JP2010280103A - Laminate, molding, fuel hose and method for manufacturing the laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate achieving high fuel barrier performance using a novel fluororesin. <P>SOLUTION: The laminate includes a layer (A) made of a fluororesin and a layer (B) made of an elastomer. The fluororesin is a copolymer containing copolymerization units of tetrafluoroethylene, vinylidene fluoride and optionally an ethylenic unsaturated monomer(s) other than tetrafluoroethylene and vinylidene fluoride and has a storage modulus E' at 170°C of 60-400 MPa, through the measurement of the dynamic viscoelasticity. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a laminate, a molded article, a fuel hose, and a method for manufacturing the laminate.

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. Thermoplastic resins such as polyphenylene sulfide resins, ethylene vinyl alcohol resins, and liquid crystal polyester resins are used as materials with excellent fuel barrier properties, but these materials have high fuel barrier properties but are flexible. It is scarce and difficult to use for parts that require flexibility. In contrast, rubber-based materials have high flexibility but generally have poor fuel barrier properties. When used in automotive parts such as fuel hoses, volatilization and transpiration of fuel are large, and improvements are required. It has been. In order to solve these problems, in recent years, a fuel hose having a laminated structure including a resin layer having a high fuel barrier property and an elastomer layer having a high flexibility has been proposed.

For example, Patent Documents 1 and 2 include a first layer comprising a fluoroplastic, wherein the first layer is substantially in contact with a second layer comprising a mixture of a curable elastomer and a dehydrofluorinated composition. A layered product has been proposed. In Patent Document 1, it is useful that the fluoroplastic is a copolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene. In Patent Document 2, hexafluoropropylene, tetrafluoroethylene is used as the fluoroplastic. Fluoropolymers derived from ethylene and copolymerized units containing ethylene have been found useful.

Patent Document 3 proposes a layered molded body made of a fluororesin composed of propylene hexafluoride, ethylene tetrafluoride, and vinylidene fluoride, and epichlorohydrin rubber.

In Patent Document 4, an inner layer, which is a molded product of a ternary fluororesin of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride, 1,8-diazabicyclo (5.4.0) undecene-7 salt, and organic phosphonium salt An outer layer which is a cross-linked molded product of a cross-linking composition of epichlorohydrin rubber or NBR / PVC blend blended with NBR, NBR blended with 1 · 8-diazabicyclo (5.4.0) undecene-7 salt and organic phosphonium salt A hose for automobile fuel piping has been proposed in which the innermost layer, which is a cross-linked molded product of a cross-linking composition of a rubber or fluoro rubber, is firmly bonded.

In Patent Document 5, (1) a crosslinked rubber composition in which 1,8-diazabicyclo (5,4,0) undecene-7 or a weak acid salt thereof is blended with epichlorohydrin rubber, and (2) tetra A laminate comprising fluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer fluorine-containing resin has been proposed.

JP 2001-526972 A Special table 2001-527104 gazette JP-A-8-118549 Japanese Patent Laid-Open No. 8-169085 JP-A-8-294998

Thus, a laminate in which a fluororesin having a high fuel barrier property is laminated with an elastomer layer having a high flexibility is known. However, these laminates do not have sufficient fuel barrier properties.

Accordingly, the present invention provides a laminate that achieves high fuel barrier properties and strong adhesion to elastomers by using a novel fluororesin.

The present invention is a laminate comprising a layer (A) made of a fluororesin and a layer (B) made of an elastomer, wherein the fluororesin comprises tetrafluoroethylene, vinylidene fluoride, and optionally an ethylenically unsaturated monomer. A copolymer containing copolymerized units of a monomer (excluding tetrafluoroethylene and vinylidene fluoride), and a storage elastic modulus (E ′) at 170 ° C. by dynamic viscoelasticity measurement of 60 to 400 MPa. It is the laminated body characterized by being.

This invention is also a molded article formed from the said laminated body.

This invention is also a fuel hose formed from the said laminated body.

This invention is also a manufacturing method of the said laminated body.

The laminate of the present invention includes a fluororesin layer (A) and an elastomer layer (B), and is particularly characterized by including a fluororesin layer (A) formed from a novel fluororesin. Due to this feature, the laminate of the present invention exhibits excellent adhesion between the fluororesin layer and the elastomer layer, has high fuel barrier properties, and is advantageous in terms of cost.

(A) Fluororesin layer The layer (A) is formed from a fluororesin. A fluororesin is a copolymer containing copolymerized units of tetrafluoroethylene, vinylidene fluoride, and optionally an ethylenically unsaturated monomer (excluding tetrafluoroethylene and vinylidene fluoride), The storage elastic modulus (E ′) at 170 ° C. by dynamic viscoelasticity measurement is 60 to 400 MPa.

Conventionally, a fluororesin which is laminated with an elastomer and imparts barrier properties has a relatively high flexibility, and therefore has a relatively low crystallinity. For example, Dyneon's THV resin is a copolymer of tetrafluoroethylene, vinylidene fluoride, and hexafluoropropylene (and may contain perfluoro (propyl) vinyl ether), and has a crystallization heat of 20 mj / mg or less. It is a resin with relatively low crystallinity. Generally, when crystallinity is lowered, the barrier property is deteriorated.

On the other hand, the fluororesin used in the present invention has high crystallinity by copolymerizing tetrafluoroethylene, vinylidene fluoride, and an ethylenically unsaturated monomer at a specific composition ratio. Therefore, the laminate of the present invention including the layer (A) made of the fluororesin has excellent barrier properties.

Since the fluororesin used in the present invention has high crystallinity, it exhibits a high storage elastic modulus even at a high temperature of 170 ° C., and has excellent barrier properties even at a high temperature. In addition, a fluororesin having a low elastic modulus was conventionally used as a fluororesin laminated with an elastomer so as not to impair the flexibility of the elastomer. However, the fluororesin used in the present invention has excellent fuel permeability. A thin layer can be used, and even if the elastic modulus is high, the layers can be laminated without impairing the flexibility of the elastomer. This problem can also be solved by adopting the fluororesin used in the present invention in a layer constituting a sandwich structure such as elastomer / fluororesin / elastomer.

