JP2015178258A - Laminate and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in an adhesive property between a fluororesin layer and rubber layer, and a production method of the same.SOLUTION: Provided is the laminate formed of a fluororesin layer (A) and a rubber layer (B) formed on the fluororesin layer (A). The fluororesin layer (A) is formed of fluororesin (a1) whose fuel permeability coefficient is equal to or less than 2.0 g mm/m/day. The rubber layer (B) is formed of specific rubber (b1) and a lamination surface on the fluororesin layer (A) with the rubber layer (B) is subjected to discharge treatment.

Description

The present invention relates to a laminate and a method for producing the same.

With 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 the need for materials with excellent fuel barrier properties is increasing. is there.
In particular, in fuel transportation rubber hoses, laminated hoses with a fluororesin as a barrier layer (rubber other than the barrier layer) are used in order to improve low fuel permeability, but due to the recent strong demand for reducing environmental impact, A further low fuel permeability is required.

When a fluororesin having a lower fuel permeability is used as the barrier layer, there is a problem that it is difficult to bond the rubber of the outer and inner layers as a counterpart material.

Patent Document 1 discloses a method for manufacturing a hose having a three-layer structure in which an inner rubber layer, a resin layer, and an outer rubber layer are coaxially laminated in order from the inside, and includes the following (A) by extrusion molding. After forming the resin layer consisting of the following (B) on the outer peripheral surface of the inner rubber layer, prior to extruding the outer rubber layer consisting of the following (C), the outer peripheral surface of the resin layer is subjected to the direct atmospheric pressure plasma. A method of manufacturing a hose characterized by processing is described.
(A) Acrylonitrile-butadiene copolymer rubber or a blend material of acrylonitrile-butadiene copolymer rubber and polyvinyl chloride.
(B) Fluororesin.
(C) A blend material of acrylonitrile-butadiene copolymer rubber and polyvinyl chloride, or hydrin rubber.

Japanese Patent No. 4759404

This invention is made | formed in view of the said present condition, and aims at providing the laminated body excellent in the adhesiveness of a fluororesin layer and a rubber layer, and its manufacturing method.

The present inventors perform discharge treatment on the laminated surface of the fluororesin layer with the rubber layer, so that the fluororesin layer and the rubber layer are separated even when a fluororesin excellent in low fuel permeability is used. The inventors have found that they can be firmly bonded, and have reached the present invention.

That is, the present invention is a laminate comprising a fluororesin layer (A) and a rubber layer (B) formed on the fluororesin layer (A),
The fluororesin layer (A) is made of a fluororesin (a1) having a fuel permeability coefficient of 2.0 g · mm / m ² / day or less, and the rubber layer (B) is made of styrene-butadiene rubber (SBR) or chloroprene rubber. (CR), butadiene rubber (BR), natural rubber (NR), isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, acrylic rubber, chlorinated polyethylene (CPE), ethylene It is composed of at least one rubber (b1) selected from the group consisting of propylene diene rubber (EPDM) and fluororubber, and the laminate surface of the fluororesin layer (A) with the rubber layer (B) is subjected to discharge treatment. It is the laminated body characterized by these.

The present invention is a method for producing the laminate, wherein the step (1) of forming the fluororesin layer (A), the step (2) of performing a discharge treatment on at least one surface of the fluororesin layer (A), and It is also a method for producing a laminate comprising a step (3) of forming a rubber layer (B) on the surface of the fluororesin layer (A) subjected to the discharge treatment.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in the adhesiveness of a fluororesin layer and a rubber layer and its manufacturing method can be provided.

Hereinafter, the present invention will be specifically described.

The laminate of the present invention comprises a fluororesin layer (A) and a rubber layer (B) formed on the fluororesin layer (A), and is laminated with the rubber layer (B) in the fluororesin layer (A). The surface is discharged. Thereby, the fluororesin layer (A) and the rubber layer (B) are firmly bonded. Examples of the discharge treatment include plasma discharge treatment and corona discharge treatment. The discharge treatment is preferably performed in a nitrogen atmosphere.

As the discharge treatment, plasma discharge treatment is preferable in that the adhesion becomes stronger. The plasma generating gas is not particularly limited as long as plasma is generated. Examples thereof include nitrogen, argon, oxygen, air, water vapor, and the like. These may be used alone or in combination of two or more. . Of these, nitrogen is preferable from the viewpoint of enhancing the adhesive strength. That is, the discharge treatment is preferably a plasma discharge treatment under a nitrogen atmosphere.

The plasma discharge treatment is preferably performed under normal pressure. That is, it is preferable that the discharge treatment is an atmospheric pressure plasma discharge treatment. “Normal pressure” means that the processing chamber in the plasma discharge processing apparatus is not depressurized or pressurized with a pump or the like to generate plasma, and the pressure in the processing chamber is not necessarily It is not always the same as the atmospheric pressure outside the processing chamber.
The discharge treatment is preferably a normal pressure plasma discharge treatment under a nitrogen atmosphere.

The discharge in the discharge treatment is preferably performed at a line speed of 0.001 to 1000 m / min and a discharge intensity of 0.1 to 100 kW. The line speed is more preferably from 0.01 to 500 m / min, even more preferably from 0.1 to 500 m / min. The discharge intensity is more preferably from 0.1 to 80 kW, still more preferably from 0.1 to 60 kW.
The treatment temperature can be arbitrarily set within a range of a lower limit of 0 ° C. and an upper limit of 100 ° C.

In the above discharge treatment, the AC voltage applied to the electrodes is applied in a pulsed manner at a low voltage in the glow discharge region below the piezoelectric in the lightning discharge region. Further, the frequency is not particularly limited as long as atmospheric pressure plasma is generated, but it is set in a range of 0.5 to 200 kHz. The gas flow rate is set to 1 to 500 liters / minute. Furthermore, the distance between the discharge electrode and the counter electrode is preferably 0.5 to 500 mm, more preferably 1 to 100 mm.

(Fluorine resin layer (A))
The fluororesin layer (A) constituting the laminate of the present invention comprises a fluororesin (a1) having a fuel permeability coefficient of 2.0 g · mm / m ² / day or less. When the fuel permeability coefficient is 2.0 g · mm / m ² / day or less, an excellent low fuel permeability coefficient is exhibited. Therefore, for example, the laminate of the present invention can be suitably used as a fuel hose or the like.

The fuel permeability coefficient is preferably 1.5 g · mm / m ² / day or less, more preferably 0.8 g · mm / m ² / day or less, and 0.55 g · mm / m ² / day. It is more preferably not more than day, and particularly preferably not more than 0.5 g · mm / m ² / day.

The fuel permeability coefficient is a SUS316 fuel permeability coefficient measuring cup made of SUS316 with an inner diameter of 40 mmφ and a height of 20 mm charged with 18 mL of an isooctane / toluene / ethanol mixed solvent in which isooctane, toluene and ethanol are mixed at a volume ratio of 45:45:10. Is a value calculated from a mass change measured at 60 ° C. by incorporating a fluororesin sheet (diameter: 45 mm, thickness: 120 μm) prepared from the measurement target resin by the following method.
(Production method of fluororesin sheet)
Each of the resin pellets is put into a mold having a diameter of 120 mm, set in a press machine heated to 300 ° C., and melt-pressed at a pressure of about 2.9 MPa to obtain a fluororesin sheet having a thickness of 0.12 mm.

