JP2018015935A - Laminate, method for producing laminate and fluororubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which uses a fluororesin excellent in low fuel permeability, and can strongly bond a fluororesin layer and a fluororubber layer even when using a VdF/HFP/TFE copolymer having a coefficient of absorptivity at 1720 cmof more than 0.35 which was measured after having contacted triethylamine as a fluororubber.SOLUTION: A laminate has a fluororubber layer (A) and a fluororesin layer (B) laminated on the fluororubber layer (A), where the fluororubber layer (A) is a layer formed from a fluororubber composition, the fluororubber composition contains a fluororubber (a1), hydrotalcite and a basic polyfunctional compound which contains at least two nitrogen atoms in the molecule and has a distance between nitrogen atoms and nitrogen atoms in the molecule of 5.70 Å or more, the fluororubber (a1) is a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer, and the fluororesin layer (B) is composed of a fluororesin (b1) having a coefficient of fuel permeability of 2.0 g mm/m/day or less.SELECTED DRAWING: None

Description

The present invention relates to a laminate, a method for producing the laminate, and a fluororubber composition.

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

Moreover, since fluororubber is excellent in various properties such as heat resistance, oil resistance, and aging resistance, it has been proposed to use it as a rubber other than the above-described barrier layer.

However, when a fluororesin, particularly a fluororesin excellent in low fuel permeability, is used as the barrier layer, it is difficult to bond the fluororubber of the outer and inner layers as the counterpart material. Therefore, Patent Document 1 aims to provide a laminate capable of firmly bonding a fluororesin layer and a fluororubber layer even when a fluororesin excellent in low fuel permeability is used. , A laminate comprising a fluororubber layer (A) and a fluororesin layer (B) laminated on the fluororubber layer (A), wherein the fluororubber layer (A) is made of a fluororubber composition. The fluororubber composition is a layer to be formed, the fluororubber composition contains at least two nitrogen atoms in the molecule, and the distance between the nitrogen atom and the nitrogen atom in the molecule is 5.70Å. The fluororubber (a1) contains a basic polyfunctional compound as described above, and the extinction coefficient at 1720 cm ⁻¹ measured after contacting with triethylamine is 0.35 or less, and the fluororesin layer (B) is The fuel permeability coefficient The laminate is characterized by being composed of a fluororesin (b1) that is 2.0 g · mm / m ² / day or less.

International Publication No. 2015/072491

However, in the method described in Patent Document 1, the fluororubber that can be used is limited to those having an extinction coefficient of 1720 cm ⁻¹ measured after contacting with triethylamine of 0.35 or less. Fluorine rubber layer even when a vinylidene fluoride (VdF) / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) copolymer having a fuel barrier property and fuel resistance of more than 0.35 is used A laminate in which the fluororesin layer and the fluororesin layer are firmly bonded is desired.

In view of such a current situation, the present invention uses a fluororesin excellent in low fuel permeability and has a VdF / HFP with an extinction coefficient of 1720 cm ⁻¹ measured after contacting with triethylamine as a fluororubber of more than 0.35. It is an object to provide a laminate capable of firmly bonding a fluororesin layer and a fluororubber layer even when a / TFE copolymer is used.

The present inventors have intensively studied a laminate in which a fluororesin excellent in low fuel permeability and a VdF / HFP / TFE copolymer are firmly bonded, and a fluororubber composition for forming a fluororubber layer. Focused on. When the VdF / HFP / TFE copolymer is used as a fluororubber, the fluororubber composition contains a hydrotalcite and a specific basic polyfunctional compound to thereby form a fluororesin layer and a fluororubber layer. The present invention has been completed by finding that it is possible to bond firmly.

That is, the present invention is a laminate comprising a fluororubber layer (A) and a fluororesin layer (B) laminated on the fluororubber layer (A), wherein the fluororubber layer (A) A layer formed from a fluororubber composition, wherein the fluororubber composition contains at least two nitrogen atoms in the fluororubber (a1), hydrotalcite, and molecules; It contains a basic polyfunctional compound having a distance between nitrogen atoms of 5.70 mm or more, the fluororubber (a1) is a VdF / HFP / TFE copolymer, and the fluororesin layer (B) is fuel permeable. A laminate comprising a fluororesin (b1) having a coefficient of 2.0 g · mm / m ² / day or less.

The fluororesin (b1) is at least one selected from the group consisting of polychlorotrifluoroethylene, chlorotrifluoroethylene-based copolymers, and tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymers. In the tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer, the copolymerization ratio (mole% ratio) of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride is tetrafluoroethylene / hexafluoropropylene / fluoride. It is preferable that it is vinylidene chloride = 75-95 / 0.1-10 / 0.1-19.

The fluororubber composition preferably contains a peroxide vulcanizing agent.

The basic polyfunctional ^{_{compounds, -NH 2, -NH 3 +,}} -NHCOOH, -NHCOO -, in -N = ^CR 1 ^{R 2} (wherein, ^{R 1} and ^{R 2} are independently a carbon number 0 -NR ³ R ⁴ (wherein R ³ and R ⁴ are each independently an organic group having 0 to 12 carbon atoms), and -NR ³ R ⁴ R ^5. It is preferable to have two or more functional groups (wherein R ³ , R ⁴ and R ⁵ are independently an organic group having 0 to 12 carbon atoms).

The basic polyfunctional compound is —NH ₂ , —NH ₃ ⁺ , —N═CR ¹ R ² (wherein R ¹ and R ² are independently an organic group having 0 to 12 carbon atoms). ) And -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). Is preferred.

The basic polyfunctional compound is selected from the group consisting of N, N′-dicinnamylidene-1,6-hexamethylenediamine and NH ₂ — (CH ₂ ) _n —NH ₂ (where n is 5 to 12). It is preferable that it is at least one kind.

The basic polyfunctional compound is preferably at least one selected from the group consisting of N, N′-dicinnamylidene-1,6-hexamethylenediamine and hexamethylenediamine.

In the laminate of the present invention, the adhesive strength between the fluororubber layer (A) and the fluororesin layer (B) is preferably 12 N / cm or more.

In the laminate of the present invention, the fluororubber layer (A) is preferably laminated on both sides of the fluororesin layer (B).
In the laminate of the present invention, it is also preferred that the fluororesin layer (B) is laminated on both sides of the fluororubber layer (A).
The laminate of the present invention further includes a non-fluorinated rubber layer (C1a), and is laminated in the order of a fluororubber layer (A) -a fluororesin layer (B) -a non-fluorinated rubber layer (C1a). Is also preferable.
The laminate of the present invention further includes a non-fluorine rubber layer (D1a), in the order of non-fluorine rubber layer (D1a) -fluorine rubber layer (A) -fluorine resin layer (B) -non-fluorine rubber layer (C1a). , Fluorine rubber layer (A) -fluorine resin layer (B) -non-fluorine rubber layer (D1a) -non-fluorine rubber layer (C1a), or fluorine rubber layer (A) -fluorine resin layer (B) -non The layers are preferably laminated in the order of fluororubber layer (C1a) -non-fluorine rubber layer (D1a).

