、式（１）において、ｎは平均値であり、０．１〜３が好ましく、０．１〜０．５がより好ましく、０．１〜０．３がさらに好ましい。ｎが０．１未満であると、フッ素樹脂（ｂ）との接着力が低下する傾向がある。一方、ｎが３をこえると、エポキシ樹脂（ａ３）自体の粘度が高くなり、加硫用ゴム組成物中での均一な分散が困難になる傾向がある。 Examples of the epoxy resin (a3) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and polyfunctional epoxy resin. Of these, bisphenol A type epoxy resin is preferable from the viewpoint of good chemical resistance and adhesion, and further, the formula (1):

An epoxy resin represented by the formula is particularly preferred. Here, in Formula (1), n is an average value, 0.1-3 are preferable, 0.1-0.5 are more preferable, and 0.1-0.3 are further more preferable. When n is less than 0.1, the adhesive strength with the fluororesin (b) tends to decrease. On the other hand, when n exceeds 3, the viscosity of the epoxy resin (a3) itself tends to be high, and uniform dispersion in the rubber composition for vulcanization tends to be difficult.

  The content in the case of blending the epoxy resin (a3) is preferably 1 part by mass or more with respect to 100 parts by mass of the unvulcanized rubber from the viewpoint of further improving the adhesive force with the fluororesin (b). Part or more is more preferable, and 3 parts by mass or more is particularly preferable. From the viewpoint of preventing the rubber layer from becoming too hard, the amount is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less with respect to 100 parts by mass of the unvulcanized rubber.

  The rubber composition for vulcanization in the present invention may further contain a vulcanizing agent (a4). By vulcanizing the unvulcanized rubber (a1), mechanical strength such as tensile strength of the obtained vulcanized rubber layer is improved, and good elasticity can be obtained.

  A conventionally well-known thing can be used for a vulcanizing agent (a4) according to the vulcanization system of the rubber composition for vulcanization | cure.

  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 unvulcanized rubber contains vulcanizable groups (cure sites), it is appropriately selected 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 (a4), a sulfur vulcanizing vulcanizing agent, a polyamine vulcanizing vulcanizing agent, a polyol vulcanizing vulcanizing agent, a peroxide vulcanizing vulcanizing agent, an imidazole vulcanizing agent are used in accordance with the vulcanizing system. 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 rubber (a1) is a diene-based non-fluorinated rubber (NBR, SBR, BR, etc.), a sulfur vulcanization system and a peroxide vulcanization system are usually employed, and sulfur vulcanization is also used as a vulcanizing agent. A system vulcanizing agent and a peroxide vulcanizing agent are preferably used.

  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 to 10 parts by mass with respect to 100 parts by mass of the unvulcanized rubber. If it is too small, vulcanization will be insufficient, and if it is too large, it will tend to be too hard.

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

  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-butylcumyl 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—, the decomposition temperature, and the like. A compounding quantity is 0.1-15 mass parts normally with respect to 100 mass parts of unvulcanized rubbers, Preferably it is 0.3-5 mass parts.

  Furthermore, in order to improve the vulcanization characteristics of the rubber composition for vulcanization, a vulcanization accelerator, a vulcanization assistant, a co-vulcanizer, etc. (in the present invention, these are collectively referred to as “vulcanization accelerator”). May be used in combination. The vulcanization accelerator (a5) may be selected according to the vulcanization system.

  Examples of the vulcanization accelerator (a5) include polyfunctional compounds having a plurality of allyl groups, aldehyde amines, aldehyde ammonias, thioureas, thiazoles, thiophenamides, thiolams, dithiocarbamates, 1,8- Examples thereof include diazabicyclo [5,4,0] -7-undecene (DBU) and weak acid salts of DBU.

  The compounding quantity of a vulcanization accelerator (a5) is 10 mass parts or less with respect to 100 mass parts of unvulcanized rubber, 5 mass parts or less are preferable and 3 mass parts or less are more preferable. When the amount exceeds 10 parts by mass, the vulcanization density becomes too high, and thus tends to be easily broken during compression. The lower limit of the amount is preferably 0.2 parts by mass, and if it is less than 0.2 parts by mass, the vulcanization density tends to decrease and the compression set tends to increase.

  As the vulcanization accelerator in the case of the peroxide vulcanization system, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) and a weak acid salt of DBU can be preferably used. Examples of the weak acid salt of DBU include carbonates, long chain aliphatic carboxylates, aromatic carboxylates, orthophthalates, p-toluenesulfonates, phenol salts, phenol resin salts, and the like. Among these, 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride (DBU-B), DBU-phenol salt, DBU-orthophthalate provides adhesion. From the point that the conventional vulcanization characteristics are not impaired.

  Of the rubber composition for vulcanization used in the present invention, a rubber composition for vulcanization comprising unvulcanized rubber (a1), amine compound (a2), epoxy resin (a3) and vulcanizing agent (a4). The unvulcanized rubber (a1) is an NBR blended with NBR or PVC, and the vulcanizing rubber composition in which the vulcanizing agent (a4) is a sulfur vulcanizing agent or a peroxide vulcanizing agent, It is new and particularly excellent in adhesion to other materials (especially fluorine-based materials).

  In this composition, the amine compound (a2) is preferably a diamine compound, particularly N, N′-dicinnamylidene-1,6-hexamethylenediamine, and the epoxy resin (a3) is represented by the above formula (1). Bisphenol A type epoxy resin is preferred.

  The compounding amount in the rubber composition for vulcanization is 1 to 25 parts by mass of amine compound, 1 to 25 parts by mass of epoxy resin, and sulfur vulcanizing agent with respect to 100 parts by mass of NBR or PVC blended with NBR. Or it is preferable that 1-10 mass parts of peroxide type | system | group vulcanizing agents are included.

  Furthermore, it is preferable that a DBU vulcanization accelerator is included as the vulcanization accelerator (a5) from the viewpoint that the vulcanization characteristics can be improved. In particular, when no epoxy resin (a3) is blended, it is preferable to use a DBU vulcanization accelerator. The content of the DBU vulcanization accelerator is preferably 1 to 10 parts by mass with respect to 100 parts by mass of NBR or NBR blended with PVC.

  Examples of other compounding agents related to vulcanization include acid acceptors, which can be used in the present invention. Examples of the acid acceptor include magnesium oxide and calcium hydroxide. The acid acceptor not only assists in crosslinking, but also has a function of trapping hydrofluoric acid generated from the fluororesin layer (B) when the laminate is held at a high temperature.

  Further, in the present invention, as necessary or necessary, conventional additives blended in a general vulcanizing rubber composition, such as fillers, processing aids, plasticizers, softeners, anti-aging agents, colorants, Stabilizer, 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 Various additives such as an improver, a foaming agent, a scorch inhibitor, and a lubricant 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 said thing. However, these additives are blended in such an amount that does not impair the adhesive force with the fluororesin layer (B) which is the object of the present invention.

  Fillers include metal oxides such as magnesium oxide, calcium oxide, titanium oxide, silicon oxide and aluminum oxide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide; magnesium carbonate, aluminum carbonate and carbonic acid Carbonates such as calcium and barium carbonate; silicates such as magnesium silicate, calcium silicate, sodium silicate and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; synthetic hydrotalcite and disulfide Metal sulfides such as molybdenum, iron sulfide, copper sulfide; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, wet silica, dry silica, quartz Fine powder, zinc white, ta Click, mica powder, wollastonite, 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 and sebacic acid derivatives, softeners such as lubricating oil, process oil, coal tar, castor oil, calcium stearate, and anti-aging agents such as phenylenediamines and phosphates, Examples include quinolines, cresols, phenols, and dithiocarbamate metal salts.