Since the said fluororesin (a1) can obtain the laminated body which has the outstanding low fuel permeability, a polychlorotrifluoroethylene (PCTFE), a chlorotrifluoroethylene (CTFE) copolymer, and tetrafluoroethylene ( It is preferably at least one selected from the group consisting of TFE) / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) copolymer. From the viewpoint of flexibility, it is more preferable that it is at least one selected from the group consisting of a CTFE copolymer and a TFE / HFP / VdF copolymer. From the viewpoint of fuel permeability, the CTFE copolymer is further preferable.

Since the TFE / HFP / VdF copolymer has excellent fuel permeability when the VdF content is low, the copolymerization ratio (mole% ratio) of TFE, HFP and VdF is TFE / HFP / VdF = 75.0 to 95. 0.0 / 0.1 to 10.0 / 0.1 to 19.0, preferably 77.0 to 95.0 / 1.0 to 8.0 / 1.0 to 17.0 (molar ratio) It is more preferable that it is 77.0-95.0 / 2.0-6.5 / 2.0-15.5 (molar ratio). The TFE / HFP / VdF copolymer may contain 0 to 20.0 mol% of other monomers (excluding CTFE). Other monomers include perfluoro (alkyl vinyl ether) (PAVE) (eg perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether)), 2-chloropentafluoropropene, perfluorinated Fluorine-containing monomers such as modified vinyl ethers (for example, perfluoroalkoxy vinyl ethers such as CF ₃ OCF ₂ CF ₂ CF ₂ OCF = CF ₂ ), perfluoro-1,3-butadiene, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, ethylene , Propylene, and at least one monomer selected from the group consisting of alkyl vinyl ethers.

The PCTFE is a chlorotrifluoroethylene homopolymer.

Examples of the CTFE copolymer include a copolymer unit derived from CTFE (CTFE unit), TFE, HFP, PAVE, VdF, vinyl fluoride, hexafluoroisobutene, a 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), ethylene, propylene, 1-butene, 2-butene, chloride It is preferable that it contains a copolymer unit derived from at least one monomer selected from the group consisting of vinyl and vinylidene chloride.
Further, the CTFE copolymer is more preferably a perhalopolymer.

More preferably, the CTFE copolymer contains CTFE units and copolymer units derived from at least one monomer selected from the group consisting of TFE, HFP and PAVE. More preferably, it consists only of copolymerized units. From the viewpoint of low fuel permeation, it is preferable not to include a monomer having a CH bond such as ethylene, vinylidene fluoride, and vinyl fluoride.
Perhalopolymers containing no CH-bonded monomers are usually difficult to adhere to rubber, but according to the configuration of the present invention, even if the fluororesin layer (A) is a layer made of perhalopolymer, The adhesion between the resin layer (A) and the rubber layer (B) is strong.

The CTFE copolymer preferably has 10 to 90 mol% of CTFE units based on the total monomer units.

As the CTFE copolymer, those containing a CTFE unit, a TFE unit, and a monomer (α) unit derived from a monomer (α) copolymerizable therewith are particularly preferred.

“CTFE unit” and “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) in the molecular structure of the CTFE copolymer.

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 (in the formula, , Rf ¹ is a PAVE represented by C1-C8 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, differently, 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), a vinyl monomer represented by CF ₂ = CF—O—Rf ² And alkyl perfluorovinyl ether derivatives represented by the formula (wherein Rf ² is a C 1-5 perfluoroalkyl group).
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—OCF ₂ —CF ₂ CF ₃ is more preferable.

The monomer (α) is preferably at least one selected from the group consisting of PAVE, the above vinyl monomer, and alkyl perfluorovinyl ether derivatives, and more preferably from the group consisting of PAVE and HFP. More preferably, it is at least one selected, and PAVE is particularly preferable.

The ratio of CTFE units to TFE units in the CTFE copolymer is 85 to 10 mol% of TFE units relative to 15 to 90 mol% of CTFE units, and more preferably 20 to 90 mol% of CTFE units. And the TFE unit is 80 to 10 mol%. Moreover, what is comprised from 15-25 mol% of CTFE units and 85-75 mol% of TFE units is also preferable.

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

The fluororesin (a1) is at least one selected from the group consisting of PCTFE, CTFE / TFE / PAVE copolymer and TFE / HFP / VdF copolymer from the viewpoint of fuel permeability and adhesiveness. More preferred is at least one selected from the group consisting of a CTFE / TFE / PAVE copolymer and a TFE / HFP / VdF copolymer, and a CTFE / TFE / PAVE copolymer is particularly preferred.
The CTFE / TFE / PAVE copolymer is a copolymer consisting essentially of CTFE, TFE and PAVE.

In the CTFE / TFE / PAVE copolymer, the PAVE includes perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (butyl vinyl ether). Among these, at least one selected from the group consisting of PMVE, PEVE and PPVE is preferable.
In the CTFE / TFE / PAVE copolymer, the PAVE unit is preferably 0.5 mol% or more, and preferably 5 mol% or less of the total monomer units.

Content of structural units, such as a CTFE unit, is a value obtained by performing a ¹⁹ F-NMR analysis.

In the fluororesin (a1), at least one reactive functional group selected from the group consisting of a carbonyl group, a hydroxyl group, a heterocyclic group, and an amino group is introduced into the main chain terminal and / or side chain of the polymer. It may be a thing.

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) -) and the like, include 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 is easy to introduce, and since the fluororesin (a1) has moderate heat resistance and good adhesion at a relatively low temperature, an amide group, carbamoyl group, hydroxyl group, carboxyl group , A carbonate group, a carboxylic acid halide group, and an acid anhydride bond are preferable, and an amide group, a carbamoyl group, a hydroxyl group, a carbonate group, a carboxylic acid halide group, and an acid anhydride bond are more preferable.

The fluororesin (a1) can be obtained by a conventionally known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization, bulk polymerization and the like. 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 fluororesin (a1).

Although melting | fusing point of a fluororesin (a1) is not specifically limited, It is preferable that it is 160-330 degreeC. The melting point of the fluororesin (a1) is determined as the 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 device (Seiko).

The molecular weight of the fluororesin (a1) is preferably in a range where the resulting laminate 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 400 ° C., which is a general molding temperature range of fluororesin, is 0.5 to 100 g / 10 min. It is preferable. More preferably, it is 1-50 g / 10min, More preferably, it is 2-35g / 10min. For example, when the fluororesin (a1) is PCTFE, CTFE copolymer, or TFE / HFP / VdF copolymer, MFR is measured at 297 ° C.
The above MFR uses a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.). For example, the weight of the polymer flowing out per unit time (10 minutes) from a nozzle of 2 mm in diameter and 8 mm in length under a load of 297 ° C. and 5 kg ( g) can be measured.