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

The present invention also includes a fluororubber (a1), a hydrotalcite, and a basic compound containing at least two nitrogen atoms in the molecule and having a distance between nitrogen atoms and nitrogen atoms in the molecule of 5.70 cm or more. A step of obtaining a fluororubber composition by mixing with a polyfunctional compound, a step of laminating an unvulcanized fluororubber layer obtained by molding the fluororubber composition, and a fluororesin layer, A step of vulcanizing the vulcanized fluororubber layer and the fluororesin layer, wherein the fluororubber (a1) is a vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer, and the fluororesin layer is It is also a method for producing a laminate, which is composed of a fluororesin (b1) having a fuel permeability coefficient of 2.0 g · mm / m ² / day or less.

The present invention further includes a fluororubber (a1), a hydrotalcite, a basic compound containing at least two nitrogen atoms in the molecule, and the distance between the nitrogen atoms and the nitrogen atoms in the molecule is 5.70 cm or more. The fluororubber (a1) is also a fluororubber composition which is a vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer.

Since the laminate of the present invention has the above-described configuration, the extinction coefficient of 1720 cm ⁻¹ measured after using a fluororesin excellent in low fuel permeability and contacting with triethylamine as fluororubber exceeds 0.35. Even when the VdF / HFP / TFE copolymer is used, the fluororesin layer and the fluororubber layer can be firmly bonded.

The laminate of the present invention comprises a fluororubber layer (A) and a fluororesin layer (B) laminated on the fluororubber layer (A).
Hereinafter, each component will be described.

(A) Fluoro rubber layer The fluoro rubber layer (A) is a layer formed from a fluoro rubber composition.
The fluororubber layer (A) is usually obtained by molding a fluororubber composition to obtain an unvulcanized fluororubber layer and then vulcanizing it.
The fluororubber composition contains fluororubber (a1), hydrotalcite, and at least two nitrogen atoms in the molecule, and the distance between the nitrogen atom and the nitrogen atom in the molecule is 5.70 cm or more. It contains a basic polyfunctional compound, and the fluororubber (a1) is a VdF / HFP / TFE copolymer. The fluororubber composition is also one aspect of the present invention.
Even when the fluororesin (b1) excellent in low fuel permeability is used by using the specific fluororubber, hydrotalcite and the basic polyfunctional compound in combination, the fluororubber layer (A) And the fluororesin layer (B) can be firmly bonded.
For example, when a VdF / TFE / perfluoro (methyl vinyl ether) copolymer is used as the fluororubber, even when hydrotalcite and the above polyfunctional compound are included, as shown in Comparative Example 3 described later. The fluororubber layer and the fluororesin layer do not adhere firmly. The present inventors have found that the combined use of hydrotalcite and the above polyfunctional compound acts specifically on the VdF / HFP / TFE copolymer, and strengthens the fluororubber layer (A) and the fluororesin layer (B). As a result, the present invention has been completed.

The fluororubber (a1) is a VdF / HFP / TFE copolymer. The fluororubber (a1) is an unvulcanized fluororubber, and usually comprises an amorphous polymer having a fluorine atom bonded to a carbon atom constituting the main chain and having rubber elasticity. . The fluororubber (a1) usually does not have a clear melting point.

The VdF / HFP / TFE copolymer includes polymerized units based on VdF (VdF units), polymerized units based on HFP (HFP units), and polymerized units based on TFE (TFE units).
Since the adhesion between the fluororubber layer (A) and the fluororesin layer (B), fuel barrier properties, and fuel resistance are excellent, VdF / HFP / TFE is 30 to 85/5 to 50/5 to 40 ( Molar ratio), VdF / HFP / TFE is preferably 35-80 / 8-45 / 8-35 (molar ratio), and VdF / HFP / TFE is 40-80 / 10-40. It is more preferable that the molar ratio is / 10 to 30 (molar ratio), and VdF / HFP / TFE is most preferably 45 to 75/10 to 35/10 to 25 (molar ratio).

The VdF / HFP / TFE copolymer may contain a polymer unit based on another monomer. Examples of the other monomer include perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (Propyl vinyl ether), chlorotrifluoroethylene, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, ethylene, propylene, alkyl vinyl ether, and at least one selected from the group consisting of monomers that give vulcanization sites And monomers. The monomer that gives the vulcanization site will be described later.
The content of polymerized units based on other monomers is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 3 mol% or less, and further preferably 2 mol% or less. Most preferably. The fluororubber (a1) is also preferably a copolymer composed of only VdF units, HFP units, and TFE units.

The fluororubber (a1) is preferably a VdF / HFP / TFE copolymer having an extinction coefficient of 1720 cm ⁻¹ measured after contact with triethylamine of more than 0.35. A VdF / HFP / TFE copolymer having an extinction coefficient exceeding 0.35 is excellent in fuel barrier properties and fuel resistance. On the other hand, when the extinction coefficient of fluororubber exceeds 0.35, the fluororubber layer (A) and the fluororesin layer (B) are difficult to adhere. However, even when the hydrotalcite and a specific basic polyfunctional compound are used in combination, even when the extinction coefficient of the fluororubber (a1) which is a VdF / HFP / TFE copolymer exceeds 0.35. The fluororesin layer and the fluororubber layer can be firmly bonded. The extinction coefficient is more preferably 0.36 or more, still more preferably 0.37 or more, and most preferably 0.38 or more. The upper limit of the extinction coefficient is, for example, 0.43, preferably 0.41, and more preferably 0.40.
The extinction coefficient of 1720 cm ⁻¹ measured after contacting with the triethylamine is measured by the following method.
First, 0.56 g of polymer (fluororubber) was completely dissolved in 10 cc of acetone, tetrahydrofuran (THF) or methyl ethyl ketone (MEK), then 4.9 g of triethylamine was added, the solution was transferred to a petri dish, and acetone, THF or MEK Then, the petri dish is heated for 3 hours in a constant temperature bath at 70 ° C., and the heated polymer film is analyzed by infrared spectroscopy (IR) in an air atmosphere.
Then, in the analysis result of the IR, the peak intensity of 1720 cm ^-1 when a 1.0 an extinction coefficient of 3000～3030Cm ^-1 and extinction coefficient of 1720 cm ^-1.

The fluorine rubber (a1) preferably has a fluorine content of 60% by mass or more, more preferably 62% by mass or more, and still more preferably 64% by mass or more. The upper limit of the fluorine content is not particularly limited, but is preferably 74% by mass or less, more preferably 73% by mass or less, and further preferably 72% by mass or less. The fluorine content can be determined by calculation from the composition of the fluororubber (a1).

The fluororubber (a1) preferably has a Mooney viscosity (ML _{(1 + 10)} (121 ° C.)) of 2 to 200, more preferably 5 to 100.
The Mooney viscosity is a value measured according to ASTM-D1646 and JISK6300.

The fluororubber (a1) preferably has a number average molecular weight (Mn) of 5,000 to 500,000, more preferably 10,000 to 500,000.
The number average molecular weight is a value measured by the GPC method.

The fluororubber (a1) is preferably a fluororubber capable of peroxide vulcanization because the fluororubber layer (A) and the fluororesin layer (B) adhere more firmly. The peroxide vulcanizable fluoro rubber is not particularly limited as long as it is a fluoro rubber having a peroxide vulcanizable site (vulcanized site).
As a method for introducing the vulcanization site, a method of copolymerizing a monomer that gives a vulcanization site during the polymerization of fluororubber, a vulcanization site such as a bromine compound or an iodine compound as a polymerization initiator or a chain transfer agent is used. The method of using the compound to give is mentioned.