  The vulcanized rubber composition comprises an unvulcanized rubber (a1), an amine compound (a2), and if necessary, an epoxy resin (a3), a vulcanizing agent (a4), a vulcanization accelerator (a5), and other additives. 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.

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

  The fluororesin layer (B) is formed from a fluororesin (b) having at least one reactive functional group selected from the group consisting of a carbonyl group and a hydroxyl group at the side chain and / or main chain terminal.

  The fluororesin (b) is obtained by introducing at least one reactive functional group selected from the group consisting of a carbonyl group and a hydroxyl group into the side chain and / or main chain terminal of the fluoropolymer (b1).

  The polymer (b1) portion constituting the fluororesin (b) other than the structural unit having a reactive functional group is a homopolymer or copolymer having a structural unit derived from at least one fluorine-containing ethylenic monomer. A polymer is preferred.

  The structural unit other than the structural unit derived from the fluorinated ethylenic monomer of the fluorinated polymer (b1) is derived from an ethylenic monomer having no fluorine atom copolymerizable with the fluorinated ethylenic monomer. The structural unit is preferably.

The fluorine-containing ethylenic monomer is not particularly limited. For example, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE), chlorotrifluoroethylene (CTFE), fluoride Vinylidene (VdF), vinyl fluoride, hexafluoroisobutene, formula:
CH ₂ = CX ¹ (CF ₂ ) _n X ²
(Wherein X ¹ is H or F, X ² is H, F or Cl, and n is an integer of 1 to 10)
And the like.

  The copolymerizable non-fluorine ethylenic monomer may be selected from ethylenic monomers having 5 or less carbon atoms from the viewpoint of maintaining the heat resistance and chemical resistance of the fluororesin (b). preferable. Specific examples include ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride, and the like.

  The ratio of the fluorinated ethylenic monomer unit to the non-fluorinated ethylenic monomer unit is 10 to 100 mol% (preferably 30 to 100 mol%) of the fluorinated ethylenic monomer unit, The body unit is preferably 0 to 90 mol% (preferably 0 to 70 mol%).

  Preferred fluoropolymers (b1) include CTFE polymers, TFE / HFP (FEP) copolymers, TFE / PAVE (PFA) copolymers, ethylene / TFE (ETFE) copolymers. Examples thereof include a copolymer, an ethylene / TFE / HFP (EFEP-based) copolymer, and a polyvinylidene fluoride-based polymer. Of these, CTFE polymer, FEP copolymer, PFA copolymer, ETFE copolymer, and EFEP copolymer are preferred because of their excellent chemical resistance, and CTFE polymer and FEP are also preferred. From the viewpoints of flexibility and low fuel permeability, CTFE polymers and FEP copolymers are particularly preferred.

  In addition, since these preferable fluoropolymers (b1) are all excellent in low fuel permeability for mixed fuel such as alcohol fuel, they can be used as fuel component materials having sufficient low fuel permeability.

  Of the preferred fluoropolymer (b1), examples of the CTFE polymer include polychlorotrifluoroethylene (PCTFE) and a CTFE copolymer.

  As a CTFE type | system | group copolymer, what has a monomer ((alpha)) unit derived from a CTFE unit, a TFE unit, and the monomer ((alpha)) copolymerizable with these is preferable.

The monomer (α) is not particularly limited as long as it is a monomer copolymerizable with CTFE and TFE, and ethylene (Et), vinylidene fluoride (VdF), CF ₂ = CF-ORf ¹ (formula Rf ¹ is perfluoro (alkyl vinyl ether) (PAVE) represented by C 1-8 perfluoroalkyl group, CX ³ X ⁴ = CX ⁵ (CF ₂ ) _n X ⁶ (wherein X ³ , X ⁴ and X ⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ⁶ is a hydrogen atom, a fluorine atom or a chlorine atom; n is an integer of 1 to 10), Examples thereof include alkyl perfluorovinyl ether derivatives represented by CF ₂ = CF—OCH ₂ —Rf ² (wherein Rf ² is a C 1-5 perfluoroalkyl group).

  Examples of the PAVE include perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (butyl vinyl ether), among others, PMVE, PEVE or PPVE is more preferred.

As the alkyl perfluorovinyl ether derivative, those in which Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ ═CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

  In the CTFE-based copolymer, the ratio of CTFE units to TFE units is 85 to 10 mol% of TFE units with respect to 15 to 90 mol% of CTFE units, and more preferably 20 to 90 mol of CTFE units. Mol%, and TFE units are 80 to 10 mol%. Moreover, what comprises 15-25 mol% of CTFE units and 85-75 mol% of TFE units is more preferable.

  The total of CTFE units and TFE units is 90 to 99.9 mol%, and the monomer (α) unit is preferably 0.1 to 10 mol%. If the monomer (α) unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and fuel crack resistance are likely to be inferior, and if it exceeds 10 mol%, fuel low permeability, heat resistance, It tends to be inferior in mechanical properties.

  When the monomer (α) is PAVE, the more preferable lower limit of the monomer (α) unit is 0.5 mol%, and the more preferable upper limit is 5 mol%.

The “CTFE unit” and the “TFE unit” are a part derived from CTFE (—CFCl—CF ₂ —) and a part derived from TFE (—CF ₂ —CF ₂ —), respectively, in the molecular structure of the CTFE copolymer. Similarly, the “monomer (α) unit” is a portion formed by adding the monomer (α) to the molecular structure of the CTFE copolymer.

A structural unit such as a CTFE unit is a value obtained by performing ¹⁹ F-NMR analysis.

  The FEP copolymer preferably has 98 to 80 mol% of TFE units and 2 to 20 mol% of HFP units.

  In addition to the TFE unit and the HFP unit, the FEP copolymer may include a structural unit derived from a monomer (α1) copolymerizable with TFE and HFP as a constituent element.

  The monomer (α1) is not particularly limited as long as it is a compound copolymerizable with TFE and HFP, and examples thereof include the same compounds as the monomer (α) described above.

  The FEP copolymer is excellent in flexibility and low fuel permeability. When the monomer (α1) unit is included, the total of the CTFE unit and the TFE unit is 90 to 99.9 mol%. And the monomer (α1) unit is preferably 0.1 to 10 mol%.

  The fluororesin (b) is obtained by introducing at least one reactive functional group selected from the group consisting of a carbonyl group and a hydroxyl group into the side chain and / or main chain terminal of the fluoropolymer (b1). is there.

In the present specification, the “carbonyl group” is a carbon divalent group composed of a carbon-oxygen double bond, and is represented by —C (═O) —. The reactive functional group containing the carbonyl group is not particularly limited. For example, a carbonate group, a carboxylic acid halide group (halogenoformyl group), a formyl group, a carboxyl group, an ester bond (—C (═O) O—), an acid. Anhydride bond (—C (═O) O—C (═O) —), isocyanate group, amide group, imide group (—C (═O) —NH—C (═O) —), urethane bond (— NH-C (= O) O- ), a carbamoyl group _{(NH 2 -C (= O)} -), a carbamoyloxy group _{(NH 2 -C (= O)} O-), a ureido group (NH ₂ -C (= O) -NH-), oxamoyl group _{(NH 2 -C (= O)} -C (= O) -) , etc., can be mentioned those containing a carbonyl group as part of the chemical structure.