The fluororesin has a storage elastic modulus (E ′) at 170 ° C. of 60 to 400 MPa as measured by dynamic viscoelasticity. The storage elastic modulus is a value measured at 170 ° C. by dynamic viscoelasticity measurement. More specifically, the storage elastic modulus is a dynamic viscoelastic device DVA220 manufactured by IT-Measurement Control Co., Ltd., having a length of 30 mm, a width of 5 mm, and a thickness of 0. This is a value obtained by measuring a 25 mm sample under the conditions of a tensile mode, a grip width of 20 mm, a measurement temperature of 25 ° C. to 250 ° C., a temperature increase rate of 2 ° C./min, and a frequency of 1 Hz. A preferable storage elastic modulus (E ′) at 170 ° C. is 80 to 350 MPa, and a more preferable storage elastic modulus (E ′) is 100 to 350 MPa.

The fluororesin used in the present invention is heated to a melting point peak plus 50 ° C. at a rate of temperature increase of 10 ° C./min according to ASTM D-4591 using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments). The amount of heat of crystallization generated when the temperature is lowered at a rate of 10 ° C./min is preferably 30 mj / mg or more. More preferably, it is 35 mj / mg or more.

The fluororesin preferably has a fuel permeability coefficient of 2.0 g · mm / m ² / day or less, and more preferably 1.8 g · mm / m ² / day or less. If the fuel permeability coefficient is too high, the barrier properties of the laminate may be inferior.

The fluororesin is a copolymer comprising only copolymerized units of tetrafluoroethylene and vinylidene fluoride, or a copolymer containing copolymerized units of tetrafluoroethylene, vinylidene fluoride and ethylenically unsaturated monomer. It is.

The ethylenically unsaturated monomer is not particularly limited as long as it is a monomer copolymerizable with tetrafluoroethylene and vinylidene fluoride, but is ethylenic represented by the following formulas (1) and (2). It is preferably at least one unsaturated monomer.

Formula (1): CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. )

Formula (2): CF ₂ = CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.)

Examples of the ethylenically unsaturated monomer represented by the formula (1) include CF ₂ = CFCl, CF ₂ = CFCF ₃ , and the following formula (3)
^{_{CH 2 = CF- (CF 2)}} n X 4 (3)
(Wherein X ⁴ and n are the same as above) and the following formula (4)
^{_{CH 2 = CH- (CF 2)}} n X 4 (4)
(Wherein X ⁴ and n are the same as above)
It is preferably at least one selected from the group consisting of: CF ₂ = CFCl, CH ₂ = CFCF ₃ , CH ₂ = CH-C ₄ F ₉ , CH ₂ = CH-C ₆ F ₁₃ , CH ₂ = _CF-C 3, more preferably _{F 6} is H and _CF 2 = CFCF _3, at least one selected from the group consisting _of, CF 2 = CFCl and _CH 2 = CFCF _3, at least one selected from the group consisting of More preferably.

The ethylenically unsaturated monomer represented by the formula (2) includes a group consisting of CF ₂ = CF-OCF ₃ , CF ₂ = CF-OCF ₂ CF ₃ and CF ₂ = CF-OCF ₂ CF ₂ CF _3. It is preferable that it is at least one selected from more.

The fluororesin is
58.0-85.0 mol% tetrafluoroethylene,
10.0-41.9 mol% vinylidene fluoride, and
0.1-5.0 mol% of ethylenically unsaturated monomer represented by formula (1) CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴ (1)
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. )
It is preferable that it is a copolymer containing the copolymerization unit of the ethylenically unsaturated monomer represented by these.

More preferably,
58.0-85.0 mol% tetrafluoroethylene,
12.0-41.9 mol% vinylidene fluoride, and
0.1 to 3.0 mol% of an ethylenically unsaturated monomer represented by the formula (1),
It is a copolymer containing the copolymerization unit.

The fluororesin is
55.0-90.0 mol% tetrafluoroethylene,
9.2-44.2 mol% vinylidene fluoride, and
0.1 to 0.8 mol% of formula (2):
CF ₂ = CF-ORf ¹ (2)
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.)
It is also preferable that it is a copolymer containing the copolymerization unit of the ethylenically unsaturated monomer represented by these.

More preferably,
58.0-85.0 mol% tetrafluoroethylene,
14.5 to 41.9 mol% vinylidene fluoride, and
0.1 to 0.5 mol% of an ethylenically unsaturated monomer represented by the formula (2),
It is a copolymer containing the copolymerization unit.

The fluororesin is 55.0-90.0 mol% tetrafluoroethylene,
6.2-44.8 mol% vinylidene fluoride,
0.1 to 3.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and
It is also preferable that it is a copolymer containing a copolymer unit of 0.1 to 0.8 mol% of an ethylenically unsaturated monomer represented by the formula (2).

More preferably,
58.0-85.0 mol% tetrafluoroethylene,
11.5-39.8 mol% vinylidene fluoride,
0.1 to 3.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and
0.1 to 0.5 mol% of an ethylenically unsaturated monomer represented by the formula (2),
It is a copolymer containing the copolymerization unit.

When the content of each monomer is within the above range, the fluororesin has higher crystallinity and 170 ° C. than a conventionally known copolymer comprising tetrafluoroethylene, vinylidene fluoride and a third component. However, because of its high storage modulus, it has excellent fuel barrier properties even at high temperatures.
In addition, a binary copolymer of tetrafluoroethylene and vinylidene fluoride containing no third component and having a tetrafluoroethylene content of more than 50 mol% is significantly inferior in crack resistance of the molded product. The coalescence is excellent in crack resistance.

The content of each copolymer unit in the copolymer can be calculated by appropriately combining NMR and elemental analysis depending on the type of monomer.

The fluororesin preferably has a melt flow rate (MFR) of 0.1 to 50 g / 10 min.

The above MFR is based on ASTM D3307-01 and uses a melt indexer (manufactured by Toyo Seiki Co., Ltd.) at 297 ° C. under a load of 5 kg and the mass of the polymer flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes. (G / 10 minutes).

The fluororesin preferably has a melting point of 180 ° C. or higher, and the upper limit may be 290 ° C. A more preferred lower limit is 200 ° C and an upper limit is 270 ° C.