Examples of the monomer that gives the vulcanization site include a general formula:
CX ¹ ₂ = CX ¹ -Rf ³ CHR ¹ X ²
(Wherein X ¹ is a hydrogen atom, a fluorine atom or —CH ₃ , and Rf ³ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group, R ¹ Is a hydrogen atom or —CH ₃ , X ² is an iodine atom or a bromine atom.) An iodine or bromine-containing monomer represented by the general formula:
CX ¹ ₂ = CX ¹ -Rf ³ X ²
(In the formula, X ¹ is a hydrogen atom, a fluorine atom or —CH ₃ , and Rf ³ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group, X ² Is an iodine or bromine-containing monomer represented by the general formula: CH ₂ ═CH (CF ₂ ) _n I (n is an integer of 2 to 8). ) Iodine-containing monomer represented by the general formula:
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 3
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ³ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, or a bromine atom). Body, general formula:
_{CH 2 = CFCF 2 O (CF} (CF 3) CF 2 O) m (CF (CF 3)) n -X 4
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁴ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ₂ OH). Monomer, general formula:
^{CR 2 R 3 = CR 4 -Z} -CR 5 = CR 6 R 7
(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z is linear or branched. An alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, an alkylene or oxyalkylene group having 1 to 10 carbon atoms that is at least partially fluorinated Or
_{- (Q) p -CF 2 O-} (CF 2 CF 2 O) m (CF 2 O) n -CF 2 - (Q) p -
(Wherein Q is an alkylene or oxyalkylene group, p is 0 or 1, m / n is 0.2 to 5), and the molecular weight is 500 to 10,000 (per) fluoro. It is a polyoxyalkylene group. ) And the like.

General formula above:
^{CR 2 R 3 = CR 4 -Z} -CR 5 = CR 6 R 7
In The compound represented by, for _{example, CH 2 = CH- (CF 2} ) 2 -CH = CH 2, CH 2 = CH- (CF 2) 4 -CH = CH 2, CH 2 = CH- (CF 2 ₆ -CH = CH ₂ , the following formula:
^{_{CH 2 = CH-Z 1 -CH}} = CH 2
(In the formula, Z ¹ is a fluoropolyoxyalkylene group represented by —CH ₂ OCH ₂ —CF ₂ O— (CF ₂ CF ₂ O) _m1 (CF ₂ O) _n1 —CF ₂ —CH ₂ OCH ₂ —). And m1 / n1 is 0.5 and the molecular weight is 2000.).

Monomers that give vulcanization sites include CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH, CF ₂ = CFOCF ₂ CF ( _{CF 3) OCF 2 CF 2 CH} 2 I, CF 2 = CFOCF 2 CF 2 CH 2 I, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CN, CH 2 = CFCF 2 OCF (CF 3 ) CF ₂ OCF (CF ₃ ) COOH, CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH, and CH ₂ ═CHCF ₂ CF ₂ I, CH ₂ ═CH (CF ₂ ) it is one of the preferred embodiments is at least one selected from the group consisting of ₂ CH = CH _2.
CF ₂ = CFOCF ₂ CF ₂ CH ₂ I is a monomer that gives the vulcanization site, and it can improve the vulcanization density and improve compression set in vulcanization using peroxide. This is particularly preferable because it can be performed.

Monomers that provide vulcanization sites may also include, for example, the general formula:
CX ¹ ₂ = CX ¹ -Rf ³ CHR ¹ X ²
(In the formula, X ¹ is a hydrogen atom, fluorine atom or —CH ₃ , Rf ³ is a fluoroalkylene group, perfluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group, and R ¹ is a hydrogen atom. Or —CH ₃ and X ² are an iodine atom or a bromine atom)
Iodine or bromine-containing monomer represented by the general formula:
CX ¹ ₂ = CX ¹ -Rf ³ X ²
(Wherein X ¹ is a hydrogen atom, a fluorine atom or —CH ₃ , Rf ³ is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and X ² is an iodine atom. Or a bromine atom)
An iodine- or bromine-containing monomer represented by (preferably an iodine-containing monomer represented by CH ₂ ═CH (CF ₂ ) _n I (n is an integer of 2 to 8)), a general formula:
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 5
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁵ is an iodine atom or a bromine atom)
And a monomer represented by the general formula:
_{CH 2 = CFCF 2 O (CF} (CF 3) CF 2 O) m (CF (CF 3)) n -X 5
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁵ is an iodine atom or a bromine atom)
It is also a preferred embodiment that the monomer is at least one monomer selected from the group consisting of: By using such an iodine or bromine-containing monomer as the other monomer, a VdF / HFP / TFE copolymer can be produced.

In the fluororubber (a1), the monomer giving the vulcanization site may be 0 mol% or more of the total monomer units, preferably 0.01 to 10 mol%, 0.01 to 2 More preferably, it is mol%. The fluororubber (a1) may be a copolymer composed only of polymerized units based on VdF, polymerized units based on HFP, polymerized units based on TFE, and polymerized units based on a monomer that provides a vulcanization site. .

Vulcanization sites can also be introduced by using bromine compounds or iodine compounds as chain transfer agents.
The VdF / HFP / TFE copolymer preferably uses a bromine compound or an iodine compound as a chain transfer agent. Examples of the polymerization method using a bromine compound or iodine compound include a method in which emulsion polymerization is carried out in an aqueous medium under pressure in the presence of a bromine compound or iodine compound in a substantially oxygen-free state. (Iodine transfer polymerization method). Representative examples of bromine compounds or iodine compounds to be used include, for example, the general formula:
R ² I _x Br _y
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ² is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro A hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms which may contain an oxygen atom). By using a bromine compound or iodine compound, iodine or bromine is introduced into the polymer and functions as a vulcanization point.

Examples of the iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5- Diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane , diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- _{propane, CF 2 Br 2, BrCF 2} CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF 2 CF _{2 Br,} BrCF ₂ CFBrO F _3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo -4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo and diiodomonobromo substituents of benzene, and (2-iodoethyl) and (2-bromoethyl) ) Substituents, etc., and these compounds may be used alone or in combination with each other.
Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are used from the viewpoint of polymerization reactivity, vulcanization reactivity, and availability. Is preferred.

The fluororubber (a1) may have at least one of an iodine atom and a bromine atom, and the total content thereof is preferably 0.001 to 10% by weight. The total content of iodine atoms and bromine atoms is more preferably 0.01 to 5% by weight, still more preferably 0.1 to 5% by weight.
The iodine content was measured by mixing 5 mg of Na ₂ SO ₃ with 12 mg of sample (fluororubber), and mixing ₃₀ mg of Na ₂ CO ₃ and K ₂ CO ₃ in a 1: 1 ratio (weight ratio) with 20 ml of pure water. Using the dissolved absorbent, it is burned in oxygen in a quartz combustion flask and allowed to stand for 30 minutes, and then measured using a Shimadzu 20A ion chromatograph. As the calibration curve, a KI standard solution, one containing 0.5 ppm of iodine ions or one containing 1.0 ppm can be used.

The bonding position of the iodine atom and bromine atom may be the end of the main chain or the side chain of the fluororubber (a1), and may be both. In such a fluororubber (a1), the iodine end or bromine end is a vulcanization point (vulcanization site), and a vulcanized fluororubber having a high vulcanization density can be obtained. It becomes possible to carry out easily.