  In the amide group, imide group, urethane bond, carbamoyl group, carbamoyloxy group, ureido group, oxamoyl group, etc., the hydrogen atom bonded to the nitrogen atom may be substituted with a hydrocarbon group such as an alkyl group, for example. .

  The reactive functional group has an amide group, a carbamoyl group, a hydroxyl group because it can be easily introduced and the obtained fluororesin (b) has appropriate heat resistance and good adhesion at a relatively low temperature. Group, carboxyl group, carbonate group, carboxylic acid halide group, and acid anhydride bond are preferable, and amide group, carbamoyl group, hydroxyl group, carbonate group, carboxylic acid halide group, and acid anhydride bond are more preferable.

  Among these, those having a carbonate group and / or a carboxylic acid halide group described in International Publication No. 99/45044 pamphlet are particularly preferable.

  The fluororesin (b) in the present invention may be composed of a polymer having a reactive functional group at either the main chain end or the side chain of the fluoropolymer (b1), the main chain end and It may consist of a polymer having reactive functional groups on both side chains. When having a reactive functional group at the end of the main chain, it may be present at both ends of the main chain or only at one of the ends. When the reactive functional group also has an ether bond, the reactive functional group may further have the reactive functional group in the main chain.

  The fluororesin (b) is composed of a polymer having a reactive functional group at the end of the main chain because it does not significantly reduce mechanical properties and chemical resistance, or is advantageous in terms of productivity and cost. Is preferable.

  The number of the reactive functional groups may be appropriately selected depending on the kind of rubber layer to be laminated, the shape, the purpose and purpose of adhesion, the application, the required adhesion force and the adhesion method between adjacent layers, and the like.

The number of reactive functional groups at the main chain end and / or side chain end is preferably 3 to 800 per 1 × 10 ⁶ main chain carbon atoms. If the number of main chain carbon atoms is less than 3 per 1 × 10 ⁶ , the adhesion may be lowered. A more preferred lower limit is 15, a further preferred lower limit is 30, and a particularly preferred lower limit is 120. The upper limit of the number of reactive functional groups at the end is preferably 200, for example, from the viewpoint of productivity.

  The number of reactive functional groups at the end is such that the thickness of the fluororesin (b) powder is 0.25 to 0.30 mm obtained by compression molding at a molding temperature of 50 ° C. higher than its melting point and a molding pressure of 5 MPa. The film sheet is subjected to infrared absorption spectrum analysis using an infrared spectrophotometer, and the type of characteristic absorption of the reactive functional group is determined by comparison with the infrared absorption spectrum of a known film. It is the number calculated by.

Number of terminal groups (per 1 × 10 ⁶ carbon atoms) = (l × K) / t
l: Absorbance K: Correction coefficient t: Film thickness (mm)
Table 1 shows correction coefficients for the terminal reactive functional groups.

The correction coefficient in Table 1 is a value determined from the infrared absorption spectrum of the model compound in order to calculate the terminal group per 1 × 10 ⁶ main chain carbon atoms.

  As a method for introducing the reactive functional group into the terminal of the main chain and / or side chain, a method of introducing the reactive functional group-containing monomer (β) by copolymerization, having a reactive functional group, or Examples thereof include a method using the resulting compound as a polymerization initiator, a method using a reactive functional group or a resulting compound as a chain transfer agent, and a method using these methods in combination.

  As the reactive functional group-containing monomer (β) in the case of introducing a reactive functional group by copolymerization, the above reaction is performed using a monomer copolymerizable with the monomer that gives the fluoropolymer (b1). If it has a functional functional group, it will not be restrict | limited in particular. Specifically, for example, the following can be exemplified.

  Examples of the first monomer (β) include aliphatic unsaturated carboxylic acids described in WO 2005/100420 pamphlet. Unsaturated carboxylic acids have at least one polymerizable carbon-carbon unsaturated bond in one molecule, and at least one carbonyloxy group (—C (═O) —O—) in one molecule. What has is preferable.

  The aliphatic unsaturated carboxylic acid may be an aliphatic unsaturated monocarboxylic acid or an aliphatic unsaturated polycarboxylic acid having two or more carboxyl groups. Examples of the aliphatic unsaturated monocarboxylic acid include unsaturated aliphatic monocarboxylic acids having 3 to 6 carbon atoms such as (meth) acrylic acid and crotonic acid.

  Examples of the aliphatic unsaturated polycarboxylic acid include 3 to 3 carbon atoms such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid, maleic anhydride, itaconic anhydride or citraconic anhydride. 6 unsaturated aliphatic polycarboxylic acids.

As the second of the monomer (β), the following general formula:
CX ⁶ ₂ = CY ¹ − (Rf ⁴ ) _n −Z ¹
(In the formula, Z ¹ is a reactive functional group; X ⁶ and Y ¹ are the same or different and are a hydrogen atom or a fluorine atom; Rf ⁴ is an alkylene group having 1 to 40 carbon atoms; A fluorine-containing oxyalkylene group having 1 to 40 carbon atoms having an ether bond, or a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms having an ether bond; n is 0 or 1) Saturated compounds.

  The content of the functional group-containing monomer (β) unit introduced by copolymerization is preferably 0.05 mol% or more, and more preferably 0.1 mol% or more. If the amount is too large, gelation or vulcanization reaction is likely to occur during heating and melting, and therefore the upper limit of the functional group-containing monomer is preferably 5 mol%, and more preferably 3 mol%.

  The fluororesin (b) can be obtained by a conventionally known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization or bulk polymerization. In the polymerization, each condition such as temperature and pressure, the polymerization initiator and other additives can be appropriately set according to the composition and amount of the desired fluororesin (b).

  Although melting | fusing point of a fluororesin (b) is not specifically limited, It is preferable that it is 160-270 degreeC.

  Further, the molecular weight of the fluororesin (b) is preferably in a range in which the obtained molded product can exhibit good mechanical properties, low fuel permeability, and the like. For example, when melt flow rate (MFR) is used as an index of molecular weight, MFR at an arbitrary temperature in the range of about 230 to 350 ° C., which is a general molding temperature range of fluororesin, is 0.5 to 100 g / 10 min. It is preferable.

  The melting point of the fluororesin (b) is determined as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a DSC apparatus (manufactured by Seiko). MFR uses a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the weight (g) of the polymer flowing out in a unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 5 kg at each temperature. taking measurement.

  In the present invention, the fluororesin layer (B) may contain one of these fluororesins (b), or may contain two or more.

The fluororesin layer (B) in the laminate of the present invention preferably has a fuel permeability coefficient of 10 g · mm / m ² / day or less when the laminate is used as a material around the fuel, and is 1.0 g · mm. / M ² / day or less is more preferable, and 0.5 g · mm / m ² / day or less is more preferable.

  The fuel permeation coefficient was obtained by incorporating a sheet obtained from the resin to be measured into a fuel permeation coefficient measuring cup charged with a mixed solvent of isooctane / toluene / ethanol in which isooctane, toluene and ethanol were mixed at a volume ratio of 45:45:10. It is a value calculated from the mass change measured at ° C.

  In the present invention, when the fluororesin (b) has a specific reactive functional group at its terminal, the adhesiveness with the rubber layer (A) is greatly improved. Therefore, it is possible to provide a molded article (for example, a fuel tank) having excellent impact resistance and strength.