The melting point is measured using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) at a heating rate of 10 ° C./min according to ASTM D-4591, and the temperature corresponding to the peak of the endothermic curve obtained is the melting point. And

The fluororesin preferably has a thermal decomposition starting temperature of 360 ° C. or higher. A more preferred lower limit is 370 ° C. If the said thermal decomposition start temperature is in the said range, an upper limit can be 410 degreeC, for example.

The thermal decomposition start temperature is a temperature at which 1% by mass of the fluororesin subjected to the heating test is decomposed, and the mass of the fluororesin subjected to the heating test using the differential thermal / thermogravimetric measuring device [TG-DTA] is This is a value obtained by measuring the temperature when the mass decreases by 1% by mass.

The fluororesin can be produced by a polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc., but is manufactured by emulsion polymerization or suspension polymerization in that it is industrially easy to implement. Is preferred.

In the above polymerization, a polymerization initiator, a surfactant, a chain transfer agent, and a solvent can be used, and conventionally known ones can be used.

As said polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical initiator can be used.

The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkyl such as diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, disec-butyl peroxydicarbonate, etc. Peroxyesters such as peroxycarbonates, t-butylperoxyisobutyrate and t-butylperoxypivalate, and dialkyl peroxides such as di-t-butylperoxide are also used as di (ω-hydro -Dodecafluoroheptanoyl) peroxide, di (ω-hydro-tetradecafluoroheptanoyl) peroxide, di (ω-hydro-hexadecafluorononanoyl) peroxide, di (perfluorobutyryl) peroxide, di (Perfull Palerill) Par Xide, Di (perfluorohexanoyl) peroxide, Di (perfluoroheptanoyl) peroxide, Di (perfluorooctanoyl) peroxide, Di (perfluorononanoyl) peroxide, Di (ω-chloro-hexafluoro Butyryl) peroxide, di (ω-chloro-decafluorohexanoyl) peroxide, di (ω-chloro-tetradecafluorooctanoyl) peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluoro Nonanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di (dichloropentafluorobutanoy ) Peroxide, di (trichlorooctafluorohexanoyl) peroxide, di (tetrachloroundecafluorooctanoyl) peroxide, di (pentachlorotetradecafluorodecanoyl) peroxide, di (undecachlorodotriacontafluoro) Typical examples include docosanoyl) peroxide di [perfluoro (or fluorochloro) acyl] peroxides.

The water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, potassium salts, sodium salts. , T-butyl permaleate, t-butyl hydroperoxide and the like. A reducing agent such as sulfites and sulfites may be used in combination with the peroxide, and the amount used may be 0.1 to 20 times the peroxide.

As the surfactant, a known surfactant can be used. For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like can be used. Among these, fluorine-containing anionic surfactants are preferable, and may include ether-bonded oxygen (that is, oxygen atoms may be inserted between carbon atoms), linear or branched having 4 to 20 carbon atoms. A fluorine-containing anionic surfactant is more preferable. The addition amount (with respect to polymerization water) is preferably 50 to 5000 ppm.

Examples of the chain transfer agent include hydrocarbons such as ethane, isopentane, n-hexane and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; acetates such as ethyl acetate and butyl acetate; Examples include alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride. The addition amount may vary depending on the chain transfer constant of the compound used, but is usually used in the range of 0.01 to 20% by mass with respect to the polymerization solvent.

Examples of the solvent include water, a mixed solvent of water and alcohol, and the like.

In the suspension polymerization, a fluorine-based solvent may be used in addition to water. Examples of the fluorine-based solvent include hydrochlorofluoroalkanes such as CH ₃ CClF ₂ , CH ₃ CCl ₂ F, CF ₃ CF ₂ CCl ₂ H, CF ₂ ClCF ₂ CFHCl; CF ₂ ClCFClCF ₂ CF ₃ , CF ₃ CFClCFClCF _3, etc. Perfluoroalkanes such as perfluorocyclobutane, CF ₃ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , etc. Among them, perfluoroalkanes are preferable. The amount of the fluorine-based solvent used is preferably 10 to 100% by mass with respect to the aqueous medium from the viewpoint of suspendability and economy.

It does not specifically limit as polymerization temperature, It may be 0-100 degreeC. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent to be used, the polymerization temperature, etc., but may usually be 0 to 9.8 MPaG.

(B) Elastomer layer The elastomer layer is formed from an elastomer. Elastomers include acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber , Silicone rubber, butyl rubber, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, α, β-unsaturated nitrile-conjugated diene copolymer rubber, α, β-unsaturated nitrile-conjugated diene copolymer rubber Among these, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, acrylonitrile-butadiene rubber and polyvinyl chloride are preferred in view of heat resistance, oil resistance, weather resistance, and extrusion moldability. Preferably, the rubber is at least one selected from the group consisting of blend rubber, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber and acrylic rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene rubber More preferably, it is at least one selected from the group consisting of a blend rubber of styrene and polyvinyl chloride, fluororubber and epichlorohydrophosphorus rubber.

The layer (B) preferably contains at least one compound selected from the group consisting of an onium salt, an amine compound and an epoxy resin from the viewpoint of improving the adhesive strength with the layer (A).

The onium salt is not particularly limited, and examples thereof include quaternary ammonium salts, quaternary phosphonium salts, oxonium salts, sulfonium salts, cyclic amines, and monofunctional amine compounds. Among these, quaternary ammonium salts are exemplified. A quaternary phosphonium salt is 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 [5, , 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 also 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-phenylpropylene ) -1,8-diazabicyclo [5,4,0] -7-undecenium chloride, formula (5):

(In the formula, three Rs may be the same or different, and are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X ⁻ is a monovalent anion)
A compound represented by
Formula (6):

(In the formula, n is an integer of 0 to 50)
And a compound of formula (7):

Etc.

Three R in Formula (5) are the same or different, and are a hydrogen atom or a C1-C30 monovalent organic group, respectively. Although it does not specifically limit as a C1-C30 monovalent organic group, An aryl group, such as an aliphatic hydrocarbon group and a phenyl group, or a benzyl group is mention | raise | lifted. Specifically, for example, an alkyl group having 1 to 30 carbon atoms such as —CH ₃ , —C ₂ H ₅ , and —C ₃ H ₇ ; —CX ⁵ ₃ , —C ₂ X ⁵ ₅ , —CH ₂ X ⁵ , —CH ₂ CX ⁵ ₃ , —CH ₂ C ₂ X ⁵ _5, etc., a halogen atom-containing alkyl group having 1 to 30 carbon atoms (X ⁵ is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom); a phenyl group; _benzyl; -C ₆ F _{5, 1~5} phenyl groups or benzyl group hydrogen atoms are substituted with fluorine atoms, such as _{-CH 2 C 6 F 5; -C} 6 H 5-n (CF 3) n A phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with —CF ₃ such as —CH ₂ C ₆ H _5-n (CF ₃ ) _n (n is an integer of 1 to 5). . Moreover, Formula (8):

As such, it may contain a nitrogen atom.