The fluororubber composition may contain other rubber as a rubber component, but 90% by mass or more of the rubber component is preferably fluororubber (a1), and 95% by mass or more of the rubber component is fluororubber (a1). It is preferable that the rubber component is composed only of the fluororubber (a1).

Although it does not specifically limit as said hydrotalcite, General formula (1):
[(M ₁ ²⁺ ) _1-x M ³⁺ _x (OH) ₂ ] ^{x +} [A ⁿ⁻ _{x / n} · mH ₂ O] ^x− (1)
_(Wherein, ^{M 1 2+} is a divalent metal ^{ion, M 3+} is a trivalent metal ^{ion, A n-is} an n-valent anion, x is a number satisfying 0 <x <0.5 And m is a number satisfying 0 ≦ m.)
Or a compound represented by
The following general formula (2) obtained by firing the compound represented by the general formula (1):
(M ₁ ²⁺ ) _1-x M ³⁺ _x O _p (2)
(In the formula, M ₁ ²⁺ is a divalent metal ion, M ³⁺ is a trivalent metal ion, x is a number satisfying 0 <x <0.5, and p is a number satisfying 0 <p. .)
(Hydrotalcite fired product)
It is more preferable from the viewpoint of adhesiveness and availability. In the present specification, the hydrotalcite may be a natural product or a synthetic product.

M ₁ ²⁺ represents a divalent metal ion, and examples thereof include Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ or Zn ²⁺ . Among these, Mg ²⁺ and / or Zn ²⁺ are preferable because they are easily available.

M ³⁺ represents a trivalent metal ion, and examples thereof include Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ^{3+, and} In ³⁺ . Among these, Al ³⁺ is preferable because it is easily available.

A ^n- represents a n-valent anion, for ^{example, OH -, F -, Cl} -, Br -, NO 3 -, CO 3 2-, SO 4 2-, Fe (CN) 6 3-, CH 3 COO ⁻ , oxalate ion or salicinate ion can be mentioned. Among these, CO ₃ ²⁻ is preferable because it is easily available.

x is a number satisfying 0 <x <0.5, preferably a number satisfying 0.2 ≦ x ≦ 0.4, and more preferably a number satisfying 0.2 ≦ x ≦ 0.33. preferable. It is preferable that x is in this range since hydrotalcite generation is stable.

m is a number that satisfies 0 ≦ m, and preferably a number that satisfies 0 ≦ m ≦ 1.

Hydrotalcite is a non-stoichiometric compound represented by the general formula (1) or the general formula (2). Among these, Mg ₆ Al ₂ (OH) ₁₆ CO _3. 4H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .mH ₂ O (0 ≦ m), Mg _4.3 Al ₂ (OH) _12.6 CO ₃ .mH ₂ O (0 <m), Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3.5H ₂ O, Mg ₅ Al ₂ (OH) ₁₄ CO ₃ .4H ₂ O, Mg ₃ Al ₂ (OH) ₁₀ CO ₃ .1.7H ₂ O, Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ .mH ₂ O (0 ≦ m), Mg _0.7 Al _0.3 O _p (0 <p) and the like are preferable.

Specific examples of the hydrotalcite include DHT-4A, DHT-4A-2, DHT-4C, and KW-2200 manufactured by Kyowa Chemical Industry Co., Ltd.

In the fluororubber composition, the content of hydrotalcite is preferably 0.3 to 6.0 parts by weight, and 0.4 to 5.0 parts by weight with respect to 100 parts by weight of the fluororubber (a1). More preferably, it is 0.5 to 4.0 parts by weight. If the amount of hydrotalcite added is less than 0.3 parts by weight, the adhesion may be insufficient, and if it exceeds 6.0 parts by weight, the adhesion may be insufficient.

The basic polyfunctional compound contains at least two nitrogen atoms in the molecule, and the distance between the nitrogen atom and the nitrogen atom in the molecule is 5.70 cm or more. By using the basic polyfunctional compound and hydrotalcite in combination, the fluororesin (b1) constituting the fluororesin layer (B) is excellent in low fuel permeability, and the fluororubber (a) is fuel barrier property and Even if it is a VdF / HFP / TFE copolymer excellent in fuel resistance, the fluororubber layer (A) and the fluororesin layer (B) can be firmly bonded.

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 above functional groups is preferred, and —NH ₂ , —NH ₃ ⁺ , —N═CR ¹ R ² (wherein R ¹ and R ² are the above and same), ^and, in NR ³ R 4 ^{R 5 (wherein,} R 3, ^{R 4} and ^{R 5} are the same) and the That more preferably at least one selected from the _group, -NH 2, _-NH ^{3 +} and -N = ^CR 1 ^{R 2} (wherein, ^{R 1} and ^{R 2} are as defined above) is selected from the group consisting of At least one of the above is more preferred.
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 ethylene diamine, propane diamine, putrescine, cadaverine, hexamethylene diamine, heptane diamine, octane diamine, nonane diamine, decane diamine, undecane diamine, dodecane diamine, phenylene diamine, N, N′-dicine namilidene 1,6-hexamethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexamethylenediamine, N, N′-dimethyl-1,6-hexamethylenediamine, 6-aminohexylcarbamic acid Etc.

The basic polyfunctional compound contains at least two nitrogen atoms in the molecule, and the interatomic distance between nitrogen and nitrogen is 5.70 cm or more. The interatomic distance between nitrogen and nitrogen is more preferably 6.30 mm or more, further preferably 7.60 mm or more, and particularly preferably 8.60 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 *).

The basic polyfunctional compound is N, N′-dicinnamylidene-1,6-hexamethylenediamine and NH ₂ — (CH ₂ ) in terms of adhesion between the fluororubber layer (A) and the fluororesin layer (B). _{2) n} -NH ₂ (wherein, n is preferably at least one selected from the group consisting of 5 to 12), hexamethylene diamine, and, n, N'-dicinnamylidene-1,6-hexa More preferably, it is at least one compound selected from the group consisting of methylenediamine.

Since the fluororubber layer (A) and the fluororesin layer (B) are more firmly bonded, in the fluororubber composition, the content of the basic polyfunctional compound is 100 parts by mass of the fluororubber (a1). On the other hand, it is preferably 0.5 parts by mass or more, more preferably 0.6 parts by mass or more, still more preferably 0.8 parts by mass or more, and 1.0 parts by mass or more. Is particularly preferable, and is most preferably 1.5 parts by mass or more.
The content of the basic polyfunctional compound is preferably 10 parts by mass or less, particularly preferably 6.0 parts by mass or less, and 5.0 parts by mass or less from the viewpoint of vulcanization inhibition and cost. More preferably, it is most preferably 4.0 parts by mass or less.

The fluororubber composition further comprises 1,8-diazabicyclo (5.4.0) undecene-7 salt (DBU salt), 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt). ), 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), 1,5-diazabicyclo (4.3.0) -nonene-5 (DBN), and melamine. Or at least one compound (a2).
By using the compound (a2), the fluororubber layer (A) and the fluororesin layer (B) can be firmly bonded even when the content of the basic polyfunctional compound is small.