In the present invention, the fluororesin layer (A) may contain one of these fluororesins (a1), or may contain two or more.

In addition, when the fluororesin (a1) 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 (A) is a blend of various fillers such as inorganic powder, glass fiber, carbon powder, carbon fiber, and metal oxide, as long as the performance is not impaired depending on the purpose and application. There may be.

For example, in order to further reduce fuel permeability, smectite-based lamellar minerals such as montmorillonite, beidellite, saponite, nontronite, hectorite, soconite, and stevensite, and microlamellar minerals having a 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 single powders or conductive single fibers such as metal and carbon; powders of conductive compounds such as zinc oxide; surface conductive powders. 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 is described in, for example, metal powder such as copper and nickel; metal fiber such as iron and stainless steel; carbon black, carbon fiber, and JP-A-3-174018 Carbon fibrils and the like.

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 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.

(Rubber layer (B))
The rubber layer (B) constituting the laminate of the present invention comprises styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), isoprene rubber (IR), ethylene-propylene. -Group consisting of termonomer copolymer rubber, silicone rubber, butyl rubber, acrylic rubber, chlorinated polyethylene (CPE), chlorosulfonated polyethylene rubber, urethane rubber, polysulfide rubber, ethylene propylene diene rubber (EPDM) and fluoro rubber It consists of at least one rubber (b1) selected from the above.

Examples of the acrylic rubber include acrylic rubber (ACM) and ethylene acrylic rubber (AEM), and AEM is preferable.
AEM is a copolymer of acrylic acid ester and ethylene. AEM may be a copolymer of an acrylate ester, ethylene, and a monomer for forming a crosslinking point. Examples of the crosslinking point forming monomer include an epoxy group-containing vinyl monomer and a hydroxyl group-containing vinyl monomer.

Chlorinated polyethylene (CPE) is a synthetic rubber obtained by chlorinating polyethylene using chlorine gas. The vulcanizing agent for chlorinated polyethylene is not particularly limited, and a thiazole-based vulcanizing agent, a triazine-based vulcanizing agent, a peroxide-based vulcanizing agent, or the like may be used, and two or more kinds may be used.

The fluororubber usually comprises an amorphous polymer having a fluorine atom bonded to a carbon atom constituting the main chain and having rubber elasticity. Fluoro rubber usually has no clear melting point.
Examples of the fluororubber include a fluororubber capable of peroxide vulcanization, a fluororubber capable of polyol vulcanization, and a fluororubber capable of polyamine vulcanization. The peroxide vulcanizable fluoro rubber is not particularly limited as long as it is a fluoro rubber having a peroxide vulcanizable site. The peroxide vulcanizable site is not particularly limited, and examples thereof include an iodine atom and a bromine atom.
The polyol vulcanizable fluoro rubber is not particularly limited as long as it is a fluoro rubber having a polyol vulcanizable part. The polyol vulcanizable part is not particularly limited, and examples thereof include a part having a vinylidene fluoride (VdF) unit. Examples of the method for introducing the vulcanization site include a method of copolymerizing a monomer that gives a vulcanization site during the polymerization of the fluororubber.

Examples of the fluororubber include vinylidene fluoride (VdF) / hexafluoropropylene (HFP) fluororubber, VdF / HFP / tetrafluoroethylene (TFE) fluororubber, TFE / propylene fluororubber, and TFE / propylene / VdF. Fluoro rubber, ethylene / HFP fluoro rubber, ethylene / HFP / VdF fluoro rubber, ethylene / HFP / TFE fluoro rubber, VdF / TFE / perfluoroalkyl vinyl ether (PAVE) fluoro rubber, VdF / CTFE fluoro rubber, VdF / CH ₂ = CFRf ³ (wherein Rf ³ is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms) -based fluororubber.

From the viewpoint of heat resistance, compression set, workability, and cost, the fluoro rubber is more preferably fluoro rubber containing VdF units (VdF fluoro rubber) or TFE / propylene fluoro rubber, and VdF fluoro rubber is more preferable. More preferred is at least one fluororubber selected from the group consisting of VdF-HFP fluororubber and VdF-HFP-TFE fluororubber.
As said fluororubber, what was demonstrated above is not restricted to 1 type, You may use 2 or more types, The thing which vulcanized these may be used.

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

The rubber (b1) is preferably at least one selected from the group consisting of chlorinated polyethylene, acrylic rubber, and fluorine rubber containing VdF units, and is preferably a group consisting of chlorinated polyethylene and acrylic rubber. At least one selected from the above is more preferable, and chlorinated polyethylene and ethylene acrylic rubber (AEM) are more preferable.

The rubber layer (B) in the present invention is formed from a rubber composition. In the rubber composition, the rubber component may consist only of the rubber (b1) described above. The rubber composition preferably further contains an adhesive additive in that the adhesion between the fluororesin layer (A) and the rubber layer (B) becomes stronger. The rubber layer (B) is preferably a layer formed from a rubber composition containing rubber (b1) and an adhesive additive. Examples of the adhesive additive include basic polyfunctional compounds such as polyamine compounds, organoonium compounds such as organic phosphonium salts, aminosilane compounds, and reactive liquid polymers. Of these, basic polyfunctional compounds are preferred. The rubber layer (B) is preferably a layer formed from a rubber composition containing the rubber (b1) and a basic polyfunctional compound.

The basic polyfunctional compound is a compound having two or more functional groups having the same or different structures in one molecule and showing basicity.

The functional groups of the polyfunctional compound of the basic, preferably shows a basic, for ^{_{example, -NH 2, -NH 3 +,}} -NHCOOH, -NHCOO -, -N = CR 1 R 2 (Wherein R ¹ and R ² are each independently an organic group having 0 to 12 carbon atoms), —NR ³ R ⁴ (wherein R ³ and R ⁴ are independently 0 carbon atoms) -NR ³ R ⁴ R ⁵ (wherein R ³ , R ⁴ and R ⁵ are each independently an organic group having 0 to 12 carbon atoms), and by heating At least one selected from the group consisting of functional groups that change to the functional group is preferred, and —NH ₂ , —NH ₃ ⁺ , —NHCOOH, —NHCOO ⁻ , and —N═CR ¹ R ² (wherein R ¹ and R ² is at least selected from the group consisting of the same) and the 1 Still more ^{_{preferably, -NH 2, -NH 3 + -NHCOOH}} , and, -NHCOO ^- even more preferably at least one selected from the group consisting of.
R ¹ , R ² , R ³ , R ^4, and R ⁵ are each independently preferably —H or an organic group having 1 to 12 carbon atoms, and —H or 1 to 12 carbon atoms. The hydrocarbon group is preferably. The hydrocarbon group may have one or more carbon-carbon double bonds. The hydrocarbon group preferably has 1 to 8 carbon atoms.
R ¹ is —H or —CH ₃ , and R ² is —CH═CHR ⁶ (R ⁶ is a phenyl group (—C ₆ H ₅ ), a benzyl group (—CH ₂ —C ₆ H _5). ), or is preferably a -H), said ^{R 1} is -H, ^{R 2} is more preferably a _{-CH = CH-C 6 H 5} .