  In addition, when the fluororesin (b) is a perhalopolymer, chemical resistance and low fuel permeability are more excellent. A perhalopolymer is a polymer in which halogen atoms are bonded to all the carbon atoms constituting the main chain of the polymer.

  The fluororesin layer (B) is further blended with various fillers such as inorganic powder, glass fiber, carbon powder, carbon fiber, and metal oxide within a range that does not impair the performance depending on the purpose and application. It may be.

  For example, in order to further reduce fuel permeability, smectite-based lamellar viscous minerals such as montmorillonite, beidellite, saponite, nontronite, hectorite, soconite, and stevensite, and fine layered minerals with high aspect ratio such as mica are used. It may be added.

  In order to impart conductivity, a conductive filler may be added. The conductive filler is not particularly limited, and examples thereof include conductive simple powder such as metal and carbon or conductive simple fiber; powder of conductive compound such as zinc oxide; surface conductive powder. When blending the conductive filler, it is preferable to prepare a pellet in advance by melt-kneading.

  The conductive single powder or conductive single fiber is not particularly limited, and examples thereof include metal powders such as copper and nickel; metal fibers such as iron and stainless steel; carbon black, carbon fiber, and Japanese Patent Application Laid-Open No. 3-174018. Examples thereof include carbon fibrils.

  The surface conductive treatment powder is a powder obtained by conducting a conductive treatment on the surface of a nonconductive powder such as glass beads or titanium oxide.

  The method for the surface conductive treatment is not particularly limited, and examples thereof include metal sputtering and electroless plating.

  Among the conductive fillers, carbon black is preferably used because it is advantageous in terms of economy and prevention of electrostatic charge accumulation.

The volume resistivity of the fluororesin (b) composition formed by blending a conductive filler is preferably 1 × 10 ⁰ to 1 × 10 ⁹ Ω · cm. A more preferred lower limit is 1 × 10 ² Ω · cm, and a more preferred upper limit is 1 × 10 ⁸ Ω · cm.

  Moreover, you may mix | blend a heat stabilizer, a reinforcing agent, a ultraviolet absorber, a pigment, and other arbitrary additives other than a filler.

  The laminate of the present invention can be produced by laminating these rubber layer (A) and fluororesin layer (B).

  The rubber layer (A) and the fluororesin layer (B) are laminated by forming the rubber layer (A) and the fluororesin layer (B) separately and then laminating them by means such as pressure bonding. Any method of simultaneously molding and laminating the resin layer (B) may be used.

  In the method in which the rubber layer (A) and the fluororesin layer (B) are separately molded and then laminated by means such as pressure bonding, a fluororesin molding method and a vulcanization rubber composition can be employed independently. .

  Molding of the rubber layer (A) can be carried out in various forms such as sheet and tube by heat compression molding, transfer molding, extrusion molding, injection molding, calendar molding, coating, etc. A shaped molded body can be obtained.

  The fluororesin layer (B) can be molded by a method such as heat compression molding, melt extrusion molding, injection molding, or coating. For molding, commonly used fluororesin molding machines such as injection molding machines, blow molding machines, extrusion molding machines, and various coating devices can be used to produce laminates of various shapes such as sheets and tubes. Is possible. Of these, the melt extrusion molding method is preferred because of its excellent productivity.

  Further, as will be described later, when another polymer layer (C) is laminated on the fluororesin layer (B), a molding method such as multilayer extrusion molding, multilayer blow molding, multilayer injection molding or the like can be applied. It can be set as multilayer molded articles, such as a hose and a multilayer tank.

  As a method of simultaneously molding and laminating the rubber layer (A) and the fluororesin layer (B), a vulcanizing rubber composition for forming the rubber layer (A) and a fluororesin for forming the fluororesin layer (B) are used. Examples thereof include a method of laminating simultaneously with molding by a method such as multilayer compression molding, multilayer transfer molding, multilayer extrusion molding, multilayer injection molding, and doubling. In this method, the rubber layer (A) and the fluororesin layer (B), which are unvulcanized molded bodies, can be laminated at the same time, and therefore a step of closely adhering the rubber layer (A) and the fluororesin layer (B) is particularly necessary. In addition, it is suitable for obtaining strong adhesion in the subsequent vulcanization step.

  The laminate of the present invention may be a laminate of an unvulcanized rubber layer (A) and a fluororesin layer (B), but by further vulcanizing the unvulcanized laminate, Interlayer adhesion can be obtained.

  That is, the present invention also relates to a vulcanized laminate in which the rubber layer (A1) obtained by vulcanizing the unvulcanized laminate of the present invention and the fluororesin layer (B) are vulcanized and bonded.

  For the vulcanization treatment, conventionally known vulcanization methods and conditions for vulcanizing rubber compositions can be employed. For example, a method of vulcanizing an unvulcanized laminate for a long time, heat-treating the unvulcanized laminate as a pretreatment in a relatively short time (vulcanization has also occurred), and then vulcanizing for a long time. There is a way to do it. Among these, a method of subjecting an unvulcanized laminate to a heat treatment as a pretreatment in a relatively short time and then vulcanizing it for a long time includes a rubber layer (A) and a fluororesin layer (B) in the pretreatment. Since the rubber layer (A) has already been vulcanized in the pretreatment and the shape is stabilized, various methods for holding the laminate in subsequent vulcanization should be selected. This is preferable.

  The conditions for the vulcanization treatment are not particularly limited and can be performed under normal conditions, but at 130 to 260 ° C. for 10 minutes to 80 hours, steam, press, oven, air bath, infrared, microwave, The treatment is preferably performed using lead vulcanization or the like. More preferably, it is carried out at 160 to 230 ° C. over 20 to 80 hours.

  The heating conditions for the pretreatment are not particularly limited, but the treatment may be performed at 100 to 150 ° C. for 30 seconds to 1 hour using steam, press, oven, air bath, infrared ray, microwave, lead vulcanization, etc. preferable.

  In the obtained vulcanized laminate, the vulcanized rubber layer (A1) and the fluororesin layer (B) are vulcanized and bonded, and a strong interlayer adhesion is generated.

  The laminate (unvulcanized laminate and vulcanized laminate) of the present invention has a two-layer structure of a rubber layer (A, A1, hereinafter referred to as rubber layer (A)) and a fluororesin layer (B). Alternatively, a three-layer structure such as (A)-(B)-(A) or (B)-(A)-(B) may be used. Further, it may have a multilayer structure of three or more layers in which polymer layers (C) other than the rubber layer (A) and the fluororesin layer (B) are bonded.

  The polymer layer (C) may be a rubber layer (C1) other than the rubber layer (A), a resin layer (C2) other than the fluororesin layer (B), a fiber reinforced layer, or the like. Further, the rubber layer (A) and / or the fluororesin layer (B) may be further laminated via the polymer layer (C).

  Examples of the material for the rubber layer (C1) include rubbers other than the rubber used as the rubber layer (A) directly bonded to the fluororesin layer (B), and may be fluororubber or non-fluororubber. Specific examples include those given as examples of the unvulcanized rubber (a1).

  In the unvulcanized rubber composition forming the rubber layer (C1), the amine compound (a2), the epoxy resin (a3), the vulcanizing agent (a4), the vulcanization accelerator (a5), and others You may mix | blend the compounding agent of.