DBU salt and DBN salt include DBU or DBN carbonate, long chain aliphatic carboxylate, aromatic carboxylate, orthophthalate, p-toluenesulfonate, phenol salt, phenol resin salt, naphthoate Octylate, oleate, formate, phenol novolac resin salt, hydrochloride, etc., and naphthoate, orthophthalate, phenol and formate of DBU or DBN, and 8-benzyl- Preferred is at least one compound selected from the group consisting of 1,8-diazabicyclo (5.4.0) -7-undecenium chloride (DBU-B), and 1,8-diazabicyclo (5.4.0). ) Undecene-7, 1,5-diazabicyclo (4.3.0) nonene-5, 8-benzyl-1,8-diazabicyclo (5.4.0) -7 Undecenium chloride, 1,8-diazabicyclo (5.4.0) undecene-7 naphthoate, 1,8-diazabicyclo (5.4.0) undecene-7 phenol salt, 1,8-diazabicyclo ( 5.4.0) at least one compound selected from the group consisting of undecene-7 orthophthalate and 1,8-diazabicyclo (5.4.0) undecene-7 formate. More preferred.
Particularly preferably, it consists of formate of 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride and 1,8-diazabicyclo (5.4.0) undecene-7. It is at least one selected from the group.
As the compound (a2), two or more of the above compounds may be used in combination.

It is preferable that a compound (a2) is 0.5 mass part or more with respect to 100 mass parts of fluororubbers (a1). More preferably, it is 1.0 part by mass or more. If the amount of the compound (a2) is too small, the effect obtained by adding the compound (a2) may not be sufficiently exhibited.
The compound (a2) is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3.5 parts by mass or less with respect to 100 parts by mass of the fluororubber (a1). preferable.

The fluororubber composition preferably further contains a vulcanizing agent. As the vulcanizing agent, a peroxide vulcanizing agent or the like can be selected according to the purpose.

The peroxide vulcanizing agent is not particularly limited, and examples thereof include organic peroxides. 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 It can be exemplified butylperoxy isopropyl carbonate. Of these, dialkyl compounds are more 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 (a1).

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 fluororubber composition is a metal oxide, metal hydroxide, alkali metal as an acid acceptor or as a compounding agent for improving the adhesion between the fluororubber layer (A) and the fluororesin layer (B). And at least one compound selected from the group consisting of weak acid salts of alkaline earth metals.
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, zinc oxide, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, Calcium oxide (quick lime), calcium hydroxide (slaked lime), calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate, calcium phosphite, tin oxide, basic tin phosphite and the like can be mentioned.

When using an organic peroxide as a vulcanizing agent, the content of the metal oxide, metal hydroxide, alkali metal weak acid salt, alkaline earth metal weak acid salt is preferably 5 parts by mass or less, More preferably, it is 3 parts by mass or less, and from the viewpoint of acid resistance, it is even more preferable not to include it.

The above-mentioned fluororubber composition is an ordinary additive blended in the fluororubber composition as necessary, for example, filler, processing aid, plasticizer, colorant, stabilizer, adhesion aid, acid acceptor. Various additives such as mold release agents, conductivity imparting agents, thermal conductivity imparting agents, surface non-adhesives, flexibility imparting agents, heat resistance improvers, flame retardants, etc. You may contain 1 or more types of a different usual vulcanizing agent and a vulcanization accelerator.

Examples of the filler include carbon black. The content of carbon black is preferably 5 to 40 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the fluororubber (a1). The use of carbon black has the advantage of improving mechanical properties, heat resistance, and the like.

The fluororubber composition comprises a fluororubber (a1), a hydrotalcite, a basic polyfunctional compound, and, if necessary, the compound (a2), a vulcanizing agent, a vulcanizing aid, and a co-addition. Other additives such as a vulcanizing agent, a vulcanization accelerator, and a filler 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.

(B) Fluororesin layer The fluororesin layer (B) is composed of a fluororesin (b1), and the fluororesin (b1) has a fuel permeability coefficient of 2.0 g · mm / m ² / day or less. It is.
When the fuel permeability coefficient is 2.0 g · mm / m ² / day or less, excellent low fuel permeability 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 resin pellet was put into a 120 mm diameter mold, 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. The sheet was processed to a diameter of 45 mm and a thickness of 120 μm.

The fluororesin (b1) is obtained from a polychlorotrifluoroethylene (PCTFE), a CTFE copolymer, and a TFE / HFP / VdF copolymer because a laminate having excellent low fuel permeability can be obtained. It is preferably at least one selected from the group consisting of From the viewpoint of flexibility, it is more preferably at least one selected from the group consisting of a CTFE copolymer and a TFE / HFP / VdF copolymer. From the viewpoint of low fuel permeability, the CTFE copolymer More preferred is coalescence.

Since the TFE / HFP / VdF copolymer has excellent fuel low permeability when the VdF content is low, the copolymerization ratio (mole% ratio) of TFE, HFP and VdF is TFE / HFP / VdF = 75 to 95 / It is preferably 0.1 to 10 / 0.1 to 19, more preferably 77 to 95/1 to 8/1 to 17 (molar ratio), and 77 to 95/2 to 8/2 to 15 5 (molar ratio) is more preferable, and 79 to 90/5 to 5/5 to 15 (molar ratio) is most preferable. Further, the TFE / HFP / VdF copolymer may contain 0 to 20 mol% of other monomers. Other monomers include perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), chlorotrifluoroethylene, 2-chloropentafluoropropene, perfluorinated vinyl ethers (eg CF ₃ OCF ₂ CF ₂ CF ₂ perfluoroalkoxy vinyl ethers such as OCF = CF ₂₎ fluorine-containing monomers such as, perfluoroalkyl vinyl ether, perfluoro-1,3, - butadiene, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, ethylene, propylene, And at least one monomer selected from the group consisting of alkyl vinyl ethers, and examples thereof include perfluoro (methyl vinyl ether) and perfluoro (ethyl vinyl). Ether), it is preferred perfluoro (propyl vinyl ether).

The PCTFE is a chlorotrifluoroethylene homopolymer.

Examples of the CTFE copolymer include copolymer units derived from CTFE (CTFE units), TFE, HFP, PAVE, VdF, vinyl fluoride, hexafluoroisobutene,
^{_{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.
The CTFE copolymer is more preferably a perhalopolymer.

It is more preferable that the CTFE-based copolymer includes a CTFE unit and a copolymer unit derived from at least one monomer selected from the group consisting of TFE, HFP, and PAVE. More preferably, it consists only of copolymerized units of Further, from the viewpoint of low fuel permeability, it is preferable not to include a monomer having a CH bond such as ethylene, vinylidene fluoride, and vinyl fluoride.
Perhalopolymers that do not contain a monomer having a CH bond are usually difficult to adhere to fluororubber, but according to the configuration of the present invention, even if the fluororesin layer (B) is a layer made of perhalopolymer, The adhesion between the fluororesin layer (B) and the fluororubber layer (A) 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 monomer (α) unit derived from a CTFE unit, a TFE unit and a monomer (α) copolymerizable therewith are particularly preferred.

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

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) Alternatively, a vinyl monomer represented by 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), CF ₂ = CF—O—Rf ² An alkyl perfluorovinyl ether derivative represented by the formula (wherein Rf ² is a C 1-5 perfluoroalkyl group) is exemplified.
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 with respect to 15 to 90 mol% of CTFE units, and more preferably 20 to 90 mol of CTFE units. %, And TFE units are 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 CTFE unit and a TFE unit of 90 to 99.9 mol%, and a monomer (α) unit 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 (b1) is at least one selected from the group consisting of PCTFE, CTFE / TFE / PAVE copolymer and TFE / HFP / VdF copolymer from the viewpoint of low fuel permeability and adhesiveness. Is more preferable, at least one selected from the group consisting of a CTFE / TFE / PAVE copolymer and a TFE / HFP / VdF copolymer is more preferable, and a CTFE / TFE / PAVE copolymer is particularly preferable.
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.