Examples of the basic polyfunctional compound include ethylenediamine, propanediamine, putrescine, cadaverine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, phenylenediamine, and N, N-dicinenamilidene-1. , 6-hexamethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexamethylenediamine, N, N′-dimethyl-1,6-hexamethylenediamine, 6-aminohexylcarbamic acid ( Hexamethylenediamine carbamate) and the like.

The basic polyfunctional compound preferably contains at least two nitrogen atoms in the molecule, and the interatomic distance between nitrogen and nitrogen is preferably 5.70 cm or more. The interatomic distance between nitrogen and nitrogen is more preferably 6.30 mm or more, and further preferably 7.60 mm or more. The wide interatomic distance between nitrogen and nitrogen increases the flexibility of the basic polyfunctional compound and facilitates vulcanization.
Here, the interatomic distance between nitrogen and nitrogen is calculated according to the following method. That is, the structure optimization of each base is calculated using a density functional method (program: Gaussian 03, density functional: B3LYP, basis function: 6-31G *).

Since the basic polyfunctional compound can improve the adhesion between the rubber layer (B) and the fluororesin layer (A), 6-aminohexylcarbamic acid (hexamethylenediamine carbamate) and N, N-dicinnamilidene-1 , 6-hexamethylenediamine is preferable, and 6-aminohexylcarbamic acid (hexamethylenediamine carbamate) is more preferable.

Since the rubber layer (B) and the fluororesin layer (A) are more firmly bonded, the content of the basic polyfunctional compound in the rubber composition is 100 parts by mass of the rubber (b1), It is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, still more preferably 0.5 parts by mass or more, and particularly preferably 1.0 parts by mass or more. .
The content of the basic polyfunctional compound is preferably 10.0 parts by mass or less, and particularly preferably 6.0 parts by mass or less, from the viewpoints of vulcanization inhibition and cost.

The rubber composition preferably further contains a vulcanizing agent. The vulcanizing agent can be appropriately selected depending on the vulcanization system of the rubber (b1) to be blended. However, when a vulcanization method in which vulcanization proceeds without using a vulcanizing agent, such as condensation vulcanization, the vulcanizing agent may not be included.

The rubber (b1) is a non-fluorinated rubber (SBR, CR, BR, NR, IR, ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, acrylic rubber, CPE, chlorosulfonated polyethylene rubber, urethane rubber. , Polysulfide rubber, EPDM), sulfur vulcanizing agent, peroxide vulcanizing agent, amine vulcanizing agent, platinum compound, thiourea derivative, triazine vulcanizing agent, quinoid vulcanizing agent Resin-based vulcanizing agents, metal oxide-based vulcanizing agents, and the like.
When the rubber (b1) is CPE, peroxide vulcanizing agents, thiourea derivatives, triazine vulcanizing agents and combinations thereof can be used. When the rubber (b1) is an acrylic rubber, a peroxide vulcanizing agent, an amine vulcanizing agent, and a triazine vulcanizing agent can be used.
The usage-amount of the said vulcanizing agent is 0.1-10.0 mass normally with respect to 100 mass parts of rubber | gum (b1), Preferably it is 0.3-5.0 mass.

When the rubber (b1) is a fluororubber, a peroxide vulcanizing agent, a polyol vulcanizing agent, a polyamine vulcanizing agent and the like can be selected according to the purpose. It does not specifically limit as said peroxide type | system | group vulcanizing agent, For example, an organic peroxide can be mentioned. The organic peroxide is preferably one that easily generates a peroxy radical in the presence of heat or a redox system. For example, 1,1-bis (t-butylperoxy) -3,5,5-trimethyl Cyclohexane, 2,5-dimethylhexane-2,5-dihydroxy peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxy) -P-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, benzoylper Oxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t -Butyl peroxy isopropyl carbonate etc. can be illustrated. Of these, dialkyl compounds are preferred. In general, the amount used is appropriately selected from the amount of active —O—O—, the decomposition temperature, and the like. The amount used is usually 0.1 to 15 parts by mass, preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the fluororubber.

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

As a compounding quantity of the said vulcanization | cure adjuvant and a co-curing agent, 0.2-10 mass parts is preferable with respect to 100 mass parts of fluororubber, 0.3-6 mass parts is more preferable, 0.5- 5 parts by mass is more preferable. If the vulcanizing agent or co-curing agent is less than 0.2 parts by mass, the vulcanization density tends to be low and the compression set tends to be large, and if it exceeds 10 parts by mass, the vulcanization density becomes too high. For this reason, it tends to break easily during compression.

The polyol vulcanizing agent is not particularly limited, and for example, a polyhydroxy compound, particularly a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance. The polyhydroxy aromatic compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane ( (Hereinafter referred to as bisphenol AF), resorcin, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4′- Dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2, 2-bis (4-hydroxyphenyl) te Lafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 Examples include ', 5,5'-tetrabromobisphenol A. These polyhydroxy aromatic compounds may be an alkali metal salt, an alkaline earth metal salt, or the like, but when the copolymer is coagulated using an acid, it is preferable not to use the metal salt.

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

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

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

A rubber composition is used as an acid acceptor or as a compounding agent for improving the adhesion between a fluororubber layer and a non-fluororubber layer, as a metal oxide, a metal hydroxide, an alkali metal weak acid salt, and an alkaline earth. You may contain the at least 1 sort (s) of compound selected from the group which consists of the weak acid salt of a similar metal.
Examples of the metal oxides, metal hydroxides, alkali metal weak acid salts, and alkaline earth metal weak acid salts include oxides, hydroxides, carbonates, carboxylates, silicas of group (II) metals of the periodic table. Acid salts, borates, phosphites, periodic table group (IV) metal oxides, basic carbonates, basic carboxylates, basic phosphites, basic sulfites and the like. .
Specific examples of metal oxides, metal hydroxides, alkali metal weak acid salts and alkaline earth metal weak acid salts include magnesium oxide, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, calcium oxide ( Examples thereof include quick lime), calcium hydroxide (slaked lime), calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate, calcium phosphite, tin oxide, and basic tin phosphite.
When using an organic peroxide as a vulcanizing agent, the content of the above metal oxide, metal hydroxide, alkali metal weak acid salt, alkaline earth metal weak acid salt is preferably 3 parts by mass or less, More preferably, it is 1 mass part or less, and it is still more preferable not to contain from a viewpoint of acid resistance.

When a polyol vulcanizing agent is used, it is preferable to contain an alkali metal silicate. By the presence of the alkali metal silicate, crosslinking can be carried out in the same amount of time as when conventional calcium hydroxide is blended at the time of polyol crosslinking without blending calcium hydroxide. In addition, since it contains no alkali metal silicate, it is not necessary to add calcium hydroxide to increase the crosslinking speed, so the fluororubber layer is a chemical, solvent (especially acidic solvent), fuel (especially biogenic fuel) It is possible to reduce deterioration and swelling caused by contact with the like, and to expect improvement in compression set.

Examples of the alkali metal silicate include sodium silicate, potassium silicate, lithium silicate, and hydrated salts thereof.