Of these, the layer (A) and the layer (B) and the adhesion Additional DBU-B or from the viewpoint of good, three R are alkyl group or a benzyl group having 1 to 20 carbon atoms, X ^- is a monovalent Anions, halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), OH ⁻ , RO ⁻ , RCOO ⁻ , C ₆ H ₅ O ⁻ , SO ₄ ²⁻ , SO ₃ ²⁻ , SO ₂ ^- , RSO ₃ ²⁻ , CO ₃ ²⁻ , NO ₃ ⁻ (wherein R is a monovalent organic group), preferably represented by formula (5), formula (6), etc., as X ^{− in} formula (5) Is more preferably Cl ⁻ . In Formula (6), n is more preferably an integer of 0 to 10, and further preferably an integer of 1 to 5, from the viewpoint of dispersibility when kneaded with rubber.

Among these, in particular, the formula (9):

It is preferable that it is a compound shown by these.

The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter also referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl-2. -Methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride and the like can be mentioned, and among these, BTPPC is preferred from the viewpoint of good adhesion between the layer (A) and the layer (B).

Further, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a compound disclosed in JP-A-11-147891 can also be used.

The blending amount of the onium salt is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, and 0.3 to 7.0 parts by mass with respect to 100 parts by mass of the elastomer. Further preferred. If the blending amount of the onium salt is less than 0.1 parts by mass, the adhesion between the layer (A) and the layer (B) tends to be insufficient, and if it exceeds 10.0 parts by mass, the elastomer layer machine There is a tendency for physical properties to decrease.

It does not specifically limit as an amine compound, For example, a hexamethylenediamine carbamate, N, N'- dicinnamylidene-1,6-hexamethylenediamine (henceforth V3), 4,4'-bis (aminocyclohexyl) methanecarbamate Aliphatic polyamine compound derivatives such as 4,4′-diaminodiphenyl ether [4,4′-DPE], 2,2-bis [4- (4-aminophenoxy) phenyl] propane [BAPP], p-phenylenediamine , M-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, N, N'-dimethyl-1,4-phenylenediamine, 4,4'-methylenedianiline, dianilinoethane, 4,4'-methylene -Bis (3-nitroaniline), 4,4'-methylene-bis (2-chloroaniline) Emissions), diaminopyridine, an aromatic polyamine compound such as melamine may be used. Among these, V3, 4, 4'-DPE and BAPP are preferable from the viewpoint of good adhesion between the layer (A) and the layer (B).

The compounding amount of the amine compound is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, and 0.3 to 7.0 parts by mass with respect to 100 parts by mass of the elastomer. Further preferred. If the compounding amount of the amine compound is less than 0.1 parts by mass, the adhesion between the layer (A) and the layer (B) tends to be insufficient, and if the compounding amount exceeds 10.0 parts by mass, There is a tendency for mechanical properties to decrease.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and polyfunctional epoxy resin. Among these, as the bisphenol A type epoxy resin, the formula (10):

And the like. Here, in Formula (10), n is preferably 0.1 to 3, more preferably 0.1 to 0.5, and still more preferably 0.1 to 0.3. If n is less than 0.1, the adhesive strength with other materials tends to decrease. On the other hand, when n exceeds 3, the viscosity increases, and uniform dispersion in the rubber tends to be difficult.

0.1-20.0 mass parts is preferable with respect to 100 mass parts of elastomers, the compounding quantity of an epoxy resin has more preferable 0.3-15.0 mass parts, and 0.5-10.0 mass parts is. Further preferred. When the compounding amount of the epoxy resin is less than 0.1 parts by mass, the adhesion between the layer (A) and the layer (B) tends to be insufficiently expressed, while the compounding amount of the epoxy resin is 20.0 masses. When it exceeds the part, the flexibility of the layer (B) tends to decrease.

Further, the elastomer layer (B) can be either unvulcanized rubber or vulcanized.

As the vulcanizing agent, any vulcanizing agent used for ordinary elastomers can be used. For example, sulfur vulcanizing agent, peroxide vulcanizing agent, polythiol vulcanizing agent, quinoid vulcanizing agent, resin vulcanizing agent, metal oxide, diamine vulcanizing agent, polythiols, 2-mercaptoimidazoline There are vulcanizing agents such as polyol vulcanizing agents and polyamine vulcanizing agents, among which peroxide vulcanizing agents, polyol vulcanizing agents, polyamine vulcanizing agents, etc. It is preferable from the viewpoint of mechanical properties of rubber.

Peroxide-based crosslinking agents include tert-butyl hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, tert-butyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2, Examples include 5-dimethyl-2,5-di (tert-butylperoxy) hexane, benzoyl peroxide, tert-butylperoxybenzoate and the like.

Examples of the polyamine vulcanizing agent include aliphatic polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenetetramine, p-phenylenediamine, cumenediamine, N, N′-dicinenamilidene-1,6- Aromatic polyamines such as hexanediamine, and amine carbamates such as ethylenediamine carbamate and hexamethylenediamine carbamate are exemplified.

Although the usage-amount of the said crosslinking agent can be determined suitably, it is the range of 0.1-10 mass parts normally with respect to 100 mass parts of elastomers.

An acid acceptor can also be used with the said crosslinking agent. Examples of the acid acceptor include metal compounds and epoxy compounds. Examples of the metal compound include Group II metal oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, and Group IVa metal basic carbonates of the Periodic Table. , Basic carboxylates, basic phosphites, basic sulfites, tribasic sulfates, basic silicates, and the like.

Specific examples of metal compounds and epoxy compounds include magnesia, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, quicklime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate, magnesium phosphite , Calcium phosphite, zinc white, tin oxide, lisage, red lead, lead white, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic lead sulfite, basic silicic acid Examples include lead, epoxidized soybean oil, reaction products of bisphenol A and epichlorohydrin.