  The material of the resin layer (C2) includes fluororesin (excluding fluororesin (b)), polyamide resin, polyolefin resin, vinyl chloride resin, polyurethane resin, polyester resin, polyaramid resin, polyimide resin, polyamideimide resin. , Polyphenylene oxide resin, polyacetal resin, polycarbonate resin, acrylic resin, styrene resin, acrylonitrile / butadiene / styrene resin (ABS), cellulose resin, polyetheretherketone resin (PEEK), polysulfone resin, polyethersulfone resin ( PES), resins with excellent mechanical strength such as polyetherimide resin, resins made of ethylene / vinyl alcohol copolymer, polyphenylene sulfide resin, polybutylene naphthalate resin, polybutylene Terephthalate resins, polyphthalamide (PPA), such as fuel or gas permeability is low resin (hereinafter sometimes referred to low permeability resin) and the like. Of these, polyamide resins are preferred from the viewpoint of good moldability and adhesiveness. When the laminate is subjected to vulcanization treatment, it is desirable that the melting point of the resin is higher than the temperature of the heat treatment.

  Next, the layer structure of the laminate of the present invention will be described.

(1) Two-layer structure of rubber layer (A) -fluororesin layer (B) This is a basic structure, and as described above, conventionally, in order to laminate the fluororesin layer (B) and the rubber layer (A), Fluorine resin layer-rubber layer) is not sufficiently bonded, making the process complicated, such as surface treatment on the resin side, separate application of adhesive between layers, and winding and fixing a tape-like film However, vulcanization adhesion occurs by vulcanization without assembling such a complicated process, and chemically strong adhesion is obtained.

(2) Three-layer structure of rubber layer-fluorine resin layer (B) -rubber layer (A)-(B)-(A) and (A)-(B)-(C1). When sealing performance is required, it is desirable to arrange rubber layers on both sides in order to maintain the sealing performance, for example, in joints such as fuel pipes.

  Further, the fuel pipe has a (A)-(B)-(C1) type structure, a non-fluororubber layer is provided as the rubber layer (A), a fluororubber layer is provided as the rubber layer (C1), and the fluororubber layer (C1). By using as the inner layer of the pipe, chemical resistance and low fuel permeability are improved.

(3) Three-layer structure of resin layer-rubber layer (A) -resin layer (B)-(A)-(B) and (B)-(A)-(C2).

  The shape is stabilized by arranging the resin layers on both sides. Moreover, it is suitable when chemical resistance is important. Further, when different mechanical properties are required on each side, the (B)-(A)-(C2) type is preferable.

(4) Three-layer structure of resin layer (C2) -fluorine resin layer (B) -rubber layer (A)

(5) Three-layer structure of fluororesin layer (B) -rubber layer (A) -rubber layer (C1)

(6) Four-layer structure or more In addition to the three-layer structure of (2) to (5), an optional rubber layer (A) or (C1) or resin layer (B) or (C2) is laminated depending on the purpose. May be. In addition, a layer such as a metal foil may be provided, or an adhesive layer may be interposed other than between the rubber layer (A) and the fluororesin layer (B).

  Furthermore, it can be laminated with the polymer layer (C) to form a lining body.

  In addition, what is necessary is just to select the thickness of each layer, a shape, etc. suitably according to a use purpose, a use form, etc.

  The laminate of the present invention, particularly the vulcanized laminate, is excellent in low fuel permeability, heat resistance, oil resistance, fuel oil resistance, LLC resistance, steam resistance, and under severe conditions. And can be used for various purposes.

  For example, automotive engine engines, main motion systems, valve systems, lubrication / cooling systems, fuel systems, intake / exhaust systems, drive system transmission systems, chassis steering systems, brake systems, etc. Gaskets that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance, and non-contact and contact type packings (self-sealing) such as basic electrical parts, control system electrical parts, and equipped electrical parts (Packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.), etc., and suitable characteristics as bellows, diaphragm, hose, tube, electric wire, etc.

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

  Engine body cylinder head gasket, cylinder head cover gasket, oil pan packing, gaskets such as general gaskets, seals such as O-rings, packing, timing belt cover gaskets, hoses such as control hoses, anti-vibration rubber for engine mounts, etc.

  Shaft seals such as crankshaft seals and camshaft seals for main motion systems.

  Valve stem seals for engine valves, etc.

  Engine oil cooler hose, oil return hose, seal gasket, etc. for lubrication / cooling engine oil cooler, water hose around radiator, vacuum pump oil hose for vacuum pump, etc.

  Fuel system, fuel pump oil seal, diaphragm, valve, etc. Filler (neck) hose, fuel supply hose, fuel return hose, fuel hose such as vapor (evaporation) hose, fuel tank in-tank hose, filler seal, tank Carburettors such as packing, in-tank fuel pump mount, fuel piping tube main body and connector O-ring, fuel injector injector cushion ring, injector seal ring, injector O-ring, pressure regulator diaphragm, check valves, etc. Needle valve petals, acceleration pump pistons, flange gaskets, control hoses, etc., composite air control (CAC) valve seats, diaphragms, etc.

  Inlet / exhaust manifold manifold manifold packing, exhaust manifold packing, EGR diaphragm, control hose, emission control hose, BPT diaphragm, AB valve afterburn prevention valve seat, etc. Throttle body packing, turbocharger turbo oil hose (supply), turbo oil hose (return), turbo air hose, intercooler hose, turbine shaft seal etc.

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

  Steering power steering oil hose, etc.

  Brake oil seals, O-rings, packings, brake oil hoses, etc. Master back atmospheric valves, vacuum valves, diaphragms, etc. Master cylinder piston cups (rubber cups), caliper seals, boots, etc.

  Tubes for harness exterior parts such as electric wire (harness) insulators and sheaths of basic electrical components.

  Cover materials for various sensor wires of control system electrical components.

  Car equipment air conditioner O-ring, packing, cooler hose, etc.

  In addition to automobiles, for example, oil, chemical, heat, steam, or weather resistant packings, O-rings, hoses, other sealing materials, diaphragms, valves, chemicals, etc. Similar packings in plants, O-rings, seals, diaphragms, valves, hoses, rolls, tubes, chemical coatings, linings, similar packings in food plant equipment and food equipment (including household products), O- Rings, hoses, sealing materials, belts, diaphragms, valves, rolls, tubes, similar packings in nuclear power plant equipment, O-rings, hoses, sealing materials, diaphragms, valves, tubes, similar packings in general industrial parts, O-ring, hose, sealing material, diaphragm Is suitable valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, the application to a roll blade PPC copying machine. For example, the backup rubber material of PTFE diaphragm has a problem that it is worn out or torn during use because of its poor sliding property, but by using the laminate of the present invention, this problem can be improved and suitable. Can be used for

  In addition, in food rubber seal material applications, there is a problem that flavoring and rubber fragments are mixed into food in conventional rubber seal materials, but by laminating and coating rubber with fluororesin, the laminate of the present invention can be obtained. By using it, this problem can be improved and it can be used suitably. Rubber seal materials for pipes that use solvents for pharmaceutical and chemical applications have a problem that rubber materials swell in the solvent. However, the use of the laminate of the present invention improves the rubber materials. In the general industrial field, for the purpose of improving the strength, slipperiness, chemical resistance, and permeability of rubber materials, it can be suitably used for rubber rolls, O-rings, packings, sealing materials, and the like. In particular, it can be preferably used for packing of lithium ion batteries because both chemical resistance and sealing can be maintained at the same time.