When the alkali metal silicate is sodium silicate or a hydrate thereof, the composition of the sodium silicate or the hydrate is represented by a mass ratio (%) converted to Na ₂ O, SiO ₂ and H ₂ O, Na ₂ O is 0.5 to 95 wt%, SiO ₂ is 5 to 99 wt%, it is preferred _{H 2} O is 0 to 94.5 wt%. From the viewpoint of excellent effect of increasing the rate of crosslinking, Na ₂ O is 1 to 85 wt%, SiO ₂ is 2.0 to 95 wt%, and more preferably _{H 2} O is 0 to 85 wt% . Furthermore, from the viewpoint of excellent workability, Na ₂ O is 2 to 70 wt%, SiO ₂ is 7.0 to 70 mass%, more preferably _{H 2} O is 0 to 75 wt%.

Examples of sodium silicate or its hydrated salt include sodium silicate Nos. 1 to 5 (Fuji Chemical Co., Ltd.), sodium metasilicate pentahydrate, 9 hydrate (Fuji Chemical Co., Ltd.), and orthosilicate. Soda (65%, 80%) (manufactured by Osaka Soda Co., Ltd.), powdered sodium silicate 1-3 (manufactured by Nippon Chemical Industry Co., Ltd.), anhydrous sodium metasilicate (manufactured by Osaka Soda Co., Ltd.) It is available.

When the alkali metal silicate is a hydrated salt of potassium silicate, the composition of the hydrated potassium silicate is represented by a mass ratio (%) converted to K ₂ O, SiO ₂ and H ₂ O. K ₂ O is 5 to 30 mass%, SiO ₂ 15 to 35 wt%, it is preferred _{H 2} O is 35 to 80 mass%.

As the hydrated salt of potassium silicate, for example, No. 1 potassium silicate, No. 2 potassium silicate (manufactured by Fuji Chemical Co., Ltd.) and the like are available.

When the alkali metal silicate is a hydrated salt of lithium silicate, the composition of the hydrated salt of lithium silicate is represented by a mass ratio (%) converted to Li ₂ O, SiO ₂ and H ₂ O, li ₂ O is 0.5 to 10 mass%, SiO ₂ 15 to 25 wt%, it is preferred _{H 2} O is 65 to 84.5 wt%.

As a hydrated salt of lithium silicate, it can be obtained as, for example, lithium silicate 45 (manufactured by Nippon Chemical Industry Co., Ltd.).

Among these, sodium silicate or a hydrated salt thereof is preferable from the viewpoint that a stable crosslinking rate can be obtained and fuel resistance is excellent.

As content of alkali metal silicate, 0.1-10 mass parts is preferable with respect to 100 mass parts of fluororubber, and 0.2-7 mass parts is more preferable.

Although the present invention does not necessarily exclude the combined use of calcium hydroxide and alkali metal silicate, the combined use of calcium hydroxide does not affect the advantages and effects exhibited by the alkali metal silicate. It should be stopped to the extent. The amount should be smaller than the amount of the alkali metal silicate contained in the fluorine-containing elastomer composition, and specifically, 3 parts by mass or less, further 1 It should be not more than part by mass, and it is particularly preferable not to blend substantially.

In the rubber composition, usual additives blended in the rubber composition as necessary, for example, a filler, a processing aid, a plasticizer, a colorant, a stabilizer, an adhesion aid, an acid acceptor, Various additives such as release agents, conductivity imparting agents, thermal conductivity imparting agents, surface non-adhesives, flexibility imparting agents, heat resistance improvers, flame retardants and the like can be blended, and are different from those described above. One or more conventional vulcanizing agents and vulcanization accelerators may be blended.

Examples of the filler include carbon black. The content of carbon black is preferably 5 to 200 parts by mass and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the rubber (b1). The use of carbon black has the advantage of improving mechanical properties, heat resistance, and the like.

The rubber composition is composed of rubber (b1) and other additives such as a basic polyfunctional compound, a vulcanizing agent, a vulcanizing aid, a co-vulcanizing agent, a vulcanization accelerator, and a filler as necessary. The agent can be obtained by kneading using a commonly used rubber kneading apparatus. As the rubber kneading apparatus, a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used.

In the laminate of the present invention, the thickness of the rubber layer (B) is not limited, but is preferably 100 μm or more, for example. The upper limit of the thickness of the rubber layer (B) is, for example, 5000 μm.

Although the thickness of the said fluororesin layer (A) is not limited, For example, it is preferable that it is 10 micrometers or more. The upper limit of the thickness of the fluororesin layer (A) is, for example, 1000 μm.

The laminate of the present invention preferably has an interlayer initial adhesive strength of 5 N / cm or more. When the interlayer initial adhesive strength is 5 N / cm or more, there is an advantage that when the hose is vulcanized in a specific shape, displacement does not easily occur and peeling does not occur when an impact is applied.
The laminated body of this invention can make interlayer initial stage adhesive strength into the said range by having the said structure. The interlayer initial adhesive strength is more preferably 10 N / cm or more, and further preferably 15 N / cm or more.
The initial adhesion strength between layers was determined in accordance with JIS-K-6256 (adhesion test method for vulcanized rubber), a peel test was performed at 25 ° C. at a tensile rate of 50 mm / min, and the adhesion strength was measured. 3 is a value obtained by calculating an average value of the three data.

In the laminate of the present invention, the rubber layer (B) and the fluororesin layer (A) are preferably vulcanized and bonded. Such a laminate can be obtained by laminating the unvulcanized rubber layer (B) and the fluororesin layer (A) and then vulcanizing.

For the above vulcanization treatment, conventionally known rubber composition vulcanization methods and conditions can be employed. For example, a method in which an unvulcanized laminate is vulcanized for a long time, a heat treatment as a pretreatment is performed on the unvulcanized laminate in a relatively short period of time (vulcanization is also occurring), and then the vulcanization is performed over a long period of time. There is a method of performing sulfuration. Of these methods, a method in which the unvulcanized laminate is subjected to heat treatment as a pretreatment in a relatively short time and then vulcanized over a long period of time is a method in which the rubber layer (B) and the fluororesin layer (A ) And the rubber layer (B) has already been vulcanized in the pretreatment and the shape is stabilized, so various methods for holding the laminate in subsequent vulcanization can be selected. This is preferable.

The conditions for the vulcanization treatment are not particularly limited and can be performed under ordinary conditions, but at 140 to 250 ° C. for 2 to 80 minutes, steam, press, oven, air bath, infrared, microwave, The treatment is preferably performed using lead vulcanization or the like. More preferably, it is performed at 150 to 200 ° C. for 5 to 60 minutes. The vulcanization treatment may be performed separately for primary vulcanization and secondary vulcanization.

(Laminate manufacturing method)
This invention is a manufacturing method of the laminated body mentioned above, Comprising: The process (1) which forms a fluororesin layer (A), the process (2) which discharge-processes at least one surface of a fluororesin layer (A), and And a step (3) of forming the rubber layer (B) on the surface of the fluororesin layer (A) subjected to the discharge treatment, and a method for producing a laminate.