Although the usage-amount of the said acid acceptor can be determined suitably, it is the range of 0.1-10 mass parts normally with respect to 100 mass parts of elastomers.

Each layer constituting the laminate of the present invention is composed of polymers such as polyethylene, polypropylene, polyamide, polyester and polyurethane, inorganic fillers such as calcium carbonate, talc, celite, clay, titanium oxide, carbon black and barium sulfate, pigments, difficulty Flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, UV absorbers, antioxidants, mold release agents, foaming agents, fragrances, oils, softening agents, etc. will not affect the effects of the present invention. You may contain in the range.

In the laminate of the present invention, the layer (A) may have a thickness of 0.01 to 2.0 mm, preferably 0.1 to 2.0 mm, and the layer (B) has a thickness of 0.1 to 4.0 mm. Preferably, it is 0.1-2.0 mm.

The configuration of the laminate is not particularly limited, and for example, a two-layer configuration composed of a layer (A) and a layer (B), or a layer (A) inserted between two types of the same or different layers (B). A three-layer structure or the like can be used. It is also possible to further laminate an arbitrary material on the laminate of the present invention.

The laminate of the present invention is, for example,
Mixing an elastomer and optional additives to obtain an elastomer composition;
A step of laminating a layer (A) formed from a fluororesin and a layer (B) formed from the elastomer composition,
Heating the layer (A) and the layer (B);
It can manufacture suitably by the manufacturing method containing.

In the said manufacturing method, you may include the process of obtaining the fluororesin composition which mixes a fluororesin and arbitrary additives. The fluororesin composition is obtained by mixing a fluororesin and optional additives, and the mixing can be performed using a normal mixer such as a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, etc. it can.

The elastomer composition is obtained by mixing an elastomer and optional additives, and the mixing can be performed using a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder or the like.

The fluororesin composition and the elastomer composition may contain an optional additive. As the optional additive, in addition to the above-described onium salt, amine compound, epoxy resin, crosslinking agent and acid acceptor, a filler, a processing aid. Agent, plasticizer, colorant, stabilizer, crosslinking accelerator, crosslinking aid, co-crosslinking agent, adhesion assistant, mold release agent, conductivity imparting agent, thermal conductivity imparting agent, surface non-adhesive agent, imparting flexibility Agents, heat resistance improvers, flame retardants and the like.

As a method of laminating the layer (A) and the layer (B), a conventionally known method can be used. For example, a laminate may be obtained by co-extrusion of a fluororesin and an elastomer composition, or a layer made of a fluororesin and a layer made of an elastomer that are separately produced may be superposed.

Heating of the laminated layer (A) and layer (B) may be performed at a temperature and time sufficient for crosslinking of the elastomer, and can usually be performed at a temperature of 150 to 300 ° C. for 1 minute to 24 hours. . If necessary, secondary vulcanization at 150 ° C. for 1 to 3 hours may be performed in a thermostatic bath.

The heating method can be performed by a normal heating method such as pressure molding with a mold, steam, microwave, hot air furnace, salt bath method or the like. In addition, the crosslinking reaction can be carried out under normal conditions, under pressure, under reduced pressure, or in air.

In the step of laminating the layer (A) and the layer (B) and the step of heating, for example, (1) the layers constituting the laminated body are co-extruded in a molten state to thermally bond (melt) the layers. A method of forming a laminate in one step (coextrusion molding), (2) a method of laminating each layer separately produced by an extruder and bonding the layers by thermal fusion, (3) a layer produced in advance A method of forming a laminate by extruding a molten resin on the surface of the substrate by an extruder, (4) electrostatic coating of a polymer constituting the layer adjacent to the layer on the surface of the layer prepared in advance After that, by heating the obtained coated product as a whole or from the coated side, the polymer used for coating can be heated and melted to form a layer, or the like.

In the method (1), the melt may be heat-fused at a temperature and for a time sufficient to crosslink the elastomer by means of increasing the temperature of the product, such as an oven or a heated liquid bath.

In the methods (2) and (3), one or both surfaces of the layer (A) and the layer (B) may be treated. Such surface treatment may consist of a solution treatment such as a solvent. When the solvent contains a base such as 1,8-diazo [5.4.0] bicycloundec-7-ene (DBU), some dehydrofluorination occurs in the fluororesin. Such dehydrofluorination is believed to be advantageous in promoting adhesion to subsequently applied elastomers.

A molded product formed from the laminate is also one aspect of the present invention. The molded article of the present invention is a molded article having excellent fuel barrier properties and mechanical strength, chemical resistance, oil resistance, heat resistance and flexibility.

The laminate of the present invention is a laminate having excellent adhesion to an elastomer layer and having chemical resistance, oil resistance, heat resistance, and cold resistance, and is useful as a multilayer fuel tube or multilayer fuel container. In particular, it is useful as a multilayer fuel tube or multilayer fuel container for automobile engines and peripheral devices, AT devices, fuel systems and peripheral devices. For example, fuel tubes such as automobile filler hoses, evaporation hoses, breather hoses, etc .; fuel containers for automobiles, fuel containers for motorcycles, fuel containers for small generators, fuel containers for lawn mowers, etc. It is done.

The laminated body is further used as an engine body of an automobile engine, a main motion system, a valve system, a lubricant / cooling system, a fuel system, an intake / exhaust system; a drive system transmission system; a chassis steering system; Brake system: Gaskets and non-contact types that require heat resistance, oil resistance, fuel oil resistance, antifreeze resistance for engine cooling, and steam resistance, such as basic electrical parts of control equipment, control system electrical parts, equipment electrical parts, etc. Sealing materials such as contact type packings (self-seal packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.) are included.

The sealing material used for the engine body of the automobile engine is not particularly limited, but includes, for example, a cylinder head gasket, a cylinder head cover gasket, an oil pan packing, a gasket such as a general gasket, an O-ring, a packing, a timing belt cover gasket, and the like. For example, a sealing material.

The seal material used in the main motion system of the automobile engine is not particularly limited, and examples thereof include a shaft seal such as a crankshaft seal and a camshaft seal.

The seal material used in the valve system of an automobile engine is not particularly limited, and examples thereof include a valve stem oil seal for an engine valve.