  The fuel pipe made of the laminate in the present invention can be produced by a usual method and is not particularly limited. Further, the fuel pipe of the present invention includes a corrugated tube.

  Among these, the fuel pipe made of the laminate is particularly preferable in terms of heat resistance and low fuel permeability.

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

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

(1) Polymer composition
^It was measured by ¹⁹ F-NMR analysis.

(2) Melting point Using a Seiko DCS device, the melting peak when the temperature was raised at a rate of 10 ° C / min was recorded, and the temperature corresponding to the maximum value was taken as the melting point.

(3) MFR (Melt Flow Rate)
Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the weight (g) of the polymer flowing out in a unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under various temperatures and 5 kg load was measured.

(4) Measurement of single layer fuel permeation Each of the resin pellets was placed in a mold having a diameter of 120 mm, set in a press machine heated to 300 ° C., melt-pressed at a pressure of about 2.9 MPa, thickness 0 A 15 mm sheet was obtained. Put the obtained sheet into a SUS316 transmission coefficient measuring cup made of SUS316 with an inner diameter of 40 mmφ and a height of 20 mm containing 18 mL of CE10 (fuel obtained by mixing 10% by volume of ethanol in a 50:50 volume ratio of isooctane and toluene) The mass change at 60 ° C. was measured up to 1000 hours. The fuel permeation coefficient (g · mm / m ² / day) was calculated from the change in mass per hour, the surface area of the sheet in contact with the liquid, and the thickness of the sheet.

(5) Functional group analysis by infrared absorption spectrum A sheet having a thickness of 0.15 to 0.30 mm is prepared, and the infrared absorption spectrum is analyzed using a Perkin-Elmer FT-IR spectrometer 1760X (manufactured by PerkinElmer). did. The obtained infrared absorption spectrum was analyzed using Perkin-Elmer Spectrum for windows Ver. The baseline was automatically determined using 1.4C, and the absorbance of a predetermined peak was measured to identify the functional group of the fluororesin. The film thickness was measured using a micrometer.

(6) Vulcanization characteristics A vulcanization curve at 170 ° C. is obtained using a JSR curlastometer type II and evaluated according to the following criteria.
○: The vulcanization curve is normal, and the amplitude becomes constant after the optimum curing time.
Δ: The vulcanization curve is normal, but the vulcanization gradually proceeds with time and the amplitude is not constant.
X: The vulcanization curve is abnormal, and curing does not proceed even after a lapse of time.

Synthesis Example 1 (Synthesis of fluororesin 1)
51.5 kg of demineralized pure water was charged in a jacketed stirring polymerization tank capable of containing 174 kg of water, the interior space was sufficiently replaced with pure nitrogen gas, and then the nitrogen gas was removed in vacuum. Next, 40.6 kg of octafluorocyclobutane, 1.3 kg of chlorotrifluoroethylene (CTFE), 4.5 kg of tetrafluoroethylene (TFE), and 2.8 kg of perfluoro (propyl vinyl ether) (PPVE) were injected. 0.075 kg of n-propyl alcohol (PrOH) was added as a chain transfer agent, the temperature was adjusted to 35 ° C., and stirring was started. Here, 0.44 kg of a 50 mass% methanol solution of di-n-propyl peroxydicarbonate (NPP) was added as a polymerization initiator to initiate polymerization. During the polymerization, a mixed monomer prepared to have the same composition as the desired copolymer composition is polymerized while being additionally charged so that the pressure in the tank is maintained at 0.66 MPa, and then the residual gas in the tank is exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain 30.5 kg of a granular powder CTFE copolymer. Next, melt kneading was performed at a cylinder temperature of 290 ° C. using a φ50 mm short axis extruder to obtain pellets. Next, the obtained pellet-like CTFE copolymer was heated at 190 ° C. for 24 hours. Table 2 shows the physical properties of the obtained polymer. The number of functional groups with respect to 10 ⁶ main chain carbons was 180.

Synthesis Example 2 (Synthesis of fluororesin 2)
200 L of deoxygenated pure water was put into an autoclave made of glass lining having an internal volume of 820 L and evacuated. Then, 113 kg of 1-fluoro-1,1-dichloroethane, 95 kg of hexafluoropropylene, and 85 kg of cyclohexane were charged. Furthermore, after charging 292 g of perfluoro (1,1,5-trihydro-1-pentene) represented by the formula (i): CH ₂ ═CF (CF ₂ ) ₃ H, the temperature in the tank was stirred at 35 ° C. The speed was kept at 200 rpm.

Further, tetrafluoroethylene was pressed into 7.25 kgf / cm ² G, and then ethylene (Et) was pressed into 0.78 MPa. Subsequently, the polymerization was started by charging 1.9 kg of a 50% methanol solution of dinormalpropyl peroxycarbonate. Since the pressure decreases as the polymerization proceeds, a mixed gas of tetrafluoroethylene / ethylene / perfluorocyclobutane (molar ratio = 39.2: 43.6: 17.2, where perfluorocyclobutane is a chain transfer agent) is additionally injected. The polymerization was continued while maintaining the polymerization pressure at 0.78 MPa, and the compound of the formula (i) was divided into 1100 g 20 times and charged with a micropump, and the polymerization was carried out for a total of 32 hours. After completion of the polymerization, the contents were collected, washed with water, filtered, and dried under reduced pressure at 80 ° C. for 8 hours to obtain 95 g of a powdery polymer. Next, melt kneading was performed at a cylinder temperature of 230 ° C. using a φ50 mm short-axis extruder to obtain pellets. Subsequently, the obtained pellet-shaped copolymer was heated at 120 ° C. for 24 hours. Table 2 shows the physical properties of the obtained polymer. The number of functional groups for 10 ⁶ main chain carbon atoms was 355.

Synthesis Example 3 (Synthesis of fluororesin 3)
After putting 1.3 L of deoxygenated pure water into an autoclave made of glass lining having an internal volume of 4 L and evacuating it, 0.8 kg of 1-fluoro-1,1-dichloroethane and 1.3 g of cyclohexane were charged. Furthermore, after charging 4.2 g of perfluoro (1,1,5-trihydro-1-pentene) represented by the formula (i): CH ₂ ═CF (CF ₂ ) ₃ H, the temperature in the tank was 35 ° C. Kept.

Further, under stirring, a tetrafluoroethylene / ethylene mixed gas (molar ratio = 95: 5) was injected under pressure to 1.28 MPa. Next, 12.7 g of a 50% methanol solution of dinormalpropyl peroxycarbonate was charged to initiate polymerization. Since the pressure decreases as the polymerization proceeds, a mixed gas of tetrafluoroethylene / ethylene / perfluorocyclobutane (molar ratio = 64.0: 33.5: 2.5) is additionally injected to bring the polymerization pressure to 1.28 MPa. While maintaining the polymerization, the polymerization was carried out for a total of 30 hours. After the completion of the polymerization, about 30 g of 28% ammonia aqueous solution was added and treated at 80 ° C. for 5 hours. The contents were collected, washed with water, filtered, and dried under reduced pressure at 80 ° C. for 8 hours to obtain 300 g of a powdery polymer. Table 2 shows the physical properties of the obtained polymer. The number of functional groups per 10 ⁶ main chain carbons was 34.