In the step (1), the fluororesin layer (A) is formed by molding the fluororesin (a1). The method for molding the fluororesin (a1) is not particularly limited, and examples thereof include methods such as heat compression molding, melt extrusion molding, injection molding, and coating (including powder coating). For molding, commonly used fluororesin molding machines, such as injection molding machines, blow molding machines, extrusion molding machines, various coating devices, etc., 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.
When using various additives, the fluororesin composition is prepared by mixing with the fluororesin (a1) in advance and then molded.

In the step (2), at least one surface of the fluororesin layer (A) formed in the step (1) is subjected to a discharge treatment. The method and conditions for the discharge treatment are as described above. The discharge treatment may be performed only on one surface of the fluororesin layer (A) or on both surfaces.

In the step (3), the rubber layer (B) is formed on the surface of the fluororesin layer (A) subjected to the discharge treatment. For example, a rubber layer (B) is formed from the rubber composition separately from the fluororesin layer (A), and then the rubber layer (B) is overlaid on the surface of the fluororesin layer (A) subjected to discharge treatment. A method of laminating by means such as bonding and pressure bonding (method (i)) and a method of extruding the rubber composition on the surface of the fluororesin layer (A) subjected to discharge treatment (method (ii)). Can be mentioned. From the viewpoint of economy, the method (ii) is preferable.

In the above method (i), the rubber layer (B) can be formed by a normal rubber composition molding method, such as a heat compression molding method, transfer molding method, extrusion molding method, injection molding method, calendar molding. Law, painting method and the like.

The step (3) may include a step of vulcanizing the laminated unvulcanized rubber layer (B) and the fluororesin layer (A). Thereby, since the rubber layer (B) and the fluororesin layer (A) are vulcanized and bonded, the interlayer adhesion is further improved. The method and conditions for the vulcanization treatment are as described above.

In the step (3), for example, a sheet of an unvulcanized rubber composition is formed using a roll kneader or the like, and the sheet is placed on the surface subjected to the discharge treatment of the fluororesin layer (A). You may superimpose and then perform vulcanization processes, such as press vulcanization.

(Laminated structure of laminated body)
The laminate of the present invention may have a two-layer structure of a fluororesin layer (A) and a rubber layer (B), or a rubber layer (B) laminated on both sides of the fluororesin layer (A). Alternatively, the fluororesin layer (A) may be laminated on both sides of the rubber layer (B).

The laminate of the present invention may have a two-layer structure of a rubber layer (B) and a fluororesin layer (A), or may have a rubber layer (B) laminated on both sides of the fluororesin layer (A). Alternatively, the fluororesin layer (A) may be laminated on both sides of the rubber layer (B). In any embodiment, it is important that the laminate surface of the fluororesin layer (A) with the rubber layer (B) is subjected to a discharge treatment. Only one side of the fluororesin layer (A) may be discharged, or both sides may be discharged.

The layer structure of the laminate of the present invention is, for example, rubber layer (B) -fluorine resin layer (A) -rubber layer (B) or fluorine resin layer (A) -rubber layer (B) -fluorine resin layer (A). Such a three-layer structure may be used.
Further, it may be a multilayer structure of three or more layers in which a polymer layer (C) other than the rubber layer (B) and the fluororesin layer (A) is bonded, or the rubber layer (B) and the fluororesin layer (A). The polymer layer (D) may be provided on one side or both sides of a three-layer multilayer structure to which a polymer layer (C) other than the above is adhered. The polymer layer (C) and the polymer layer (D) may be the same or different.

The laminate of the present invention may have a polymer layer (C) on one side or both sides of a three-layer structure of rubber layer (B) -fluororesin layer (A) -rubber layer (B).

The polymer layers (C) and (D) may be rubber layers (C1) or (D1) other than the rubber layer (B). Examples of the rubber layer (C1) or (D1) include a rubber layer (C1a) or (D1a) formed from a rubber (b2) other than the rubber (b1). The rubber layer (C1a) and the rubber layer (D1a) may be formed from the same rubber or may be formed from different rubbers.
The laminate of the present invention may be laminated in the order of rubber layer (B) -fluororesin layer (A) -rubber layer (C1a).
Further, the rubber layer (D1a) is further included. The rubber layer (D1a) -the rubber layer (B) -the fluororesin layer (A) -the rubber layer (C1a) in this order, the rubber layer (B) -the fluororesin layer (A ) -Rubber layer (D1a) -rubber layer (C1a), or rubber layer (B) -fluorine resin layer (A) -rubber layer (C1a) -rubber layer (D1a). It may be a thing.

Examples of the rubber (b2) include acrylonitrile-butadiene rubber (NBR) or a hydride thereof (HNBR), epichlorohydrin rubber, acrylonitrile-butadiene rubber and vinyl chloride polyblend (PVC-NBR), acrylonitrile-butadiene rubber and acrylic rubber. And polyblends. In addition, you may mix | blend a vulcanizing agent and another compounding agent also in the unvulcanized rubber composition which forms rubber layer (C1), (D1).

The polymer layers (C) and (D) may be resin layers (C2) and (D2) other than the fluororesin layer (A).

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

(1) Basic structure of two-layer structure of rubber layer (B) -fluorine resin layer (A). Conventionally, in order to laminate the fluororesin layer (A) and the rubber layer (B), an interlayer (rubber layer-fluorine Since the adhesion of the resin layer) was insufficient, it was necessary to separately apply an adhesive between the layers or to wrap and fix the tape-like film. According to the present invention, such a process is combined. First, a strong bond is obtained.

(2) Rubber layer-Fluororesin layer (A) -Rubber layer three-layer structure Rubber layer (B) -Fluororesin layer (A) -Rubber layer (B) three-layer structure and rubber layer (B)- There is a three-layer structure of a fluororesin layer (A) -rubber layer (C1).
When sealing performance is required, it is desirable to arrange rubber layers on both sides in order to maintain the sealing performance of, for example, a joint such as a fuel pipe. The inner and outer rubber layers may be the same type or different types.
In the case of a three-layer structure of rubber layer (B) -fluorine resin layer (A) -rubber layer (C1), the rubber layer (C1) is composed of acrylonitrile butadiene rubber, hydrogenated acrylonitrile butadiene rubber, acrylic rubber, fluoro rubber, and epichlorohydrin. A layer made of at least one rubber selected from the group consisting of rubbers is preferred.
In particular, the fuel pipe has a three-layer structure of rubber layer (B) -fluororesin layer (A) -rubber layer (C1), and a fluororubber layer is provided as the rubber layer (B) or (C1) to form a fluororubber layer By using the rubber layer (B) or (C1) as the inner layer of the pipe, chemical resistance and low fuel permeability are improved.

(3) Three-layer structure of resin layer-rubber layer (B) -resin layer Three-layer structure of fluororesin layer (A) -rubber layer (B) -fluorine resin layer (A), and fluororesin layer (A) -The three-layer structure of rubber layer (B) -resin layer (C2) is mentioned. The inner and outer resin layers may be of the same type or different types.