There are no particular limitations on applications other than automotive applications,
Films, sheets; food films, food sheets, chemical films, chemical sheets, diaphragm pump diaphragms and various packing tubes, hoses; solvent tubes or solvent hoses, paint tubes or paint hoses, Automotive radiator hose, air conditioner hose, brake hose, wire covering material, food and beverage tube or food and beverage hose, underground underground tube or hose for gas station, subsea oil field tube or hose bottles, containers, tanks, etc. Tanks, paint tanks, chemical containers such as semiconductor chemical containers, food and drink tanks, etc .; various mechanical seals such as seals for hydraulic equipment, gears, etc. Among the above, it can be suitably used particularly for tubes or hoses. .

The tube or hose may have a corrugated region in the middle. Such a corrugated region is an appropriate region in the middle of the hose body formed into a corrugated shape, a corrugated shape, a convoluted shape, or the like.

The tube or hose of the present invention has a region in which a plurality of corrugated folds are arranged in an annular shape, so that one side of the annular shape can be compressed and the other side can be extended outwardly in that region. Therefore, it can be easily bent at any angle without stress fatigue or delamination.

The method for forming the corrugated region is not limited, but it can be easily formed by first forming a straight tube and then performing molding or the like to obtain a predetermined corrugated shape.

The laminated body of the present invention can be suitably used for applications where there is a portion that comes into contact with fuel when using a fuel hose (tube), a tank, or the like.

A fuel hose formed from the laminate is also one aspect of the present invention. As described above, the laminate of the present invention is firmly bonded between layers, and has flexibility, high mechanical strength, and fuel barrier properties. Therefore, the laminate for a fuel hose used for a fuel piping tube for an automobile is used. Can be suitably used. In this case, the portion in contact with the fuel is preferably the layer (A). That is, the innermost layer is preferably the layer (A).

The innermost layer of the fuel hose is liable to accumulate an electrostatic charge due to contact with a flammable liquid such as gasoline, but the innermost layer preferably contains a conductive filler in order to avoid igniting by the electrostatic charge.

The conductive filler is not particularly limited, and examples thereof include conductive simple powders or conductive single fibers such as metals and carbons; powders of conductive compounds such as zinc oxide; surface conductive powders.

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 Laid-Open No. 3-174018. Examples of the carbon fibrils are listed.

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 conducting the conductive treatment is not particularly limited, and examples thereof include metal sputtering and electroless plating. Among the conductive fillers described above, carbon black is preferably used because it is advantageous in terms of economy and prevention of electrostatic charge accumulation.

Hereinafter, the present invention will be described in more detail with reference to examples. Each physical property was measured by the following method.

Using fluorine resin monomer composition nuclear magnetic resonance apparatus AC300 (manufactured by Bruker-Biospin), the measurement temperature is (polymer melting point + 20) ° C., and ¹⁹ F-NMR measurement is performed. In some cases, the elemental analysis was appropriately combined.

Using a melting point differential scanning calorimeter RDC220 (manufactured by Seiko Instruments), heat measurement was performed at a heating rate of 10 ° C./min in accordance with ASTM D-4591, and the melting point was obtained from the peak of the obtained endothermic curve.

Heat of crystallization (ΔTc)
Using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments), the temperature was raised to the melting point peak plus 50 ° C. at a rate of temperature rise of 10 ° C./min according to ASTM D-4591, and then the temperature was lowered at a rate of 10 ° C./min. It was determined from the peak area (mj / mg) of the crystallization calorific value generated when

Using a crystallization temperature differential scanning calorimeter RDC220 (manufactured by Seiko Instruments), the temperature was raised to the melting point peak plus 50 ° C. at a temperature rising rate of 10 ° C./min according to ASTM D-4591, and then at a rate of 10 ° C./min. It was obtained from the peak of the exothermic curve generated when the temperature was lowered at.

Melt flow rate [MFR]
MFR is based on ASTM D3307-01, and uses a melt indexer (manufactured by Toyo Seiki Co., Ltd.) at a mass of 297 ° C. under a 5 kg load from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes. g / 10 min) was defined as MFR.

Measurement of fuel permeability coefficient 50 mmφ, 0.2-0.3 mm thick sheet was molded with a melt press and the inner diameter was charged with 18 ml of CE10 fuel (isooctane / toluene / ethanol: 45/45/10 (volume%)) The obtained sheet was put in a transmission coefficient measuring cup made of SUS316 having a diameter of 40 mm and a height of 20 mm, and 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 the wetted part, and the thickness of the sheet.

Storage modulus (E ')
The storage elastic modulus is a value measured at 170 ° C. by dynamic viscoelasticity measurement. A sample having a length of 30 mm, a width of 5 mm, and a thickness of 0.25 mm is pulled in a tensile mode using a dynamic viscoelastic device DVA220 manufactured by IT-Measurement Control Co., Ltd. The measurement was performed under the conditions of a grip width of 20 mm, a measurement temperature of 25 ° C. to 250 ° C., a heating rate of 2 ° C./min, and a frequency of 1 Hz.

Thermal decomposition start temperature (1% mass loss temperature)
The thermal decomposition start temperature was defined as the temperature at which the mass of the fluororesin subjected to the heating test using a differential thermal / thermogravimetric measuring device [TG-DTA] decreased by 1 mass%.

<Preparation of sheet-shaped test piece (fluororesin layer)>
Various fluororesins are set in a mold, held at 270 to 300 ° C. for 15 to 30 minutes by a heat press machine, and after the fluororesin is melted, a 3 MPa load is applied for 1 minute and compression molding is performed. A sheet-shaped test piece having a thickness was prepared.

<Preparation of sheet specimen (elastomer layer)>
Various compounding agents such as a vulcanizing agent and a filler were added to various raw rubbers with an 8-inch open roll to produce a full compound. A sheet-shaped test piece having a predetermined thickness was produced from the full compound using an open roll.

<Production of laminate>
A sheet-shaped test piece of a fluororesin sheet having a thickness of 0.5 mm and an elastomer composition having a thickness of 1.5 mm was produced by the above method. These sheet-like test pieces were stacked and set in a mold heated to 170 ° C., and a 3 MPa load was applied for 20 minutes at 170 ° C. with a heat press machine to prepare a fluororesin layer-elastomer layer laminate.