Synthesis Example 4 (Synthesis of fluororesin 4)
After evacuating a polymerization tank equipped with a stirrer having an internal volume of 100 L, 71.3 kg of 1-hydrotridecafluorohexane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane were added. 20.4 kg, formula (ii): 562 g of CH ₂ ═CH (CF ₂ ) ₂ F and 3.4 g of itaconic anhydride were charged, and the temperature in the polymerization tank was raised to 66 ° C. Next, the pressure was increased to 1.5 MPa with a mixed gas of tetrafluoroethylene / ethylene (molar ratio = 89: 11). As a polymerization initiator, 1 L of a 0.5% 1-hydrotridecafluorohexane solution of ter-butylperoxypivalate was charged to initiate polymerization. Since the polymerization pressure decreased with the progress of the polymerization, a tetrafluoroethylene / ethylene mixed gas (molar ratio = 59.5: 40.5) was continuously charged so that the pressure became constant at 1.5 MPa. Also, CH ₂ ═CH (CF ₂ ) ₂ F in an amount corresponding to 3.3 mol% and anhydrous in an amount corresponding to 0.3 mol% with respect to the total number of moles of tetrafluoroethylene and ethylene charged during the polymerization. Itaconic acid was continuously charged. The polymerization was carried out for about 8.5 hours. When 7.3 kg of the monomer mixed gas was charged, the polymerization temperature was cooled to room temperature and purged to normal pressure. The obtained contents are put into a 200 L granulation tank containing 80 kg of water, heated to 105 ° C. while stirring, granulated while distilling and removing the polymerization medium, and then dried at 150 ° C. for 15 hours. As a result, 7.9 kg of a powdery polymer was obtained. Subsequently, extrusion was performed at 280 ° C. with a twin-screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd., Labo Plast Mill) to produce pellets. Table 2 shows the physical properties of the obtained polymer.

で示されるパーフルオロ（１，１，９，９−テトラハイドロ−２．５−ビストリフルオロメチル−３，６−ジオキサ−８−ノネノール）を５．０ｇ、パーフルオロ（プロピルビニルエーテル）（ＰＰＶＥ）を１３０ｇ、メタノールを１８０ｇ、窒素ガスを用いて圧入し、系内の温度を３５℃に保った。撹拌を行いながら、テトラフルオロエチレンガス（ＴＦＥ）を内圧が０．７８ＭＰａとなるように圧入した。ついでジ−ｎ−プロピルパーオキシジカーボネートの５０％メタノール溶液を０．５ｇ、窒素を用いて圧入して反応を開始した。重合反応の進行に伴って圧力が低下するので、０．７４ＭＰａまで低下した時点でテトラフルオロエチレンガスで０．７８ＭＰａまで再加圧し、降圧、昇圧を繰り返した。テトラフルオロエチレンの供給を続けながら、重合開始からテトラフルオロエチレンガスが約６０ｇ消費されるごとに、前記のヒドロキシ基を有する含フッ素エチレン性単量体（iii）の２．５ｇを計９回（合計２２．５ｇ）圧入して重合を継続し、重合開始よりテトラフルオロエチレンが約６００ｇ消費された時点で供給を止めてオートクレーブを冷却し、未反応モノマーおよび１，２−ジクロロ１，１，２，２−テトラフルオロエタンを放出した。得られた共重合体を水洗、メタノール洗浄を行ったのち、真空乾燥することにより７１０ｇの白色固体（粉末）を得た。 Synthesis Example 5 (Synthesis of fluororesin 5)
Into a 6 L glass-lined autoclave equipped with a stirrer, a valve, a pressure gauge, and a thermometer, 1500 mL of pure water was placed, thoroughly replaced with nitrogen gas, evacuated, and 1,2-dichloro 1,1,2,2- 1500 g of tetrafluoroethane was charged. Then, formula (iii):

Perfluoro (1,1,9,9-tetrahydro-2.5-bistrifluoromethyl-3,6-dioxa-8-nonenol) represented by the formula: 5.0 g perfluoro (propyl vinyl ether) (PPVE) 130 g, 180 g of methanol, and nitrogen gas were used for press-fitting, and the temperature inside the system was maintained at 35 ° C. While stirring, tetrafluoroethylene gas (TFE) was injected so that the internal pressure was 0.78 MPa. Next, 0.5 g of a 50% methanol solution of di-n-propyl peroxydicarbonate was injected with nitrogen to initiate the reaction. Since the pressure decreased with the progress of the polymerization reaction, when the pressure decreased to 0.74 MPa, the pressure was again increased to 0.78 MPa with tetrafluoroethylene gas, and the pressure reduction and pressure increase were repeated. While supplying tetrafluoroethylene, every time about 60 g of tetrafluoroethylene gas is consumed from the start of polymerization, 2.5 g of the fluorine-containing ethylenic monomer (iii) having a hydroxy group is totaled 9 times ( The polymerization was continued by press-fitting, and when about 600 g of tetrafluoroethylene was consumed from the start of the polymerization, the supply was stopped and the autoclave was cooled, and the unreacted monomer and 1,2-dichloro 1,1,2 , 2-tetrafluoroethane was released. The obtained copolymer was washed with water and methanol, and then vacuum-dried to obtain 710 g of a white solid (powder).

  The obtained white powder was extruded at 350 to 370 ° C. with a twin screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd., Labo Plast Mill) to produce pellets. Table 2 shows the physical properties of the obtained polymer.

  The chemical | medical agent used except the said fluororesins 1-5 is shown below.

  Rubber 1: A rubber composition composed of acrylonitrile-butadiene rubber (NBR) (manufactured by N530 JSR) (30 parts by mass of carbon black, 5 parts by mass of zinc oxide, 15 parts by mass of wet silica, 100 parts by mass of stearin), stearin 1 part by weight of acid, 2 parts by weight of anti-aging agent, 15 parts by weight of oil, 2 parts by weight of peroxide vulcanizing agent, 2 parts by weight of wax)

  Rubber 2: A rubber composition composed of acrylonitrile-butadiene rubber (NBR) (manufactured by N530 JSR) (100 parts by mass of PVC, 100 parts by mass of PVC, 30 parts by mass of carbon black, 5 parts by mass of zinc oxide, wet silica 15) (Contains 1 part by mass, 1 part by mass of stearic acid, 2 parts by mass of anti-aging agent, 15 parts by mass of oil, 2 parts by mass of peroxide vulcanizing agent, 2 parts by mass of wax)

Epoxy resin: JER828, epoxy resin (formula (1)) (made by Japan Epoxy Resin Co., Ltd.)

Amine compound: N, N-dicinnamylidene-1,6-hexamethylenediamine (formula (2)) (manufactured by Daikin Industries, Ltd.)

DBU vulcanization accelerator No. 1: 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride (DBU-B) (formula (3)) (manufactured by Wako Pure Chemical Industries, Ltd.)

DBU vulcanization accelerator No. 2: DBU-orthophthalate (formula (4)) (trade name SA-810, manufactured by San Apro Co., Ltd.)

DBU vulcanization accelerator No. 3: DBU-phenol salt (formula (5)) (trade name SA-1, manufactured by San Apro Co., Ltd.)

Production Example 1 (Manufacture of rubber layer)
An epoxy resin and an amine compound are added to the rubber 1 so as to have a blending ratio shown in Tables 3 and 4, and kneaded at 25 to 70 ° C. by a normal method using a kneading roll machine equipped with two 8-inch rolls. did. This was left at room temperature for about 20 hours, then kneaded again in the same roll machine, and finally sheeted to a thickness of about 3 mm to take out an unvulcanized rubber sheet (rubber layer).