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

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

(6) Four-layer structure or more In addition to the three-layer structure of (2) to (5), an optional rubber layer (B), rubber layer (C1), fluororesin layer (A) or resin layer (C2) You may laminate | stack according to the objective. Moreover, layers, such as metal foil and a reinforcement thread | yarn, may be provided, and you may interpose an adhesive bond layer other than the interlayer of a rubber layer (B) and a fluororesin layer (A).

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.
In addition, for the purpose of improving pressure resistance, a reinforcing layer such as a reinforcing yarn may be provided as appropriate.

(Use of laminates)
The laminate of the present invention is excellent in low fuel permeability, heat resistance, oil resistance, fuel oil resistance, LLC resistance, steam resistance, weather resistance, ozone resistance, and under severe conditions. Can be used for various purposes.

For example, the engine body of a car engine, main motion system, valve system, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, etc. Gaskets that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, steam resistance, non-contact type and contact type packings (self-sealing) such as basic electric parts, control system electric parts, equipment electric parts, etc. (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, hydrogen Sealing material for high pressure valves in storage systems.

Shaft seals such as crankshaft seals and camshaft seals for the main motion system.

Valve stem seals for valve valves and engine valves.

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

Fuel seals, fuel pump oil seals, diaphragms, valves, etc. Filler (neck) hoses, fuel supply hoses, fuel return hoses, vapor (evaporation) hose fuel hoses, fuel tank in-tank hoses, filler seals, tanks Packing, in-tank fuel pump mount, fuel pipe tube body, connector O-ring, etc. 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. Especially, it is suitable as an in-tank hose of a fuel hose and a fuel tank.

Intake / exhaust manifold manifold manifold packing, exhaust manifold packing, EGR diaphragm, control hose, emission control hose, BPT diaphragm, AB valve after-burn prevention valve seat, throttle, 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, etc. AT transmission oil hoses, ATF hoses, O-rings, packings, etc.

Steering power steering oil hose, etc.

Brake system oil seal, O-ring, packing, brake oil hose, etc., master back atmospheric valve, vacuum valve, diaphragm, etc., master cylinder piston cup (rubber cup), caliper seal, boots, etc.

Tubes of harness exterior parts, such as insulators and sheaths of electric wires (harnesses) of basic electrical components.

Coating materials for various sensor wires for control system electrical components.

Car air conditioner O-rings, packings, cooler hoses, exterior wiper blades, 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. For similar packing, O-rings, seals, diaphragms, valves, hoses, rolls, tubes, chemical resistant coatings, linings in plants, hoses or gaskets in the chemical processing field, food plant equipment and food equipment (household products) In the same packing, O-rings, hoses, seals, belts, diaphragms, valves, rolls, tubes in nuclear power plant equipment, and similar packings, O-rings, hoses, seals, diaphragms, valves, tubes in nuclear power plant equipment , OA equipment, general industrial parts Suitable for use in kin, O-ring, hose, sealing material, diaphragm, valve, roll, tube, lining, mandrel, electric wire, flexible joint, belt, rubber plate, weather strip, roll blade of PPC copying machine, etc. . For example, the backup rubber material of the PTFE diaphragm has a problem of being worn or torn during use because of its poor sliding property, but this problem can be improved by using the laminate of the present invention, and is suitable. Can be used for

In addition, in food rubber seal material applications, there is a problem that flavor and rubber fragments are mixed into food in conventional rubber seal materials, but by using the laminate of the present invention, this problem can be improved and preferably Can be used. 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. It can also be used to protect rubber materials used in containers, syringes, etc. from chemicals. 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. In addition, it can be suitably used in applications where slidability with low friction is required.

Among these, the laminate is particularly preferably used as a tube or a hose. That is, the laminate is preferably a tube or a hose. Among tubes, it can be suitably used as a fuel piping tube or hose for automobiles in terms of heat resistance and low fuel permeability.

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

A laminate (a) having the following characteristics can also be used as a laminate used for protecting a rubber material used for a container, a syringe and the like from a chemical solution. That is, a laminate comprising a fluororesin layer (A) and a rubber layer (B) formed on the fluororesin layer (A), wherein the fluororesin layer (A) is tetrafluoroethylene / hexafluoropropylene. The rubber layer (B) is composed of at least one fluororesin selected from the group consisting of a copolymer (FEP) and a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA). The laminate (a) is characterized in that the laminate surface of the fluororesin layer (A) and the rubber layer (B) is subjected to a discharge treatment.

In the laminate (a), neither FEP nor PFA contains CTFE units or VdF units. In the laminate (a), the rubber layer (B) is preferably made of silicone rubber. In the laminate (a), the discharge treatment is preferably a discharge treatment in an atmosphere in which a reactive organic compound is mixed with an inert gas. Examples of the inert gas include nitrogen gas, helium gas, and argon gas. The reactive organic compound is a polymerizable or non-polymerizable organic compound containing an oxygen atom, for example, vinyl esters such as vinyl acetate and vinyl formate; acrylic acid esters such as glycidyl methacrylate; vinyl ethyl ether, vinyl Ethers such as methyl ether and glycidyl methyl ether; Carboxylic acids such as acetic acid and formic acid; Alcohols such as methyl alcohol, ethyl alcohol, phenol, and ethylene glycol; Ketones such as acetone and methyl ethyl ketone; Carboxes such as ethyl acetate and ethyl formate Acid esters; acrylic acids such as acrylic acid and methacrylic acid; and the like, and vinyl acetate or glycidyl methacrylate is preferred. The discharge treatment is preferably a corona discharge treatment.

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

In the experimental examples, each physical property value was measured by the following method.

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

(2) Using a melting point Seiko type DSC apparatus, 10 ° C./min. The melting peak when the temperature was raised at a speed of 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 a load of 297 ° C. and 5 kg was measured.

(4) Measurement of fuel permeability coefficient of fluororesin Each fluororesin pellet was placed in a mold with a diameter of 120 mm, set in a press machine heated to 300 ° C., melt-pressed at a pressure of about 2.9 MPa, A sheet having a thickness of 0.15 mm 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 unit time (part where the mass change at the beginning of measurement was constant), the surface area of the wetted part sheet, and the sheet thickness.