<Adhesion evaluation test>
The obtained laminate was cut into strips each having a width of 1.0 cm and a width of 10 cm to produce a test piece for adhesion test, and an autograph (AGS-J 5kN, manufactured by Shimadzu Corporation) was used for this test piece. Then, in accordance with the method described in JIS-K-6256 (vulcanized rubber adhesion test method), a peel test was conducted at 25 ° C. at a tensile rate of 50 mm / min, and the adhesive strength was measured. Moreover, the peeling mode was observed and evaluated according to the following criteria.

(Adhesion evaluation)
A ... The fluororesin layer / elastomer layer interface did not peel, and the elastomer layer was destroyed.
○: Peeled at the fluororesin layer / elastomer layer interface, but was sufficiently adhered and difficult to peel.
Δ: Peeled relatively easily at the fluororesin layer / elastomer layer interface.
X: The fluororesin layer and the elastomer layer did not exhibit adhesiveness.

Fluoropolymer production example 1 (A-1)
Distilled water (52.2 L) was charged into a 174 L autoclave and sufficiently purged with nitrogen. Then, 39.1 kg of perfluorocyclobutane was charged, and the temperature in the system was maintained at 35 ° C. and a stirring speed of 200 rpm. Subsequently, 0.07 kg of chlorotrifluoroethylene [CTFE], 6.22 kg of tetrafluoroethylene [TFE] and 0.68 kg of vinylidene fluoride [VDF] were sequentially added, and then a polymerization initiator di-n-propyl peroxydicarbonate. Polymerization was initiated by adding 130 g of a 50 wt% methanol solution of [NPP]. Simultaneously with the start of polymerization, 0.6 kg of ethyl acetate was charged. Since the internal pressure decreases with the progress of polymerization, TFE / VDF / CTFE mixed gas monomer (TFE / VDF / CTFE: 72.5 / 26.7 / 0.8 (mol%)) is charged, and the internal pressure is reduced. The pressure was kept at 0.9 MPa. When the additional amount of the mixed gas monomer finally reached 8 kg, the polymerization was stopped, and the pressure was released to return to atmospheric pressure. Then, the obtained TFE / VDF / CTFE copolymer was washed with water and dried to obtain 7 .5 kg of powder was obtained.

Next, melt kneading was performed at a cylinder temperature of 300 ° C. using a φ20 mm single screw extruder to obtain pellets. The resulting pellet was then heated at 150 ° C. for 12 hours.

The obtained pellet (A-1) had the following composition and physical properties.
TFE / VDF / CTFE: 72.4 / 26.9 / 0.7 (mol%)
Melting point: 254 ° C
Crystallization temperature: 232 ° C
Amount of heat of crystallization: 43 mj / mg
MFR: 1.1 g / 10 min (297 ° C.-5 kg)
Storage elastic modulus at 170 ° C. (E ′): 152 MPa
Thermal decomposition start temperature (1% mass loss temperature): 392 ° C.
Fuel permeation coefficient: 1.5 g · mm / m ² / day

Fluoropolymer production example 2 (A-2)
Distilled water (52.2 L) was charged into a 174 L autoclave and sufficiently purged with nitrogen. Then, 39.1 kg of perfluorocyclobutane was charged, and the temperature in the system was maintained at 35 ° C. and a stirring speed of 200 rpm. Subsequently, 0.02, kg of 2,3,3,3-tetrafluoropropene, 5.0 kg of TFE and 0.7 kg of VDF were sequentially added, and then 50% by mass of a polymerization initiator di-n-propyl peroxydicarbonate [NPP]. Polymerization was started by adding 130 g of the solution. Simultaneously with the initiation of polymerization, 0.30 kg of ethyl acetate was charged. Since the internal pressure decreases with the progress of polymerization, a mixed gas monomer of TFE / VDF / 2,3,3,3-tetrafluoropropene (TFE / VDF / 2,3,3,3-tetrafluoropropene: 66.0 /33.5/0.5 (mol%)) and the internal pressure of the system was kept at 0.8 MPa. When the additional charge of the mixed gas monomer finally reached 8 kg, the polymerization was stopped, the pressure was released and the pressure was returned to atmospheric pressure, and then the obtained TFE / VDF / 2,3,3,3-tetrafluoropropene The copolymer was washed with water and dried to obtain 8.5 kg of powder.

Next, melt kneading was performed at a cylinder temperature of 300 ° C. using a φ20 mm single screw extruder to obtain pellets. The resulting pellet was then heated at 150 ° C. for 12 hours.

The obtained pellet (A-2) had the following composition and physical properties.
TFE / VDF / 2,3,3,3-tetrafluoropropene: 69.1 / 30.4 / 0.5 (mol%)
Melting point: 232.2 ° C
Crystallization temperature: 211.3 ° C
Amount of heat of crystallization: 41.2 mj / mg
MFR: 1.8 g / 10 min (297 ° C.-5 kg)
Storage elastic modulus at 170 ° C. (E ′): 167 MPa
Thermal decomposition start temperature (1% mass loss temperature): 382 ° C.
Fuel permeation coefficient: 1.6 g · mm / m ² / day

Elastomer composition formulation example 1
FKM full compound (B-1)
Raw rubber of ternary fluoropolymer (VDF / TFE / HFP = 58/20/22 mol%, Mooney viscosity 40), 100 parts by mass of bisphenol AF (manufactured by Daikin Industries), 2.2 parts by mass, DBU-B (Japanese 0.56 parts by mass of Kojun Pharmaceutical Co., Ltd.), 13 parts by mass of carbon black (Shiest S, manufactured by Tokai Carbon Co., Ltd.), 3.0 parts by mass of magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.), Calcium hydroxide (Caldic 2000, manufactured by Omi Chemical Co., Ltd.) 6.0 parts by mass, salt of 3-hydroxy-2-naphthoic acid and 1,8-diazabicyclo [5,4,0] undec-7-ene (DA500, manufactured by Daiso Co., Ltd.) 0.5 parts by mass was added and kneaded using an 8-inch open roll to obtain an elastomer composition B-1.