Examples 1-8 and Comparative Examples 1-9
An unvulcanized rubber sheet (rubber layer) shown in Tables 3 and 4 having a thickness of about 3 mm and each fluororesin film (fluorine resin layer) having thicknesses shown in Tables 3 and 4 are overlapped, and one end portion After sandwiching a fluororesin film (thickness: 10 μm, Daikin Industries, Ltd., trade name: Polyflon PTFE M731 skive film) between both sheets, a metal spacer so that the resulting sheet has a thickness of 2 mm Was inserted into a metal mold and pressed at the pressing temperature and pressing time shown in Tables 3 and 4 to vulcanize to obtain a sheet-like laminate. The obtained laminate was cut into a strip shape having a width of 10 mm and a length of 40 mm, and a fluororesin film was peeled off to prepare a test piece for gripping. Using this test piece, a T peel test was performed at 23 ° C. at a peel rate of 50 mm / min, and the adhesive strength was measured. Moreover, the peeling mode was observed and adhesion | attachment evaluation was performed on the following references | standards.

(Peeling mode)
○: Material fracture fractured due to strong adhesion.
Δ: The interface between the fluororesin layer and the rubber layer was sufficiently adhered and difficult to peel.
X: Peeled at the interface between the fluororesin layer and the rubber layer.

(Appearance of rubber layer)
○: Vulcanization was sufficient and surface condition was good.
X: Insufficient vulcanization and poor surface condition due to foaming.

Production Example 2 (Production of rubber layer)
An epoxy resin, an amine compound, and a DBU vulcanization accelerator shown in Table 5 are added to the rubber 1 so as to have a blending ratio shown in Table 5, and a conventional method using a kneading roll machine equipped with two 8-inch rolls. It knead | mixed at 25-70 degreeC. This was left at room temperature for about 20 hours, then kneaded again in the same roll machine, and finally sheeted to a thickness of about 3 mm to take out an unvulcanized rubber sheet (rubber layer). The vulcanization characteristics of these unvulcanized rubbers were examined. The results are shown in Table 5.

Production Example 3 (Production of rubber layer)
An amine compound and a DBU vulcanization accelerator shown in Table 5 are added to rubber 1 so as to have a blending ratio shown in Table 5, and 25 to 25 by a conventional method using a kneading roll machine equipped with two 8-inch rolls. It knead | mixed at 70 degreeC. This was left at room temperature for about 20 hours, then kneaded again in the same roll machine, and finally sheeted to a thickness of about 3 mm to take out an unvulcanized rubber sheet (rubber layer). The vulcanization characteristics of these unvulcanized rubbers were examined. The results are shown in Table 5.

Examples 9-14
An unvulcanized rubber sheet (rubber layer) shown in Table 5 having a thickness of about 3 mm and a film (fluororesin layer) of each fluororesin 1 having a thickness shown in Table 5 are overlapped, and a width of about 10 is provided at one end. A gold spacer with a metal spacer so that the resulting sheet has a thickness of 2 mm after sandwiching a fluororesin film (thickness of 10 μm, Daikin Industries, Ltd., trade name: Polyflon PTFE M731 skive film) between both sheets. It was inserted into a mold and vulcanized by pressing at a pressing temperature and pressing time shown in Table 5 to obtain a sheet-like laminate. The obtained laminate was cut into a strip shape having a width of 10 mm and a length of 40 mm, and a fluororesin film was peeled off to prepare a test piece for gripping. Using this test piece, the adhesion was evaluated in the same manner as in Example 1. The results are shown in Table 5.

Claims (17)

A rubber layer (A) formed from a rubber composition for vulcanization containing an unvulcanized rubber (a1) , an amine compound (a2) and an epoxy resin (a3) ;
At least one reactive functional group side chains and / or fluorocarbon resin layer formed of a fluorine resin (b) having a main chain terminus is selected from the group consisting of carbonyl and hydroxyl groups (B) are laminated ,
The amine compound (a2) is hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, or 4,4′-bis (aminocyclohexyl) methanecarbamate.
Laminated body. Laminate according to claim 1 Symbol placement unvulcanized rubber (a1) is a non-fluorine rubber. The laminate according to claim 1 or 2, wherein the unvulcanized rubber is acrylonitrile-butadiene rubber. The laminate according to any one of claims 1 to 3 , wherein the content of the amine compound (a2) in the rubber layer (A) is 1 to 25 parts by mass with respect to 100 parts by mass of the unvulcanized rubber. The laminate according to any one of claims 1 to 4 , wherein the content of the epoxy resin (a3) in the rubber layer (A) is 1 to 25 parts by mass with respect to 100 parts by mass of the unvulcanized rubber. In the rubber composition for vulcanization, the unvulcanized rubber (a1) is acrylonitrile-butadiene rubber, and further contains a sulfur vulcanizing agent or a peroxide vulcanizing agent as the vulcanizing agent (a4). The laminated body in any one of 1-5 . The laminate according to claim 6 , wherein the rubber composition for vulcanization contains a 1,8-diazabicyclo [5,4,0] -7-undecene vulcanization accelerator as the vulcanization accelerator (a5). Chlorotrifluoroethylene-tetrafluoroethylene-perfluoro (alkyl) in which the fluororesin (b) has at least one reactive functional group selected from the group consisting of a carbonyl group and a hydroxyl group at the side chain and / or main chain terminal laminate according to any one of claims 1 to 7, which is a vinyl ether) copolymer. The laminate according to any one of claims 1 to 8 , wherein the rubber layer (A) is laminated on both sides of the fluororesin layer (B). The laminate according to any one of claims 1 to 8 , wherein the fluororesin layer (B) is laminated on both sides of the rubber layer (A). Furthermore, the polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B) is laminated on one side or both sides of the laminate described in any one of claims 9 or 10 . The laminated body in any one of 10 . A laminate in which a rubber layer (A1) obtained by vulcanizing the laminate according to any one of claims 1 to 11 and a fluororesin layer (B) are vulcanized and bonded. A rubber composition for vulcanization comprising an unvulcanized rubber (a1), an amine compound (a2) , an epoxy resin (a3) and a vulcanizing agent (a4), wherein the unvulcanized rubber (a1) is acrylonitrile-butadiene a rubber, a vulcanizing agent (a4) is a sulfur-based vulcanizing agent or peroxide vulcanizing agent der is, the amine compound (a2), hexamethylenediamine carbamate, N, N'-dicinnamylidene-1,6 A rubber composition for vulcanization which is hexamethylenediamine or 4,4′-bis (aminocyclohexyl) methane carbamate . The rubber composition for vulcanization | cure of Claim 13 which contains 1-25 mass parts of amine compounds (a2), and 1-10 mass parts of vulcanizing agents (a4) with respect to 100 mass parts of unvulcanized rubber (a1). . The rubber composition for vulcanization | cure of Claim 13 or 14 which contains 1-25 mass parts of epoxy resins (a3) with respect to 100 mass parts of unvulcanized rubber (a1). The vulcanization rubber composition according to any one of claims 13 to 15 , further comprising a 1,8-diazabicyclo [5,4,0] -7-undecene vulcanization accelerator as the vulcanization accelerator (a5). . 1 to 10 parts by mass of 1,8-diazabicyclo [5,4,0] -7-undecene vulcanization accelerator is included as a vulcanization accelerator (a5) with respect to 100 parts by mass of the unvulcanized rubber (a1). The rubber composition for vulcanization | cure in any one of Claims 13-16 .