The materials used in the experimental examples are shown below.
・ Fluorine resin (1)
CTFE / PPVE / TFE copolymer, CTFE / PPVE / TFE = 21.3 / 2.4 / 76.3 (mol%), MFR = 30 (297 ° C., 5 kg), melting point 245 ° C., fuel permeability coefficient: 0 .4 g · mm / m ² / day
・ Rubber (1)
VdF / HFP copolymer, trade name: G802, manufactured by Daikin Industries, Ltd., rubber (2)
Chlorinated polyethylene (CPE), trade name: Eraslen 302NE-X5, Showa Denko Co., Ltd. rubber (3)
Ethylene acrylic rubber (AEM), trade name: Vamac DP, DuPont rubber (4)
Ethylene acrylic rubber (AEM), trade name: Vamac G, DuPont rubber (5)
Ethylene acrylic rubber (AEM), trade name: Vamac HVG, DuPont rubber (6)
Acrylonitrile-butadiene rubber (NBR), trade name: JSR N-250S, manufactured by JSR Corporation

V-1 (trade name), 6-aminohexylcarbamic acid, manufactured by Daikin Industries, Ltd., distance between N in molecule: 8.80Å
V-3 (trade name), N, N-dicinnamylidene-1,6-hexamethylenediamine, manufactured by Daikin Industries, Ltd., distance between N in molecule: 8.80Å
MT carbon black, Asahi # 15 (trade name), Seast S (trade name) manufactured by Asahi Carbon Co., Ltd., SRF carbon black, Seast SO (trade name) manufactured by Tokai Carbon Co., Ltd., FEF carbon black, Tokai Carbon Co., Ltd. Kyowamag # 150 (trade name), magnesium oxide, TAIC manufactured by Kyowa Chemical Co., Ltd., Perhexa 25B (trade name) manufactured by Nippon Kasei Co., Ltd., Thiokol TP-95 (trade name) manufactured by NOF Corporation, Rohm and Noxeller MDCA (trade name) manufactured by Haas, Noxeller TCA (trade name) manufactured by Ouchi Shinsei Chemical Co., Ltd. Noxeller DT (trade name) manufactured by Ouchi New Chemical Co., Ltd. Product name), Nouchira MZ (ZnMBT) (trade name) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. Shinsei Chemical Co., Ltd. Park Mill D40 (trade name), NOF Corporation stearic acid 50S (trade name), stearic acid, Shin Nippon Rika Co., Ltd. DOS (trade name), Shin Nippon Chemical Co., Ltd. Phosphonol RL- 210 (trade name), Toka Chemical Co., Ltd. Parkadox 14-40 (trade name), Kayaku Akzo Balnock PM-P (trade name), Ouchi Shinsei Chemical Co., Ltd. Carplex 1120 (trade name) ), Basic silica, calcium carbonate manufactured by DSL Japan, sulfur fine powder manufactured by Wako Pure Chemical Industries, Ltd., manufactured by Hosoi Chemical Co., Ltd.

Experimental example (production of rubber composition)
The materials shown in Tables 1 to 4 below were kneaded using an 8-inch open roll to obtain a sheet-like rubber composition for vulcanization having a thickness of about 2 mm. In addition, each numerical value of the compounding quantity of Tables 1-4 represents a "mass part". Also, for the rubber composition for vulcanization, the maximum torque value (MH) and the minimum torque value (ML) at 160 ° C. using a curast meter type II (model number: JSR curlastometer, manufactured by JSR). Was measured, and an induction time (T10) and an optimum vulcanization time (T90) were determined. The measurement results are shown in Tables 1 to 4. T10 is the time when {(MH) − (ML)} × 0.1 + ML, T90 is the time when {(MH) − (ML)} × 0.9 + ML, and MH and ML are JIS It is a value measured according to K 6300-2.

(Manufacture of laminates)
The materials shown in Tables 1 to 4 were kneaded using an 8-inch open roll to obtain a vulcanized rubber composition sheet (unvulcanized rubber layer) having a thickness of 3 mm. Using a plasma discharge treatment device (manufactured by Sekisui Chemical Co., Ltd.) on one side of a 0.12 mm thick sheet made of fluororesin (1), normal pressure in a nitrogen atmosphere with the number of heads and the line speed shown in Table 5 Plasma discharge treatment was performed. The treatment temperature was 20 ° C. A sheet of the fluororesin (1) is overlaid on the surface subjected to the discharge treatment, and the vulcanized rubber composition sheet is superposed on one end and a fluororesin film having a width of about 10 to 15 mm (thickness 10 μm, Daikin). Kogyo Co., Ltd. product name Polyflon PTFE M731 skive film) was sandwiched between both sheets, and then inserted into a metal mold with a metal spacer so that the resulting sheet had a thickness of 2 mm, and at 160 ° C. for 45 minutes. The sheet-like laminated body which consists of a fluororesin layer and a rubber layer was obtained by pressing.
Further, a sheet-like laminate was obtained in the same manner as described above except that the sheet made of the fluororesin (1) was not subjected to the discharge treatment.

(Adhesion evaluation)
The obtained laminate was cut into strips having a width of 10 mm, a length of 40 mm, and 3 sets, and a fluororesin film was peeled off to prepare a sample piece that was grasped. About this test piece, according to the method as described in JIS-K-6256 (adhesion test method of vulcanized rubber) using an autograph (AGS-J 5kN manufactured by Shimadzu Corporation), 50 mm at 25 ° C. A peeling test was conducted at a tensile speed of / min, and the peeling mode was observed and evaluated according to the following criteria. The results are shown in Table 5.
○ ... The rubber layer or fluororesin layer was destroyed at the interface of the laminate, and it was impossible to peel off at the interface.
Δ: The peel strength at the interface of the laminate was 5 N / cm or more.
X: The peel strength at the interface of the laminate was less than 5 N / cm.

Claims (10)

A laminate comprising a fluororesin layer (A) and a rubber layer (B) formed on the fluororesin layer (A),
The fluororesin layer (A) is made of a fluororesin (a1) having a fuel permeability coefficient of 2.0 g · mm / m ² / day or less,
The rubber layer (B) is made of styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, At least one selected from the group consisting of silicone rubber, butyl rubber, acrylic rubber, chlorinated polyethylene (CPE), chlorosulfonated polyethylene rubber, urethane rubber, polysulfide rubber, ethylene propylene diene rubber (EPDM), and fluorine rubber Made of rubber (b1),
A laminate in which a laminate surface of the fluororesin layer (A) and the rubber layer (B) is subjected to a discharge treatment. The laminate according to claim 1, wherein the discharge treatment is a plasma discharge treatment. The laminate according to claim 1 or 2, wherein the discharge treatment is a normal pressure plasma discharge treatment. The laminate according to claim 1, 2 or 3, wherein the discharge treatment is performed in a nitrogen atmosphere. The rubber (b1) is at least one selected from the group consisting of chlorinated polyethylene, acrylic rubber, and fluororubber containing vinylidene fluoride (VdF) units. Laminated body. The fluororesin (a1) is at least one selected from the group consisting of polychlorotrifluoroethylene, chlorotrifluoroethylene copolymer, and tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer. Item 6. The laminate according to Item 1, 2, 3, 4 or 5. The fluororesin (a1) is at least one selected from the group consisting of a chlorotrifluoroethylene copolymer and a tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer. The laminate according to 4, 5, or 6. The laminate according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the rubber layer (B) is a layer formed from a rubber composition containing the rubber (b1) and an adhesive additive. The laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the rubber layer (B) is a layer formed from a rubber composition containing the rubber (b1) and a basic polyfunctional compound. body. A method for producing a laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8, or 9.
Step (1) of forming the fluororesin layer (A),
A step (2) of subjecting at least one surface of the fluororesin layer (A) to a discharge treatment, and
A step (3) of forming a rubber layer (B) on the surface of the fluororesin layer (A) subjected to the discharge treatment;
The manufacturing method of the laminated body which consists of.