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

In the fluororesin (b1), 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 (b1) has moderate heat resistance and good adhesion at a relatively low temperature, an amide group, a carbamoyl group, a hydroxyl group, a 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 (b1) can be obtained by a conventionally known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization or bulk polymerization. In the polymerization, each condition such as temperature and pressure, the polymerization initiator and other additives can be appropriately set according to the composition and amount of the fluororesin (b1).

Although melting | fusing point of a fluororesin (b1) is not specifically limited, It is preferable that it is 160-270 degreeC. The melting point of the fluororesin (b1) is determined as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a DSC device (Seiko).

Further, the molecular weight of the fluororesin (b1) is preferably in a range where the obtained 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 350 ° 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 (b1) is a 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 (B) may contain one of these fluororesins (b1), or may contain two or more.

In addition, when the fluororesin (b1) is a perhalopolymer, chemical resistance and low fuel permeability are more excellent. A perhalopolymer is a polymer in which halogen atoms are bonded to all the carbon atoms constituting the main chain of the polymer.

The fluororesin layer (B) is 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 fine layered minerals with high aspect ratio such as mica are used. It may be added.

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

The conductive single powder or conductive single fiber is not particularly limited, and 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 Japanese Patent Laid-Open No. 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.

In one preferred embodiment of the laminate of the present invention, the hydrotalcite is Mg _4.3 Al ₂ (OH) _12.6 CO ₃ · mH ₂ O (0 <m), and the basic Is at least one selected from the group consisting of N, N′-dicinnamylidene-1,6-hexamethylenediamine and hexamethylenediamine, and the fluororubber (a1) is VdF / HFP / TFE. It is a copolymer and the said fluororesin layer (B) is comprised from the fluororesin (b1) which is a CTFE / TFE / PAVE copolymer.

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

Although the thickness of the said fluororesin layer (B) 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 (B) is, for example, 1000 μm.

In the laminate of the present invention, the adhesive strength between the fluororubber layer (A) and the fluororesin layer (B) is preferably 12 N / cm or more. When the adhesive strength is 12 N / cm or more, there is an advantage that displacement does not easily occur when the hose is vulcanized in a specific shape, and peeling does not occur when an impact is applied.
The laminated body of this invention can make adhesive strength into the said range by having the said structure. The adhesive strength is more preferably 14 N / cm or more, and further preferably 15 N / cm or more.
The above adhesive strength is obtained by cutting the laminate into strips of 10 mm width × 40 mm length × 3 sets, creating a sample piece, and using this autograph (AGS-J 5kN, manufactured by Shimadzu Corporation) for this test piece. A value obtained by performing a peel test at a tensile speed of 50 mm / min at 25 ° C. and observing the peel mode in accordance with the method described in JIS-K-6256 (Adhesion test method for vulcanized rubber). It is.

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

For the vulcanization treatment, conventionally known vulcanization methods and conditions for fluororubber compositions can be employed. For example, a method of vulcanizing an unvulcanized laminate for a long time, a heat treatment as a pretreatment is performed on the unvulcanized laminate in a relatively short time (vulcanization is also occurring), and then vulcanization is performed over a long time. There is a method of performing sulfuration. Among these, 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 fluororubber layer (A) and the fluororesin layer ( Adhesion with B) can be easily obtained, and since the fluororubber layer (A) has already been vulcanized in the pretreatment and the shape is stabilized, there are various methods for holding the laminate in subsequent vulcanization. It is preferable that it can be selected.

The conditions for the vulcanization treatment are not particularly limited and can be performed under normal conditions, but at 140 to 180 ° 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 170 ° C. for 5 to 60 minutes. The vulcanization treatment may be performed separately for primary vulcanization and secondary vulcanization.

The present invention also includes a fluororubber (a1), a hydrotalcite, and a basic compound containing at least two nitrogen atoms in the molecule and having a distance between nitrogen atoms and nitrogen atoms in the molecule of 5.70 cm or more. A process for obtaining a fluororubber composition by mixing with a polyfunctional compound, a process for laminating an unvulcanized fluororubber layer obtained by molding a fluororubber composition, and a fluororesin layer, a laminated unvulcanized A step of vulcanizing the fluororubber layer and the fluororesin layer, wherein the fluororubber (a1) is a VdF / HFP / TFE copolymer, and the fluororesin layer has a fuel permeability coefficient of 2.0 g · It is also the manufacturing method of the laminated body characterized by being comprised from the fluororesin (b1) which is below mm / m < ² > / day.
By the production method of the present invention, the above-described laminate of the present invention can be produced.
In the production method of the present invention, the conditions for the vulcanization treatment are the same as those described above.

The step of obtaining the fluororubber composition by mixing the fluororubber (a1), hydrotalcite and the basic polyfunctional compound includes, for example, fluororubber (a1), hydrotalcite and basic polyfunctional compound. Are kneaded using a generally 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 addition to the fluororubber (a1), the hydrotalcite and the basic polyfunctional compound, the above-mentioned mixing is carried out as necessary in addition to the compound (a2), a vulcanizing agent, a vulcanizing aid, a co-vulcanizing agent, It may be mixed with other additives such as a sulfur accelerator and a filler.
The temperature of the said mixing is 20-200 degreeC, for example. The mixing time is, for example, 2 to 80 minutes.

The unvulcanized fluororubber layer and the fluororesin layer are laminated by separately molding the unvulcanized fluororubber layer and the fluororesin layer by means such as pressure bonding. And a method in which a fluororesin layer is formed by applying a fluororesin to an unvulcanized fluororubber layer.

In the method in which the unvulcanized fluororubber layer and the fluororesin layer are separately molded and then laminated by means such as pressure bonding, a fluororesin molding method and a fluororubber composition molding method can be employed.

Molding of the unvulcanized fluororubber layer can be done in various shapes such as sheet, tube, etc. by heat compression molding method, transfer molding method, extrusion molding method, injection molding method, calendar molding method, coating method, etc. It can be set as this molded object.

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

As a method of simultaneously molding and laminating an unvulcanized fluororubber layer and a fluororesin layer, a fluororubber composition that forms an unvulcanized fluororubber layer and a fluororesin (b1) that forms a fluororesin layer are used. Examples thereof include a method of laminating simultaneously with molding by a method such as a multilayer compression molding method, a multilayer transfer molding method, a multilayer extrusion molding method, a multilayer injection molding method, and a doubling method. In this method, since an unvulcanized fluororubber layer and a fluororesin layer, which are unvulcanized molded bodies, can be laminated at the same time, a step of closely adhering the unvulcanized fluororubber layer and the fluororesin layer is not particularly necessary. It is suitable for obtaining strong adhesion in the subsequent vulcanization step. When the adhesion is insufficient, an adhesion process such as lapping may be performed.

(Laminated structure of laminated body)
The laminate of the present invention may have a two-layer structure of a fluororubber layer (A) and a fluororesin layer (B), or a fluororubber layer (A) laminated on both sides of the fluororesin layer (B). Alternatively, the fluororesin layer (B) may be laminated on both sides of the fluororubber layer (A).
For example, a three-layer structure of fluororubber layer (A) -fluororesin layer (B) -fluororubber layer (A) or fluororesin layer (B) -fluororubber layer (A) -fluororesin layer (B) may be used.
Furthermore, it may be a multilayer structure of three or more layers in which polymer layers (C) other than the fluororubber layer (A) and the fluororesin layer (B) are bonded, or the fluororubber layer (A) and the fluororesin layer ( 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 B) is bonded. 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 a fluororubber layer (A) -a fluororesin layer (B) -a fluororubber layer (A).