Elastomer composition formulation example 2
FKM full compound (B-2)
Raw rubber of ternary fluoropolymer (VDF / TFE / HFP = 58/20/22 mol%, Mooney viscosity 40), 100 parts by mass of bisphenol AF (manufactured by Daikin Industries), 2.2 parts by mass, DBU-B (Japanese 0.56 parts by mass of Kojun Pharmaceutical Co., Ltd.), 13 parts by mass of carbon black (Shiest S, manufactured by Tokai Carbon Co., Ltd.), 3.0 parts by mass of magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.), 6.0 parts by mass of calcium hydroxide (Caldick 2000, manufactured by Omi Chemical Co., Ltd.), 2 parts by mass of N, N′-dicinenamylidene-1,6-hexamethylenediamine (V3, manufactured by Daikin Industries, Ltd.) The resultant was added and kneaded using an 8-inch open roll to obtain an elastomer composition B-2.

Elastomer composition formulation example 3
NBR full compound (B-3)
100 parts by mass of acrylonitrile-butadiene rubber (Nipol 1041, manufactured by JSR Corporation), 30 parts by mass of carbon black (N990, manufactured by Cancarb Ltd.), 5 parts by mass of zinc oxide (manufactured by Hystec Co., Ltd.), wet silica (Nipsil VN3) 15 parts by mass, manufactured by Nippon Silica Kogyo Co., Ltd., 1 part by mass of stearic acid (Lunac, manufactured by Kao Corporation), 2 parts by mass of anti-aging agent (A.O.224, manufactured by KING INDUSTRIES), plasticizer (Thiokol) TP95, manufactured by Morton International) 15 parts by mass, wax (carnauba wax, manufactured by Toa Kasei Co., Ltd.), peroxide (Park Mill D-40, manufactured by Nippon Oil & Fats Co., Ltd.) 2 parts by mass were added to carry out kneader kneading. Thereafter, an onium salt reagent (8-benzyl-1,8-diazabicyclo [5,4 0] -7-undecenium chloride (DBU-B), 5 parts by weight of Wako Pure Chemical Industries, Ltd., and 5 parts by weight of an epoxy compound (JER828, manufactured by Japan Epoxy Resin Co., Ltd.) are added to an 8-inch open roll. Was used for kneading to obtain an elastomer composition B-3.

Elastomer composition formulation example 4
ECO full compound (B-4)
Epichlorohydrin rubber (Epichromer CG, manufactured by Daiso Co., Ltd.) 100 parts by mass, carbon black (N-550, manufactured by Cancarb Ltd.) 80 parts by mass, Plasticizer (ADK sizer RS-107, manufactured by Asahi Denka Kogyo Co., Ltd.) 5.0 parts by mass, 2.0 parts by mass of Lubricant (Splender R-300), 2.0 parts by mass of anti-aging agent (NOCRACK NBC, manufactured by Ouchi Shinsei Chemical Co., Ltd.), synthetic hydrotalcite (DIIT-4A) , Manufactured by Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass, magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass, 1.5 parts by mass of DBU phenol resin salt (P-152), 6-Methylquinoxaline-2,3-dithiocarbonate (Daisonette XL-21S, manufactured by Daiso Corporation) Was added parts by weight were kneaded by using an 8-inch open roll to obtain an elastomer composition B-4.

Examples 1-5
A laminate was prepared by the combination of the fluororesin layer and the elastomer layer shown in Table 1 according to the above method. The adhesive strength of this laminate was measured and evaluated by the method described above.

Comparative Example 1
Copolymer (A-3) of tetrafluoroethylene and hexafluoropropylene (trade name: NEOFLON FEP NP-20, manufactured by Daikin Industries, Ltd., melting point 271 ° C., MFR 6.4 g / 10 min (372 ° C.-5 kg)) A laminate was prepared in the same manner as in the example, with the fluororesin layer and the elastomer layer being B-1. However, the sheet molding temperature of the fluororesin was 350 ° C.

The results of Examples and Comparative Examples are shown in Table 1.

The laminate of the present invention is excellent in fuel barrier properties, exhibits good adhesion at the interface between laminates composed of a fluororesin layer and an elastomer layer, and is useful as a fuel peripheral material. For example, it is suitable as a fuel tube or hose. Available to:

Claims (11)

A laminate including a layer (A) made of a fluororesin and a layer (B) made of an elastomer,
The fluororesin is a copolymer comprising copolymerized units of tetrafluoroethylene, vinylidene fluoride, and optionally an ethylenically unsaturated monomer (excluding tetrafluoroethylene and vinylidene fluoride), and A laminate having a storage elastic modulus (E ′) at 170 ° C. by dynamic viscoelasticity measurement of 60 to 400 MPa. The fluororesin is 58.0-85.0 mol% tetrafluoroethylene,
10.0-41.9 mol% vinylidene fluoride, and
0.1 to 5.0 mol% of an ethylenically unsaturated monomer represented by the formula (1),
The laminate according to claim 1, wherein the laminate comprises a copolymer unit.
Formula (1): CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. ) The fluororesin is 55.0-90.0 mol% tetrafluoroethylene,
9.2-44.2 mol% vinylidene fluoride, and
0.1 to 0.8 mol% of an ethylenically unsaturated monomer represented by the formula (2),
The laminate according to claim 1, wherein the laminate comprises a copolymer unit.
Formula (2): CF ₂ = CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.) The fluororesin is 55.0-90.0 mol% tetrafluoroethylene,
6.2-44.8 mol% vinylidene fluoride,
0.1 to 3.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and
0.1 to 0.8 mol% of an ethylenically unsaturated monomer represented by the formula (2),
The laminate according to claim 1, wherein the laminate comprises a copolymer unit.
Formula (1): CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. )
Formula (2): CF ₂ = CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.) The laminate according to claim 1, 2, 3, or 4, wherein the fluororesin has a heat of crystallization of 30 mj / mg or more. The laminate according to claim 1, 2, 3, 4, or 5, wherein the fluororesin has a fuel permeability coefficient of 2.0 g · mm / m ² / day or less. Elastomers include acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber and acrylic rubber. The laminate according to claim 1, 2, 3, 4, 5 or 6, which is at least one selected from the group consisting of: The layered product according to claim 1, wherein the layer (B) contains at least one compound selected from the group consisting of an onium salt, an amine compound, and an epoxy resin. A molded article formed from the laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8. A fuel hose formed from the laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8. The manufacturing method of the laminated body of Claim 1, 2, 3, 4, 5, 6, 7 or 8.