The polymer layers (C) and (D) may be rubber layers (C1) or (D1) other than the fluororubber layer (A). Examples of the rubber layer (C1) or (D1) include a non-fluorinated rubber layer (C1a) or (D1a) formed from a non-fluorinated rubber. Non-fluorinated rubber is preferred because of its good cold resistance and excellent cost. The non-fluorine rubber layer (C1a) and the non-fluorine rubber layer (D1a) may be formed from the same non-fluorine rubber, or may be formed from different non-fluorine rubbers.
The laminate of the present invention may be laminated in the order of fluororubber layer (A) -fluororesin layer (B) -non-fluororubber layer (C1a).
Further, it includes a non-fluorine rubber layer (D1a), in the order of non-fluorine rubber layer (D1a) -fluorine rubber layer (A) -fluorine resin layer (B) -non-fluorine rubber layer (C1a), fluorine rubber layer ( A) -fluorine resin layer (B) -non-fluorine rubber layer (D1a) -non-fluorine rubber layer (C1a), or fluorine rubber layer (A) -fluorine resin layer (B) -non-fluorine rubber layer (C1a) ) -Non-fluorinated rubber layer (D1a) in this order.

Specific examples of the non-fluorine rubber include, for example, acrylonitrile-butadiene rubber (NBR) or a hydride thereof (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), and natural rubber (NR). Diene rubber such as isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, acrylic rubber, chlorinated polyethylene (CPE), acrylonitrile-butadiene rubber and vinyl chloride Examples thereof include polyblend (PVC-NBR) and ethylene propylene diene rubber (EPDM). Moreover, the rubber which mixed these non-fluororubbers and fluororubbers in arbitrary ratios is mention | raise | lifted.
The non-fluorine rubber is preferably a diene rubber or epichlorohydrin rubber from the viewpoint of good heat resistance, oil resistance, weather resistance and extrusion moldability. More preferred is NBR, HNBR or epichlorohydrin rubber. The rubber layer (C1) is preferably made of NBR, HNBR or epichlorohydrin rubber.
The rubber layer (D1) is composed of acrylonitrile-butadiene rubber, epichlorohydrin rubber, chlorinated polyethylene (CPE), acrylonitrile-butadiene rubber and vinyl chloride polyblend (PVC-NBR), ethylene propylene diene, in terms of weather resistance and cost. It is preferably made of rubber (EPDM), acrylic rubber, or a mixture thereof. 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).

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

(1) A two-layer structure basic structure of a fluororubber layer (A) -a fluororesin layer (B). Conventionally, in order to laminate the fluororesin layer (B) and the fluororubber layer (A), an interlayer (fluororubber) Layer-fluorine resin layer) is insufficiently bonded, which makes the process complicated, such as surface treatment on the resin side, separate application of adhesive between layers, and winding and fixing a tape-like film. However, vulcanization adhesion occurs by vulcanization without assembling such complicated processes, and chemically strong adhesion is obtained.

(2) Three-layer structure of rubber layer-fluororesin layer (B) -rubber layer Three-layer structure of fluororubber layer (A) -fluorine resin layer (B) -fluororubber layer (A), and fluororubber layer ( There is a three-layer structure of A) -fluorine resin layer (B) -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, for example, in joints such as fuel pipes. The inner and outer rubber layers may be the same type or different types.
In the case of a three-layer structure of fluororubber layer (A) -fluororesin layer (B) -rubber layer (C1), the rubber layer (C1) is composed of acrylonitrile butadiene rubber, hydrogenated acrylonitrile butadiene rubber, epichlorohydrin rubber, or acrylonitrile butadiene. A layer made of a mixture of rubber and acrylic rubber is preferred.
The fuel pipe has a three-layer structure of a fluororubber layer (A) -a fluororesin layer (B) -a rubber layer (C1), a fluororubber layer is provided as the rubber layer (C1), and the rubber layer (C1) is provided as a pipe. By using the inner layer, chemical resistance and low fuel permeability are improved.

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

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

(5) Four-layer structure or more In addition to the three-layer structure of (2) to (4), an optional fluororubber layer (A) or rubber layer (C1) and fluororesin layer (B) are laminated depending on the purpose. May be. Moreover, a layer such as a metal foil may be provided, or an adhesive layer may be interposed other than the interlayer between the fluororubber layer (A) and the fluororesin layer (B).

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

In addition, what is necessary is just to select the thickness of each layer, a shape, etc. suitably according to a use purpose, a use form, etc.
In addition, for the purpose of improving pressure resistance, a reinforcing layer such as a reinforcing yarn may be provided as appropriate.

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, automotive engine main body, 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, in oil, chemical, heat, steam, or weather resistant packings, O-rings, hoses, other sealing materials, diaphragms, valves, chemicals, etc. For similar packing, O-rings, sealing materials, diaphragms, valves, hoses, rolls, tubes, chemical coatings, linings in plants, hoses or gaskets in chemical processing, 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 The same in OA equipment and general industrial parts Suitable for packing, 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 PTFE diaphragm has a problem that it is worn out or torn during use because of its poor sliding property, but by using the laminate of the present invention, this problem can be improved and suitable. Can be used for

In addition, in food rubber seal material applications, there is a problem that 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. 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.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

In Examples and Comparative Examples, each physical property value was measured by the following method.

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

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

(3) MFR (Melt Flow Rate)
Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the weight (g) of the polymer flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 297 ° C. and 5 kg per unit time (10 minutes) 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 sheet in the wetted part, and the thickness of the sheet.

(5) Mooney viscosity Measured according to ASTM-D1646 and JISK6300.

(6) Absorption coefficient of 1720 cm ⁻¹ measured after contact with triethylamine First, 0.56 g of polymer (fluororubber) was completely dissolved in 10 cc of acetone, tetrahydrofuran (THF) or methyl ethyl ketone (MEK), and then triethylamine. 4.9 g was added, the solution was transferred to a petri dish, acetone, THF or MEK was vaporized, and then the whole petri dish was heated in a thermostat at 70 ° C. for 3 hours, and the IR of the polymer after heating was analyzed.
Then, in the analysis result of the IR, the peak intensity of 1720 cm ^-1 when a 1.0 an extinction coefficient of 3000～3030Cm ^-1 was extinction coefficient of 1720 cm ^-1.

The materials used in Examples and Comparative Examples are shown below.
・ Fluorine resin (1)
CTFE / PPVE / TFE copolymer, CTFE / PPVE / TFE = 21.3 / 2.4 / 76.3 (mol%), melting point: 245 ° C., MFR: 30 g / 10 min (297 ° C., 5 kg), fuel Transmission coefficient: 0.4 g · mm / m ² / day
・ Fluoro rubber (1)
VdF / HFP / TFE copolymer, VdF / HFP / TFE = 70/18/12 (mol%), fluorine content: 67% Mooney viscosity (ML _{(1 + 10)} (121 ° C.) = 26, contacted with triethylamine Later measured extinction coefficient of 1720 cm ⁻¹ : 0.39
・ Fluoro rubber (2)
VdF / TFE / PMVE copolymer, VdF / TFE / PMVE = 72/8/20, fluorine content: 66%, Mooney viscosity (ML _{(1 + 10)} (100 ° C.) = 67, measured after contact with triethylamine Absorption coefficient of 1720 cm ⁻¹ : 0.38

Basic polyfunctional compound: N, N′-dicinnamylidene-1,6-hexamethylenediamine, distance between N in molecule: 8.80 mm,
Carbon black: MT carbon, N990
Vulcanizing agent: Perhexa 25B, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane vulcanizing aid: triallyl isocyanurate (TAIC)
Hydrotalcite: DHT-4A, DHT-4A-2, DHT-4C, KW-2200 from Kyowa Chemical Industry Co., Ltd.

Comparative Examples 1-3 and Examples 1-9
(Manufacture of fluororubber composition)
The materials shown in Table 1 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. Each numerical value in Table 1 represents “part by mass”. In addition, with respect to the rubber composition for vulcanization, a maximum torque value (MH) and a minimum torque value (ML) at 160 ° C. using a curast meter type II (model number: JSR curast meter, manufactured by JSR). Was measured, and an induction time (T10) and an optimum vulcanization time (T90) were determined. The measurement results are shown in the table. 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 , Measured according to JIS K 6300-2.
(Manufacture of laminates)
A sheet of vulcanized rubber composition having a thickness of about 2 mm and a fluororesin sheet are overlaid, inserted into a mold in which the resulting sheet has a thickness of 2 mm, and pressed at 160 ° C. for 45 minutes to laminate the sheet. Got the body.

(Adhesion evaluation)
The obtained laminate was cut into strips of 10 mm width × 40 mm length × 3 sets to prepare sample pieces. 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 rate of / min, and the peeling mode was observed and evaluated according to the following criteria.
A layer formed from a sheet of a rubber composition for vulcanization or a fluororesin sheet was destroyed at the interface of the laminate and could not be peeled off at the interface.
In Table 1, the adhesive strength when the adhesion evaluation is “◯” is the strength at which the material having the lower strength of the resin layer or the rubber layer is broken.
X: The laminate was peelable at the interface, and the peel strength at the interface was 10 N / cm or less.

The laminate of the present invention has a strong structure of a fluororubber layer (A) using a VdF / HFP / TFE copolymer excellent in fuel barrier properties and fuel resistance and a fluororesin layer (B) having a low fuel permeability coefficient. Since it can adhere | attach, it can utilize especially suitably as a fuel hose, a fuel tube, an oil seal, an O-ring, packing, etc.

Claims (15)

A laminate comprising a fluororubber layer (A) and a fluororesin layer (B) laminated on the fluororubber layer (A),
The fluororubber layer (A) is a layer formed from a fluororubber composition,
The fluororubber composition contains at least two nitrogen atoms in the fluororubber (a1), hydrotalcite, and the molecule, and the distance between the nitrogen atom and the nitrogen atom in the molecule is 5.70 or more. Containing basic polyfunctional compounds,
The fluororubber (a1) is a vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer,
The said fluororesin layer (B) is comprised from the fluororesin (b1) whose fuel permeability coefficient is 2.0 g * mm / m < ² > / day or less, The laminated body characterized by the above-mentioned. The fluororesin (b1) is at least one selected from the group consisting of polychlorotrifluoroethylene, chlorotrifluoroethylene copolymers, and tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymers. ,
The tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer has a tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymerization ratio (mole% ratio) of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride. The laminate according to claim 1, wherein = 75 to 95 / 0.1 to 10 / 0.1 to 19. The laminate according to claim 1 or 2, wherein the fluororubber composition contains a peroxide vulcanizing agent. Basic polyfunctional ^{_{compounds, -NH 2, -NH 3 +,}} -NHCOOH, -NHCOO -, -N = CR 1 R 2 ( wherein, ^{R 1} and ^{R 2} are independently 0 carbon atoms -NR ³ R ⁴ (wherein R ³ and R ⁴ are each independently an organic group having 0 to 12 carbon atoms), and -NR ³ R ⁴ R ⁵ ( ^4. The laminate according to claim 1, 2 or 3, wherein R ³ , R ⁴ and R ⁵ are each independently two or more functional groups which are organic groups having 0 to 12 carbon atoms. The basic polyfunctional compound is —NH ₂ , —NH ₃ ⁺ , —N═CR ¹ R ² (wherein R ¹ and R ² are independently an organic group having 0 to 12 carbon atoms) And -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). The laminate according to 1, 2, 3 or 4. The basic polyfunctional compound is selected from the group consisting of N, N′-dicinnamylidene-1,6-hexamethylenediamine and NH ₂ — (CH ₂ ) _n —NH ₂ (where n is 5 to 12). The laminated body according to claim 1, 2, 3, 4 or 5, which is at least one kind. The basic polyfunctional compound is at least one selected from the group consisting of N, N'-dicinnamylidene-1,6-hexamethylenediamine and hexamethylenediamine. 6. The laminate according to 6. The laminate according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the adhesive strength between the fluororubber layer (A) and the fluororesin layer (B) is 12 N / cm or more. The laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the fluororubber layer (A) is laminated on both sides of the fluororesin layer (B). The laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the fluororesin layer (B) is laminated on both sides of the fluororubber layer (A). Furthermore, a non-fluorine rubber layer (C1a) is included,
The laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the fluororubber layer (A), the fluororesin layer (B) and the non-fluororubber layer (C1a) are laminated in this order. Furthermore, a non-fluorine rubber layer (D1a) is included,
Non-fluorine rubber layer (D1a) -Fluorine rubber layer (A) -Fluorine resin layer (B) -Non-fluorine rubber layer (C1a) in this order, Fluorine rubber layer (A) -Fluorine resin layer (B) -Non-fluorine rubber layer Laminated in the order of (D1a) -non-fluorine rubber layer (C1a) or in the order of fluororubber layer (A) -fluorine resin layer (B) -non-fluorine rubber layer (C1a) -non-fluorine rubber layer (D1a) The laminated body according to claim 11. The fluororubber layer (A) and the fluororesin layer (B) are vulcanized and bonded to each other, wherein the fluororubber layer (A) and the fluororesin layer (B) are vulcanized and bonded. 12. The laminate according to 12. A fluorine-containing rubber (a1), a hydrotalcite, a basic polyfunctional compound containing at least two nitrogen atoms in the molecule and having a distance between nitrogen atoms and nitrogen atoms in the molecule of 5.70 cm or more; A process of obtaining a fluororubber composition by mixing
A step of laminating an unvulcanized fluororubber layer obtained by molding a fluororubber composition and a fluororesin layer; and
Vulcanizing the laminated unvulcanized fluororubber layer and fluororesin layer,
The fluororubber (a1) is a vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer,
The said fluororesin layer is comprised from the fluororesin (b1) whose fuel permeability coefficient is 2.0 g * mm / m < ² > / day or less, The manufacturing method of the laminated body characterized by the above-mentioned. A fluorine-containing rubber (a1), a hydrotalcite, a basic polyfunctional compound containing at least two nitrogen atoms in the molecule and having a distance between nitrogen atoms and nitrogen atoms in the molecule of 5.70 cm or more; Including
The fluororubber composition, wherein the fluororubber (a1) is a vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer.