JP2010234777A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate having flexibility, high mechanical strength, and high fuel barrier properties which cannot be attained by a conventional laminate structure. <P>SOLUTION: In the laminate, a fluororesin layer (A), a fluororesin non-containing resin layer (B) and an elastomer layer (C) are bonded in this order. The invention also relates to the laminate in which the elastomer layer (C), the fluororesin non-containing resin layer (B), the fluororesin layer (A), the fluororesin non-containing resin layer (B), and the elastomer layer (C) are bonded in this order. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a laminate.

As fuel transfer piping materials such as gasoline, use of resin laminates is becoming mainstream from the viewpoint of processability, rust prevention, weight reduction, economy, etc., but with stricter fuel transpiration regulations, There is a growing demand for improved fuel permeation resistance.

As the fuel-permeable resin laminate, at least one selected from the group consisting of polybutylene terephthalate [PBT], polybutylene naphthalate [PBN], polyethylene terephthalate [PET] and polyethylene naphthalate [PEN] is mainly used. A resin tube (for example, refer to Patent Document 1) formed by laminating a layer containing a component and a layer containing PBT as a main component, a resin layer containing polyphenylene sulfide [PPS] as a main component, and PBT as a main component. A resin tube including a resin layer is disclosed (for example, see Patent Document 2). However, there is a problem that heat resistance, chemical resistance, solvent resistance and the like are insufficient.

Fluororesin is a resin with excellent heat resistance, chemical resistance, and solvent resistance. However, since fluororesin is inferior in mechanical strength and dimensional stability and expensive, it is desirable to laminate it with other organic materials. .

A laminate of a fluororesin and another organic material and having fuel permeability resistance includes a layer made of polyamide 12 [PA12], tetrafluoroethylene [TFE] / perfluoro (methyl vinyl ether) [PMVE] A layer composed of a polymer and a three-layer laminate composed of a layer obtained by imparting conductivity to an ethylene / TFE copolymer [ETFE], or a layer composed of PA12, a TFE / hexafluoropropylene [HFP] copolymer There has been proposed a three-layer laminate composed of a layer formed of a combined [FEP] and a layer formed by imparting conductivity to ETFE (for example, see Patent Document 3).

For the purpose of high fuel permeation resistance, a laminate of a fluororesin layer and a fluorine-free organic material layer, wherein the fluororesin layer includes a chlorotrifluoroethylene [CTFE] copolymer layer, a TFE / It is disclosed that lamination with a perfluoro (alkyl vinyl ether) [PAVE] copolymer or a TFE / HFP / PAVE copolymer is possible due to interlayer adhesion due to compatibility without introducing an adhesive functional group. (For example, refer to Patent Document 4).

In order to impart flexibility to the laminated resin molded body, a three-layer laminate comprising a thermoplastic elastomer layer, a polyamide resin layer, and a fluorine-containing ethylenic polymer layer is disclosed (for example, see Patent Document 5). . In addition, in a resin laminate in which a polyamide resin layer is an outer layer and a fluorine-containing ethylenic polymer layer is an inner layer, it is described that a rubber layer may be provided on the outermost layer (see, for example, Patent Document 6). .)

A laminate having a layer composed of a fluorine-containing ethylenic polymer, a layer composed of a chlorotrifluoroethylene copolymer, and a layer composed of a fluorine-free organic material is disclosed for the purpose of high fuel permeation resistance and crack resistance. (For example, refer to Patent Document 7).

JP 2002-213655 A JP 2002-267054 A International Publication No. 01/18142 Pamphlet International Publication No. 2004/098880 Pamphlet International Publication No. 2004/110756 Pamphlet International Publication No. 01/58686 Pamphlet International Publication No. 2006/135091 Pamphlet

An object of the present invention is to provide a laminate having flexibility, high mechanical strength, and high fuel barrier properties that cannot be realized by a conventional laminate structure.

The present invention relates to a laminate in which a fluororesin layer (A), a fluorine-free resin layer (B), and an elastomer layer (C) are bonded in this order.

The present invention also applies to a laminate in which an elastomer layer (C), a fluorine-free resin layer (B), a fluorine resin layer (A), a fluorine-free resin layer (B) and an elastomer layer (C) are bonded in this order. Related.

The fluororesin layer (A) is preferably made of a fluorinated polymer having at least one adhesive functional group selected from the group consisting of a carbonyl group, a hydroxyl group and an amino group.

The fluororesin layer (A) is composed of an ethylene / tetrafluoroethylene copolymer, a chlorotrifluoroethylene / tetrafluoroethylene copolymer, a tetrafluoroethylene / hexafluoropropylene copolymer, and a vinylidene fluoride / tetrafluoroethylene / It is preferably made of at least one fluorine-containing polymer selected from the group consisting of hexafluoropropylene copolymers.

The fluororesin layer (A) is composed of an ethylene / tetrafluoroethylene copolymer, a chlorotrifluoroethylene / tetrafluoroethylene copolymer, a tetrafluoroethylene / hexafluoropropylene copolymer, and a vinylidene fluoride / tetrafluoroethylene / 50.01 to 99.99 parts by mass of at least one fluoropolymer selected from the group consisting of hexafluoropropylene copolymer, and selected from the group consisting of ethylene / vinyl alcohol copolymer, polyamide and polyolefin It is preferable to comprise 0.01 to 49.99 parts by mass of at least one fluorine-free polymer.

The fluorine-free resin layer (B) is preferably made of at least one fluorine-free polymer selected from the group consisting of an ethylene / vinyl alcohol copolymer, polyamide and polyolefin.

The elastomer layer (C) is made of acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber. And an elastomer composition containing at least one elastomer selected from the group consisting of acrylic rubbers.

The laminate of the present invention may be a laminate in which the layer (D) is bonded to the outside of the layer (A).

The laminate of the present invention may be a laminate in which the layer (D) is bonded to the outside of the layer (C).

The present invention also relates to a molded article formed from the laminate.

The present invention also relates to a fuel tube formed from the laminate.

The present invention also relates to a method for manufacturing the laminate.

The laminate of the present invention is firmly bonded between the layers, and has flexibility, high mechanical strength, and high fuel barrier properties.

It is a schematic diagram which shows the structure of a laminated body of 3 layers. It is a schematic diagram which shows the structure of a laminated body of 5 layers.

The present invention is a laminate of at least three layers in which a fluororesin layer (A), a non-fluorine-containing resin layer (B), and an elastomer layer (C) are bonded in this order.

A three-layer laminate is shown in FIG. Each layer is laminated in the order of the fluororesin layer 1, the fluorine-free resin layer 2, and the elastomer layer 3. The fluorine-free resin layer 2 is firmly bonded to the fluorine resin layer 1 and the elastomer layer 3. The fluororesin layer 1 imparts high fuel barrier properties to the laminate, and the elastomer layer 3 imparts flexibility to the laminate. A layer (D) may be laminated on the outer side of the fluororesin layer 1 or the elastomer layer 3.

In the present invention, the elastomer layer (C), the fluorine-free resin layer (B), the fluorine resin layer (A), the fluorine-free resin layer (B) and the elastomer layer (C) are adhered in this order at least 5 layers It is also a laminated body.

The elastomers constituting the two elastomer layers (C) may be the same type of elastomer or different types of elastomers. Similarly, the fluorine-free resin constituting the two fluorine-free resin layers (B) may be the same type of fluorine-free resin or different types of fluorine-free resin.

A five-layer laminate is shown in FIG. This laminate is composed of a fluororesin layer 1, a non-fluorine-containing resin layer 2, and an elastomer layer 3. The elastomer layer 3, the non-fluorine-containing resin layer 2, the fluororesin layer 1, the non-fluorine-containing resin layer 2, and the elastomer layer 3 Are stacked in this order. The fluorine resin layer 1, the fluorine-free resin layer 2, and the elastomer layer 3 are firmly bonded to each other. The fluororesin layer 1 imparts high fuel barrier properties to the laminate, and the elastomer layer 3 imparts flexibility to the laminate. A layer (D) may be laminated on the outer side of the elastomer layer 3.

Since the laminate of the present invention has the characteristic layer structure as described above, the layers are firmly bonded, and has flexibility, high mechanical strength, and high fuel barrier properties.

The fluororesin layer (A) is preferably made of a fluorinated polymer having at least one adhesive functional group selected from the group consisting of a carbonyl group, a hydroxyl group and an amino group.

The “carbonyl group” is a carbon divalent group composed of a carbon-oxygen double bond, and is represented by a group represented by —C (═O) —. The carbonyl group is not particularly limited, and examples thereof include a carbonate group, a halogenoformyl group, a formyl group, a carboxyl group, an ester bond [—C (═O) O—], and 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-], Carbamoyl group [NH ₂ —C (═O) —], carbamoyloxy group [NH ₂ —C (═O) O—], ureido group [NH ₂ —C (═O) —NH—], oxamoyl group [NH ₂ -C (= O) -C (= O)-] and the like which are part of the chemical structure.

The amide group has the following general formula

(Wherein R ² represents a hydrogen atom or an organic group, and R ³ represents an organic group).

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

The above-mentioned adhesive functional group is easy to introduce, and the coating film to be obtained has moderate heat resistance and good adhesion at a relatively low temperature, so that it has an amide group, a carbamoyl group, a hydroxyl group. A carboxyl group and a carbonate group are preferable, and a carbonate group is more preferable.

The carbonate group is a group having a bond generally represented by [—OC (═O) O—], and a —OC (═O) O—R group (wherein R represents an organic group). It is represented by Examples of the organic group represented by R in the above formula include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms having an ether bond, and preferably an alkyl group having 1 to 8 carbon atoms. And an alkyl group having 2 to 4 carbon atoms having an ether bond. Examples of the carbonate group include —OC (═O) O—CH ₃ , —OC (═O) O—C ₃ H ₇ , —OC (═O) O—C ₈ H ₁₇ , —OC (═O ) such as _{OCH 2 CH 2 CH 2 OCH 2} CH 3 and the like.

When the fluoropolymer has an adhesive functional group, it may be composed of a polymer having the adhesive functional group at either the main chain terminal or the side chain, or the main chain. You may consist of a polymer which has both a terminal and a side chain. In the case of having an adhesive functional group at the end of the main chain, it may be present at both ends of the main chain or only at one of the ends. The fluorine-containing polymer has the above-mentioned adhesive functional group at the end of the main chain and / or the side chain, or in place of it, the adhesive functional functional group has a structure commonly referred to as a bond such as an ether bond The adhesive functional group may be present in the main chain. The above fluoropolymer is composed of a polymer having an adhesive functional group at the end of the main chain because it does not significantly reduce mechanical properties and chemical resistance, or is advantageous in terms of productivity and cost. Is preferable.

When the fluoropolymer is composed of a polymer having an adhesive functional group in the side chain, it can be obtained by copolymerizing an adhesive functional functional group-containing monomer. In the present specification, the “adhesive functional functional group-containing monomer” means a polymerizable monomer having an adhesive functional functional group.

As the adhesive functional group-containing monomer, the following general formula CX ¹² ₂ = CY ^1- (R ¹ ) _n -Z ¹
(In the formula, Z ¹ represents a functional group having a hydroxyl group, a carbonyl group or an amino group, X ¹ and Y ¹ are the same or different and each represents a hydrogen atom or a fluorine atom, and R ¹ represents a hydrogen atom, An alkylene group having 1 to 40 carbon atoms, an oxyalkylene group having 1 to 40 carbon atoms, an alkylene group having 2 to 40 carbon atoms having an ether bond, or ether, which may be partially or completely substituted with fluorine atoms Represents an oxyalkylene group having 2 to 40 carbon atoms having a bond, and n represents 0 or 1.). In the present specification, the “functional group having a hydroxyl group, a carbonyl group or an amino group” may be a hydroxyl group, a carbonyl group, an amino group, It means that it may be a functional group having any of these adhesive functional functional groups.

As the adhesive functional group-containing monomer, for example, in the case of a functional group having a carbonyl group, perfluoroacrylic acid fluoride, 1-fluoroacrylic acid fluoride, acrylic acid fluoride, 1-trifluoromethacrylic acid fluoride, Monomers having fluorine such as perfluorobutenoic acid; and monomers having no fluorine such as acrylic acid chloride and vinylene carbonate.

Examples of the adhesive functional group-containing monomer further include unsaturated carboxylic acids. In the present specification, the unsaturated carboxylic acid as the adhesive functional group-containing monomer is a carbon-carbon unsaturated bond (hereinafter referred to as “copolymerizable carbon-carbon unsaturated bond” that enables copolymerization). And at least one carbonyloxy group [—C (═O) —O—] in one molecule is preferable.

Examples of the unsaturated carboxylic acids include aliphatic unsaturated carboxylic acids and acid anhydrides thereof. The aliphatic unsaturated carboxylic acid may be an aliphatic unsaturated monocarboxylic acid or an aliphatic unsaturated polycarboxylic acid having two or more carboxyl groups.

As said aliphatic unsaturated monocarboxylic acid, C3-C20 aliphatic monocarboxylic acid etc., such as propionic acid, acrylic acid, methacrylic acid, crotonic acid, those acid anhydrides, etc. are mentioned, for example. Examples of the aliphatic unsaturated polycarboxylic acid include maleic acid, fumaric acid, mesaconic acid, citraconic acid [CAC], itaconic acid, aconitic acid, itaconic anhydride [IAH] and citraconic anhydride [CAH].

Examples of the adhesive functional group at the end of the main chain (hereinafter sometimes referred to as “unstable end group”) include carbonate group, —COF, —COOH, —COOCH ₃ , —CONH ₂ , —CH _2. OH etc. are mentioned. The unstable terminal group is usually formed at the end of the main chain by addition of a chain transfer agent or a polymerization initiator used during polymerization, and is derived from the structure of the chain transfer agent or polymerization initiator. is there.

The fluoropolymer is a polymer having an adhesive functional group at the end of the main chain, and when the adhesive functional functional group is a polymer having a carbonate group, polymerization of peroxycarbonate is started. It can obtain by the method of superposing | polymerizing using as an agent. Use of the above method is preferable from the viewpoints of very easy introduction and control of introduction of carbonate groups, quality, such as economical efficiency, heat resistance, and chemical resistance.

As the peroxycarbonate, the following formula

(In the formula, R ⁴ and R ⁵ are the same or different, and are linear or branched monovalent saturated hydrocarbon groups having 1 to 15 carbon atoms, or those having 1 to 15 carbon atoms having an alkoxyl group at the terminal. Represents a linear or branched monovalent saturated hydrocarbon group, and R ⁶ represents a linear or branched divalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a carbon number having an alkoxyl group at the terminal. 1 to 15 linear or branched divalent saturated hydrocarbon groups) are preferred.

Among these, as the peroxycarbonate, diisopropyl peroxycarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di- 2-ethylhexyl peroxydicarbonate and the like are preferable.

When the fluorine-containing polymer is a polymer having an adhesive functional group at the end of the main chain, and the adhesive functional functional group is a polymer other than a carbonate group, As in the case of introduction, by using a peroxide such as peroxycarbonate, peroxydicarbonate, peroxyester, and peroxyalcohol as a polymerization initiator, an adhesive functional group derived from the peroxide is obtained. Can be introduced. In addition, “derived from peroxide” is directly introduced from the functional group contained in the peroxide or indirectly by converting the functional group introduced directly from the functional group contained in the peroxide. It means being introduced.

The amount of the polymerization initiator used, such as peroxycarbonate and peroxyester, varies depending on the type and composition of the target fluoropolymer, the molecular weight, the polymerization conditions, the type of initiator used, etc., but the resulting polymer It is preferable that it is 0.05-5 mass parts with respect to 100 mass parts, and an especially preferable minimum is 0.1 mass part, and an especially preferable upper limit is 1 mass part.

The number of the adhesive functional functional groups can be appropriately selected depending on the type, shape, purpose of application, application, required adhesive force, adhesion method with other layers, and the like.

The number of unstable terminal groups is preferably 3 to 800 per 1 × 10 ⁶ main chain carbon atoms when melt molding at a molding temperature of less than 320 ° C. Adhesiveness may fall that it is less than 3 per 1 × 10 ⁶ main chain carbon atoms. A more preferred lower limit is 50, a still more preferred lower limit is 80, and a particularly preferred lower limit is 120. When melt molding is performed at a molding temperature of less than 320 ° C., the number of unstable terminal groups can be set to 500, for example, from the viewpoint of productivity if the number is within the above range.

The number of the unstable end groups is determined by compressing the fluoropolymer powder at a molding temperature 50 ° C. higher than the melting point at a molding pressure of 5 MPa, and a film sheet having a thickness of 0.25 to 0.30 mm. Infrared absorption spectrum analysis using an infrared spectrophotometer [IR], the type is determined by comparison with the infrared absorption spectrum of a known film, and the number calculated from the difference spectrum by the following equation.
Number of terminal groups (per 1 × 10 ⁶ carbon atoms) = (l × K) / t
l: Absorbance K: Correction coefficient t: Film thickness (mm)
Table 1 shows the correction coefficients of the target end groups.

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

The fluororesin layer (A) is made of a fluoropolymer. The fluorine-containing polymer is not particularly limited, but preferably has a repeating unit derived from at least one fluorine-containing ethylenic monomer. Examples of the fluorine-containing ethylenic monomer include tetrafluoroethylene [TFE], formula (1):
CF ₂ = CF-R _f ¹ (1)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
One or more perfluoroolefins such as perfluoroethylenically unsaturated compounds represented by: chlorotrifluoroethylene [CTFE], trifluoroethylene, hexafluoroisobutene, vinylidene fluoride [VdF], vinyl fluoride Formula (2):
^{_{CH 2 = CX 2 (CF 2}} ) n X 3 (2)
(In the formula, X ² represents a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 1 to 10.)
And the like.

The fluorinated polymer may have a repeating unit derived from a monomer copolymerizable with the fluorinated ethylenic monomer. Examples of such a monomer include the fluoroolefin and perfluoroolefin. Non-fluorine ethylenic monomers other than can be mentioned. Examples of the non-fluorine ethylenic monomer include ethylene, propylene, and alkyl vinyl ethers. Here, the alkyl vinyl ether refers to an alkyl vinyl ether having an alkyl group having 1 to 5 carbon atoms.

The fluoropolymer is easy to mold, and the resulting molded product has excellent heat resistance, chemical resistance, and oil resistance.
(1) Ethylene / TFE copolymer consisting of ethylene and TFE [ETFE]
(2) TFE and formula (1):
CF ₂ = CF-R _f ¹ (1)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
A copolymer comprising one or more perfluoroethylenically unsaturated compounds represented by the formula, for example, a copolymer [PFA] comprising TFE and perfluoro (alkyl vinyl ether) [PAVE] or TFE and hexafluoropropylene Copolymer comprising [HFP] [FEP]
(3) TFE, VdF and equation (1):
CF ₂ = CF-R _f ¹ (1)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
A copolymer comprising one or more perfluoroethylenically unsaturated compounds represented by the formula: for example, TFE / VdF / HFP copolymer (4) polyvinylidene fluoride [PVDF]
(5) Copolymer comprising CTFE and TFE [CTFE / TFE copolymer]
It is preferable that it is either.

The fluoropolymer is more preferably at least one selected from the group consisting of ETFE, CTFE / TFE copolymer, PFA, FEP, and TFE / VdF / HFP copolymer, ETFE, CTFE / TFE. More preferably, it is at least one selected from the group consisting of a copolymer, FEP and TFE / VdF / HFP copolymer.

ETFE
ETFE is preferable in terms of improving mechanical properties and fuel barrier properties. The content molar ratio of the TFE unit to the ethylene unit is preferably 20:80 to 90:10, more preferably 37:63 to 85:15, and still more preferably 38:62 to 80:20.

ETFE may be a copolymer composed of TFE, ethylene, and a monomer copolymerizable with TFE and ethylene. As the copolymerizable monomer, the following formulas CH ₂ = CX ⁴ R _f ³ , CF ₂ = CFR _f ³ , CF ₂ = CFOR _f ³ , CH ₂ = C (R _f ³ ) ₂
(In the formula, X ⁴ represents a hydrogen atom or a fluorine atom, and R _f ³ represents a fluoroalkyl group that may contain an etheric oxygen atom.)
Among them, a fluorine-containing vinyl monomer represented by CF ₂ = CFR _f ³ , CF ₂ = CFOR _f ³ and CH ₂ = CX ⁴ R _f ³ is preferable, and HFP, CF ₂ = CF-OR _f ⁴ (wherein R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms), and perfluoro (alkyl vinyl ether) [PAVE] and R _f ³ have 1 carbon atom. 8 is a fluoroalkyl group _CH 2 ⁼ CX ₄ fluorine-containing vinyl monomer represented by _R ^{f 3} is more preferable.

Specific examples of the fluorine-containing vinyl monomer represented by the above formula include 1,1-dihydroperfluoropropene-1, 1,1-dihydroperfluorobutene-1, 1,1,5-trihydroperfluoropentene-1. 1,1,7-trihydroperfluoroheptene-1,1,1,2-trihydroperfluorohexene-1,1,1,2-trihydroperfluorooctene-1,2,2,3 3,4,4,5,5-octafluoropentyl vinyl ether, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), hexafluoropropene, perfluorobutene-1, 3,3,3-trifluoro-2- (trifluoromethyl) propene -1,2,3,3,4,4,5,5- heptafluoro-1-pentene _(CH 2 = CFC ₂ CF ₂ CF ₂ H), and the like.

The monomer copolymerizable with TFE and ethylene may be an aliphatic unsaturated carboxylic acid such as itaconic acid or itaconic anhydride described above.

The monomer copolymerizable with TFE and ethylene is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 5 mol%, particularly preferably from 0.2 to 4 mol%, based on the fluoropolymer. preferable.

CTFE / TFE copolymer The CTFE / TFE copolymer preferably has a CTFE / TFE unit molar ratio of CTFE: TFE = 2: 98 to 98: 2 and 5:95 to 90:10. It is more preferable. If the CTFE unit is less than 2 mol%, the low chemical liquid permeability tends to deteriorate and melt processing tends to be difficult. If it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate.

CTFE / TFE copolymer, CTFE, TFE, and may be a copolymer comprising CTFE and TFE monomer copolymerizable with _{ethylene, VdF, HFP, CF 2 =} CF-OR f 4 (Wherein R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms.) Represented by perfluoro (alkyl vinyl ether) [PAVE], CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (Wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, X ⁸ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10) And a vinyl monomer represented by CF ₂ ═CF—OCH ₂ —Rf ⁵ (wherein Rf ⁵ represents a perfluoroalkyl group having 1 to ⁵ carbon atoms). Perfluorovinyl Examples include ether derivatives, among which PAVE is preferable.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

The CTFE / TFE copolymer has a monomer unit derived from CTFE and a monomer copolymerizable with TFE in an amount of 0.1 to 10 mol%, and a total of CTFE units and TFE units of 90 to 99.99. It is preferably 9 mol%. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

FEP
FEP is particularly preferable in that it has excellent heat resistance and exhibits excellent fuel barrier properties. Although it does not specifically limit as FEP, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of HFP units, 80-97 mol% of TFE units, and 3-20 mol% of HFP units. More preferably, it is a copolymer comprising If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

FEP may be a copolymer comprising TFE, HFP, and a monomer copolymerizable with TFE and HFP, and the monomer is exemplified as a monomer copolymerizable with CTFE and TFE. Monomer may be used. As the monomer, perfluoro (alkyl vinyl ether) [PAVE] represented by CF ₂ = CF—OR _f ⁴ (wherein R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms). , CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, and X ⁸ represents a hydrogen atom, fluorine represents an atom or a chlorine atom, n represents a vinyl monomer represented by the representative.) the integer from 2 to 10, _{and, CF 2 = CF-OCH 2} -Rf 5 ( wherein, Rf ⁵ is 1 to carbon atoms 5 represents a perfluoroalkyl group, and the like. Among them, PAVE is preferable.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

FEP has 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and HFP, and 90 to 99.9 mol% of TFE units and HFP units in total. Is preferred. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

PFA
PFA is particularly preferable in that it has excellent heat resistance and exhibits excellent fuel barrier properties. Although it does not specifically limit as PFA, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of PAVE units, 80-97 mol% of TFE units, and 3-20 mol% of PAVE units. More preferably, it is a copolymer comprising If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE, and even more preferably PMVE.

PFA may be a copolymer composed of TFE, PAVE, and a monomer copolymerizable with TFE and PAVE, and the monomer is exemplified as a monomer copolymerizable with CTFE and TFE. Monomer may be used. As the monomer, HFP, CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, X ⁸ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10.), and CF ₂ = CF—OCH ₂ —Rf ⁵ (wherein , Rf ⁵ represents a perfluoroalkyl group having 1 to ⁵ carbon atoms), and the like. Among them, PAVE is preferable.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

PFA has a monomer unit derived from a monomer copolymerizable with TFE and PAVE in an amount of 0.1 to 10 mol%, and a total of TFE unit and PAVE unit is 90 to 99.9 mol%. Is preferred. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

TFE / VdF / HFP copolymer The TFE / VdF / HFP copolymer is particularly preferable in terms of expressing flexibility. Although it does not specifically limit as a TFE / VdF / HFP copolymer, It is preferable that it is a copolymer which consists of 20-85 mol% of TFE units, 10-80 mol% of VdF units, and 1-30 mol% of HFP units, More preferably, the copolymer is composed of 20 to 80 mol% of TFE units, 15 to 70 mol% of VdF units, and 3 to 20 mol% of HFP units. If the TFE unit is less than 20 mol%, the mechanical properties tend to decrease, and if it exceeds 85 mol%, the melting point becomes too high and the moldability tends to decrease.

In addition, the ratio of each monomer unit of the fluoropolymer is obtained by appropriately combining ¹⁹ F-NMR analysis, infrared spectrophotometer [IR], elemental analysis, and fluorescent X-ray analysis depending on the type of monomer. Value.

The melting point of the fluoropolymer is preferably 150 to 340 ° C, more preferably 150 to 330 ° C, and further preferably 170 to 320 ° C. When the melting point of the fluoropolymer is less than 150 ° C., the heat resistance tends to decrease. When the melting point exceeds 340 ° C., the functional group is thermally deteriorated under the melting conditions of the fluoropolymer, There is a tendency that adhesiveness cannot be fully developed. Here, the melting point is a temperature corresponding to a melting peak when the temperature is increased at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].

The melt flow rate (MFR) of the fluoropolymer is preferably 0.2 to 50 g / 10 minutes, and more preferably 1 to 25 g / 10 minutes. If the MFR is less than 0.2 g / 10 min, the fluidity tends to deteriorate and the moldability tends to decrease. Here, MFR is a value when it is carried out under conditions of 297 ° C. and 5000 g load using a melt flow rate measuring device manufactured by Toyo Seiki Seisakusho.

The fluoropolymer preferably has a fuel permeability coefficient of 20 (g · mm) / (m ² · day) or less when the fluoropolymer is used as a sheet, and 15 (g · mm) / more preferably ^(m 2 · day) or less, 10 (g · ^{mm) /} further preferably (m 2 · day) or ^{less, 5 (g · mm) /} (m 2 · day) or less It is particularly preferred. The lower limit value of the fuel permeability coefficient is not particularly limited, and the lower the value, the better. When the fuel permeation coefficient exceeds 20 (g · mm) / (m ² · day), the fuel permeation resistance is low. Therefore, in order to suppress the fuel permeation amount, it is necessary to increase the thickness of the molded product. Economically unfavorable. Note that the lower the fuel permeation coefficient, the better the fuel permeation prevention capability. On the other hand, when the fuel permeation coefficient is large, the fuel easily permeates, so it is not suitable as a molded product such as a fuel tube.

The fuel permeability coefficient is measured by a method according to the cup method in the moisture permeability test method for moisture-proof packaging materials. Here, the cup method is a moisture permeability test method defined in JIS Z 0208, and is a method for measuring the amount of water vapor that passes through a membranous substance of a unit area in a certain time. In the present invention, the fuel permeation coefficient is measured according to this cup method. As a specific method, CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) as a simulated fuel is placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL. 18 mL, and a sheet-like test piece is set in the container opening and sealed to obtain a test specimen. The test specimen is placed in a thermostatic device (60 ° C.), the weight of the test specimen is measured, and when the weight loss per unit time becomes constant, the fuel permeability is obtained by the following formula.

The fluororesin layer (A)
It consists of ethylene / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene copolymer, and vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer. At least one fluorine-containing polymer selected from the group, 50.01 to 99.99 parts by mass;
0.01 to 49.99 parts by mass of at least one fluorine-free polymer selected from the group consisting of an ethylene / vinyl alcohol copolymer, polyamide and polyolefin;
It is also preferable that it consists of.

When the layer (A) is made of a polymer alloy containing a fluorine-containing polymer and a fluorine-free polymer, compatibility with the layer (B) is improved, and the layers (A) and (B) Can be firmly bonded. A particularly suitable polymer alloy is a polymer alloy containing a chlorotrifluoroethylene / tetrafluoroethylene copolymer and polyamide.

The fluorine-free resin layer (B) is made of a fluorine-free polymer. The fluorine-free polymer is a polymer that does not contain a fluorine atom. The fluorine-free polymer is preferably a resin that can be coextruded with the material constituting the other layer.

The fluorine-free polymer is preferably a polymer having a high degree of crystallinity, more preferably a polymer having a high degree of crystallinity, a polar functional group, and a large intermolecular force.

The polar functional group is a functional group having polarity and capable of participating in adhesion between the layer (B) and the adjacent layer. The polar functional group may be the same functional group as the adhesive functional functional group described above as possessed by the fluoropolymer, but may be a different functional group.

The polar functional group is not particularly limited, and examples thereof include those described above as the adhesive functional group, cyano group, sulfide group, and the like. Among them, carbonyloxy group, cyano group, sulfide group, hydroxyl group are included. Preferably, a hydroxyl group is more preferable.

The fluorine-free resin layer (B) is composed of polyamide, polyolefin, ethylene / vinyl alcohol copolymer, polyurethane, polyester, polyaramid, polyimide, polyamideimide, polyphenylene oxide, polyacetal, polycarbonate, acrylic polymer, styrene polymer, acrylonitrile / Selected from the group consisting of butadiene / styrene copolymer [ABS], vinyl chloride polymer, cellulose polymer, polyetheretherketone polymer [PEEK], polysulfone, polyethersulfone [PES], polyetherimide and polyphenylene sulfide. At least one kind is preferable, and since the adhesiveness with the layer (A) and the layer (C) is excellent, an ethylene / vinyl alcohol copolymer, a polyamide, and a polymer are used. More preferably composed of at least one of fluorine-containing polymer is selected from the group consisting of olefins.

The polyamide is a polymer having an amide bond [—NH—C (═O) —] as a repeating unit in the molecule.
As the polyamide, so-called nylon composed of a polymer in which an amide bond in a molecule is bonded to an aliphatic structure or an alicyclic structure, or a so-called polymer composed of a polymer in which an amide bond in a molecule is bonded to an aromatic structure. Any of aramid may be sufficient.

The nylon is not particularly limited. For example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 66/12, nylon 46, nylon 6T, nylon 9T, metaxili. What consists of polymers, such as a range amine / adipic acid copolymer, is mentioned, You may use combining 2 or more types from these.
The aramid is not particularly limited, and examples thereof include polyparaphenylene terephthalamide and polymetaphenylene isophthalamide.

The polyamide may be composed of a polymer in which a structure having no amide bond as a repeating unit is block-copolymerized or graft-copolymerized in a part of the molecule. Examples of such polyamides include polyamide elastomers such as nylon 6 / polyester copolymers, nylon 6 / polyether copolymers, nylon 12 / polyester copolymers, and nylon 12 / polyether copolymers. Etc. These polyamide-based elastomers are obtained by block copolymerization of nylon oligomers and polyester oligomers via ester bonds, or by block copolymerization of nylon oligomers and polyether oligomers via ether bonds. It is obtained. Examples of the polyester oligomer include polycaprolactone and polyethylene adipate, and examples of the polyether oligomer include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the polyamide elastomer, nylon 6 / polytetramethylene glycol copolymer and nylon 12 / polytetramethylene glycol copolymer are preferable.

As the above polyamide, sufficient mechanical strength can be obtained even if the layer made of polyamide is thin. Among them, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6T, nylon 9T , Nylon 6/66, nylon 66/12, nylon 6 / polyester copolymer, nylon 6 / polyether copolymer, nylon 12 / polyester copolymer, nylon 12 / polyether copolymer, etc. Two or more of them may be used in combination.

The polyolefin is a resin having a monomer unit derived from a vinyl group-containing monomer having no fluorine atom. The vinyl group-containing monomer having no fluorine atom is not particularly limited. For example, the fluorine-free ethylenic monomer described above with respect to the fluororesin may be used. Those having a polar functional group are preferred.

Examples of the polyolefin include, but are not limited to, polyethylene, polypropylene, high-density polyolefin, and the like, and acid-modified polyolefins such as maleic anhydride-modified polyolefin and epoxy-modified polyolefin are preferable from the viewpoint of excellent adhesiveness.

The fluorine-free resin layer (B) is particularly preferably made of a polyamide having an amine value of 10 to 60 (equivalent / 10 ⁶ g). When the amine value is within the above range, even when co-extrusion is carried out at a relatively low temperature, the interlayer adhesion with other layers can be made excellent. If the amine value is too small, the interlayer adhesion may be insufficient when co-extrusion is performed at a relatively low temperature. If the amine value is too large, the resulting laminate is insufficient in mechanical strength, tends to be colored during storage, and has poor handling properties. A preferred lower limit is 15 (equivalent / 10 ⁶ g), a preferred upper limit is 50 (equivalent / 10 ⁶ g), and a more preferred upper limit is 35 (equivalent / 10 ⁶ g).

The amine value is a value obtained by dissolving 1 g of a polyamide-based resin in 50 ml of m-cresol and titrating with 1/10 N p-toluenesulfonic acid aqueous solution and using thymol blue as an indicator. Unless otherwise indicated, it means the amine value of the polyamide-based resin before lamination. Of the number of amino groups in the polyamide-based resin before lamination, a part is considered to be consumed for adhesion to other layers, but the number is very small with respect to the whole, so the above-mentioned lamination is performed. The amine value of the previous polyamide and the amine value of the laminate of the present invention are substantially the same.

The elastomer layer (C) is composed of an elastomer composition containing an elastomer. Examples of the elastomer include acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, and fluorine rubber. , Epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, silicone rubber, butyl rubber, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, α, β-unsaturated nitrile-conjugated diene copolymer Examples thereof include a combined rubber and a hydride of an α, β-unsaturated nitrile-conjugated diene copolymer rubber.

The elastomer layer (C) is made of acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber. And an elastomer composition containing at least one elastomer selected from the group consisting of acrylic rubbers.
When the laminated body of this invention has a structure of 5 layers or more as shown in FIG. 2, it is preferable that two layers (C) consist of an elastomer composition containing a mutually different kind of elastomer.

It is preferable that the said elastomer composition contains the at least 1 sort (s) of compound chosen from the group which consists of an onium salt, an amine compound, and an epoxy resin from the point of the adhesive force improvement with a layer (B).

The onium salt is not particularly limited, and examples thereof include quaternary ammonium salts, quaternary phosphonium salts, oxonium salts, sulfonium salts, cyclic amines, and monofunctional amine compounds. Among these, quaternary ammonium salts are exemplified. A quaternary phosphonium salt is preferred.

The quaternary ammonium salt is not particularly limited. For example, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5, 4,0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5 , 4,0] -7-Undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5,4,0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 , 4,0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [5, , 0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [5,4 , 0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride (hereinafter also referred to as DBU-B), 8-benzyl-1, 8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8- (3-phenylpropylene ) -1,8-diazabicyclo [5,4,0] -7-undecenium chloride, formula (3):

(In the formula, three Rs may be the same or different, and are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X ⁻ is a monovalent anion)
A compound represented by
Formula (4):

(In the formula, n is an integer of 0 to 50)
And a compound of formula (5):

Etc.

Three R in Formula (3) are the same or different, respectively, and are a hydrogen atom or a C1-C30 monovalent organic group. Although it does not specifically limit as a C1-C30 monovalent organic group, An aryl group, such as an aliphatic hydrocarbon group and a phenyl group, or a benzyl group is mention | raise | lifted. Specifically, for example, an alkyl group having 1 to 30 carbon atoms such as —CH ₃ , —C ₂ H ₅ , and —C ₃ H ₇ ; —CX ⁹ ₃ , —C ₂ X ⁹ ₅ , —CH ₂ X ^{9 _{, -CH 2 CX 9 3, -CH}} 2 C 2 X 9 5 halogen atom-containing alkyl group having 1 to 30 carbon atoms, such as ^{(X 9} is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom); a phenyl group; _benzyl; -C ₆ F _{5, 1~5} phenyl groups or benzyl group hydrogen atoms are substituted with fluorine atoms, such as _{-CH 2 C 6 F 5; -C} 6 H 5-n (CF 3) n A phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with —CF ₃ such as —CH ₂ C ₆ H _5-n (CF ₃ ) _n (n is an integer of 1 to 5). . Moreover, Formula (6):

As such, it may contain a nitrogen atom.

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

Among these, in particular, formula (7):

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

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

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

The blending amount of the onium salt is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, and 0.3 to 7.0 parts by mass with respect to 100 parts by mass of the elastomer. Further preferred. When the amount of the onium salt is less than 0.1 parts by mass, the adhesiveness with the layer (B) tends to be insufficient, and when it exceeds 10.0 parts by mass, the dispersibility in the elastomer composition deteriorates. There is a tendency that the mechanical properties of the rust layer (C) are lowered.

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

The compounding amount of the amine compound is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, and 0.3 to 7.0 parts by mass with respect to 100 parts by mass of the elastomer. Further preferred. If the compounding amount of the amine compound is less than 0.1 parts by mass, the adhesiveness with the layer (B) tends to be insufficient, and if it exceeds 10.0 parts by mass, the dispersibility in the elastomer composition deteriorates. There is a tendency that the mechanical properties of the rust layer (C) are lowered.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and polyfunctional epoxy resin. Among these, as the bisphenol A type epoxy resin, the formula (8):

And the like. Here, in Formula (8), n is preferably 0.1 to 3, more preferably 0.1 to 0.5, and still more preferably 0.1 to 0.3. If n is less than 0.1, the adhesive strength with other materials tends to decrease. On the other hand, when n exceeds 3, the viscosity increases, and uniform dispersion in the rubber tends to be difficult.

0.1-20.0 mass parts is preferable with respect to 100 mass parts of elastomers, the compounding quantity of an epoxy resin has more preferable 0.3-15.0 mass parts, and 0.5-10.0 mass parts is. Further preferred. If the blending amount of the epoxy resin is less than 0.1 parts by mass, the adhesion with the layer (B) tends to be insufficiently expressed, while the blending amount of the epoxy resin exceeds 20.0 parts by mass, There exists a tendency for the softness | flexibility of a layer (C) to fall.

The elastomer contained in the elastomer composition may be an uncrosslinked elastomer or a crosslinked elastomer, but may be an elastomer before crosslinking in terms of excellent adhesion to the layer (B). preferable. When the elastomer before cross-linking is used, high adhesion strength can be obtained by cross-linking adhesion with other layers during lamination.

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

As a compounding quantity of the crosslinking agent mix | blended in an elastomer composition, 0.2-10 mass parts is preferable with respect to 100 mass parts of elastomers, and 0.5-8 mass parts is more preferable. If the cross-linking agent is less than 0.2 parts by mass, the cross-linking density tends to be low and compression set tends to be large, and if it exceeds 10 parts by mass, the cross-linking density tends to be too high and tends to break during compression. There is.

In addition, the elastomer composition may contain additives as necessary, for example, fillers, processing aids, plasticizers, colorants, stabilizers, crosslinking aids, adhesion aids, acid acceptors, release agents, and conductivity imparting. Various additives such as additives, thermal conductivity-imparting agents, surface non-adhesives, flexibility imparting agents, heat resistance improvers, flame retardants, etc. can be blended. One or more agents may be blended.

The elastomer composition is an elastomer, an onium salt, an amine compound and / or an epoxy resin, a crosslinking agent, a crosslinking aid, a co-crosslinking agent, a crosslinking accelerator, and other compounding agents such as a filler, which are generally used. It is obtained by kneading using a kneader. As the rubber kneading apparatus, rolls, kneaders, Banbury mixers, internal mixers, twin screw extruders, and the like can be used.

In particular, when a polyol-based crosslinking agent is used as the crosslinking agent, the melting point of the crosslinking agent / crosslinking accelerator is often relatively high, and in order to disperse uniformly in the elastomer composition, the crosslinking agent / crosslinking accelerator is used. A method of kneading while being melted at a high temperature of 120 to 200 ° C. using a closed type kneader such as a kneader and then kneading other compounding agents such as a filler at a relatively low temperature below this is preferable. There is also a method of uniformly dispersing using a solid solution in which a crosslinking agent and a crosslinking accelerator are once melted to lower the melting point.

The crosslinking conditions may be appropriately determined depending on the type of the crosslinking agent to be used. Usually, firing is performed at a temperature of 150 to 300 ° C. for 1 minute to 24 hours.

In addition, as a crosslinking method, a crosslinking reaction is performed under any conditions, not only in a method commonly used such as steam crosslinking, but also under normal pressure, increased pressure, reduced pressure, and in air. be able to.

The laminate of the present invention may be a laminate in which the layer (D) is bonded in addition to the layer (A), the layer (B) and the layer (C), and the layer (D) It is preferable to adhere to the outside of the layer (C).

The layer (D) may be a layer made of any material, and may be a layer made of the same material as that constituting the layers (A) to (C).

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

In the laminate of the present invention, the thickness of the layer (A) is preferably 0.001 to 1 mm, the thickness of the layer (B) is preferably 0.001 to 5 mm, and the thickness of the layer (C) is It is preferable that it is 0.001-50 mm.

The manufacturing method of the laminated body of this invention is also one of this invention.

As a method for forming a laminate of the present invention, for example, (1) the layers constituting the laminate are co-extruded in a molten state to thermally bond the layers (melt adhesion) to form the laminate in one step. Method (co-extrusion molding), (2) Method of laminating each layer separately produced by an extruder and bonding the layers by thermal fusion, (3) Extruding molten resin onto the surface of the previously produced layer by an extruder (4) On the surface of the layer prepared in advance, the polymer constituting the layer adjacent to the layer is electrostatically coated, and the resulting coated product is entirely Alternatively, a method of forming a layer by heating and melting a polymer subjected to coating by heating from the coated side can be used.

When the laminate of the present invention is a tube or a hose, for example, as a method corresponding to the above (2), (2a) each cylindrical layer is separately formed by an extruder, and the inner layer is formed on the layer. As a method of coating the contacting layer with a heat shrinkable tube, a method corresponding to the above (3), (3a) First, an inner layer is formed by an inner layer extruder, and this layer is formed on the outer peripheral surface by an outer layer extruder. As a method corresponding to (4) above, (4a) a polymer constituting the inner layer is electrostatically coated on the inner side of the layer in contact with the layer, and then the resulting coated product is heated. A method of heating and melting the polymer constituting the inner layer by inserting a rod-shaped heating device inside the cylindrical coated article and heating from the inside by putting it in an oven and heating it as a whole , Etc.

As long as each layer constituting the laminate of the present invention can be coextruded, it is generally formed by coextrusion molding (1). Examples of the coextrusion molding include conventionally known multilayer co-extrusion manufacturing methods such as a multi-manifold method and a feed block method.

In the molding methods (2) and (3), after forming each layer, the contact surface of each layer with another layer may be surface-treated for the purpose of improving interlayer adhesion. Examples of such surface treatment include etching treatment such as sodium etching treatment; corona treatment; plasma treatment such as low temperature plasma treatment.

As the molding method, a method of performing surface treatment in the above methods (1) and (2) and (3) is preferable, and the method (1) is most preferable.

A molded product formed from the laminate is also one aspect of the present invention.

The molded article formed from the laminate of the present invention can be used for the following uses.
Films, sheets; food films, food sheets, chemical films, chemical sheets, diaphragm pump diaphragms and various packing tubes, hoses; fuel tubes such as automotive fuel tubes or automotive fuel hoses, or fuel Hose, solvent tube or solvent hose, paint tube or paint hose, automotive radiator hose, air conditioner hose, brake hose, wire covering material, food or drink tube or food hose, underground station tube Or bottles, containers, and tanks such as hoses, subsea oil field tubes or hoses; fuel tanks such as automobile radiator tanks, gasoline tanks, solvent tanks, paint tanks, chemical liquid containers such as semiconductor chemical liquid containers, and food and drink Other tanks; carburetor Lunge gaskets, various automotive seals such as O-ring of the fuel pump, various machines relation seals seal such hydraulic devices, can be suitably used in particular tube or hose Among such as gears above.

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

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

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

The laminated body of this invention can be used suitably for the use with a location which contacts a fuel at the time of use of a tube, a hose, a tank, etc. containing a fuel tube.

A fuel tube formed from the laminate is also one aspect of the present invention. As described above, the laminate of the present invention is firmly bonded between the layers, and has flexibility, high mechanical strength, and high fuel barrier properties. Therefore, the laminate for fuel tubes used for fuel piping tubes for automobiles is used. It can be suitably used as a body.

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

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

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

The surface conductive treatment powder is a powder obtained by conducting a conductive treatment on the surface of a nonconductive powder such as glass beads or titanium oxide. The method for conducting the conductive treatment is not particularly limited, and examples thereof include metal sputtering and electroless plating. Among the conductive fillers described above, carbon black is preferably used because it is advantageous in terms of economy and prevention of electrostatic charge accumulation.

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

<Preparation of sheet-shaped test piece (fluorine resin layer (A), fluorine-free resin layer (B))>
A fluororesin or non-fluorine-containing resin is set in a mold, held at 300 ° C. for 20 minutes by a heat press machine, and after the resin is melted, it is compression molded by applying a load of 3 MPa for 1 minute A sheet-like test piece was prepared.

<Preparation of sheet-shaped test piece (elastomer layer (C))>
A sheet-like test piece having a predetermined thickness was prepared from the elastomer composition with an 8-inch open roll.

<Preparation of laminate (fluorine resin layer (A) -non-fluorine-containing resin layer (B))>
A sheet-shaped test piece of fluororesin having a thickness of 1.0 mm and a sheet-shaped test piece of non-fluorine-containing resin having a thickness of 1.0 mm were prepared by the above method. These sheet-like test pieces were stacked and set in a mold heated to 260 ° C., and a load of 3 MPa was applied at 260 ° C. for 15 minutes with a heat press machine, and a fluororesin layer (A) -fluorine-free resin layer ( B) A laminate was produced.

<Preparation of laminate (fluorine-free resin layer (B) -elastomer layer (C))>
By the above method, a sheet-shaped test piece of a fluorine-free resin having a thickness of 0.5 mm and a sheet-shaped test piece of an elastomer composition having a thickness of 1.5 mm were prepared. These sheet-like test pieces were stacked and set in a mold heated to 160 ° C., and a 12 MPa load was applied for 45 minutes at 160 ° C. with a heat press machine, and a fluorine-free resin layer (B) -elastomer layer (C ) A laminate was produced.

<Production of Laminate (Fluororesin Layer (A) -Elastomer Layer (C))>
A sheet-shaped test piece of fluororesin having a thickness of 0.5 mm and a sheet-shaped test piece of an elastomer composition having a thickness of 1.5 mm were prepared by the above method. These sheet-like test pieces are stacked and set in a mold heated to 160 ° C., and a 12 MPa load is applied at 160 ° C. for 45 minutes by a heat press machine, and the fluororesin layer (A) -elastomer layer (C) is laminated The body was made.

<Adhesion evaluation test>
The obtained laminate was cut into strips each having a width of 1.0 cm and a width of 4 cm to produce a test piece for adhesion test, and an autograph (AGS-J 5kN, manufactured by Shimadzu Corporation) was used for this test piece. Then, in accordance with the method described in JIS-K-6256 (crosslinked rubber adhesion test method), a peel test was performed at 25 ° C. at a tensile rate of 50 mm / min, and the adhesive strength was measured. Moreover, the peeling mode was observed and evaluated according to the following criteria.

(Adhesion evaluation)
○: The interface of the laminate was not peeled off, and one of the layers was destroyed.
Δ: Peeled at the interface of the laminate, but was sufficiently adhered and difficult to peel.
X: Peeled relatively easily at the interface of the laminate.

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

<Measurement of composition of fluororesin copolymer>
The copolymer composition of the fluororesin was determined from ¹⁹ F-NMR and fluorine elemental analysis.

<Measurement of fuel permeability coefficient>
A sheet-like test piece having a thickness of 0.5 mm was produced by the above method. 18 mL of CE10 (toluene / isooctane / ethanol = 45/45/10 vol%), which is a simulated fuel, is placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL, and the above sheet A test specimen is prepared by setting a cylindrical test piece in the container opening and sealing it. The test specimen was placed in a thermostatic device (60 ° C.), the weight of the test specimen was measured, and when the weight loss per unit time became constant, the fuel permeability coefficient was determined by the following formula.

<Measurement of tensile modulus>
A sheet-like test piece having a thickness of 2 mm is prepared by the above method, and a dumbbell-like test piece having a width of 3.18 mm and a distance between marked lines of 1.0 mm is punched out using an ASTM V type dumbbell. Using the obtained dumbbell-shaped test piece, a tensile test was performed at 25 ° C. and a tensile speed of 50 mm / min according to ASTM D638 using an autograph (AGS-J 5 kN manufactured by Shimadzu Corporation). It was.

<Measurement of melting point of fluororesin>
Using a Seiko differential scanning calorimeter [DSC], 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.

<Measurement of melt flow rate (MFR)>
Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), at each measurement temperature, the mass (g) of the polymer flowing out per unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a 5 kg load was measured. .

<Production example>
In the examples and comparative examples, the following materials were used.

Fluororesin: CTFE-TFE copolymer having —OC (═O) OCH ₂ CH ₂ CH ₃ groups. The monomer composition is CTFE / TFE / perfluoro (propyl vinyl ether) = 23 / 74.5 / 2.5 (molar ratio). Mp 245 ° C. The MFR at 297 ° C. is 35 g / 10 min. _{-OC (= O) OCH 2 CH} 2 CH 3 radix 150 (carbon atoms per million). Tensile modulus is 600 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluorine-free resin: Polyamide 12 (Vestamid X7297, manufactured by Degussa Huls AG)

Elastomer composition: NBR full compound. 100 parts by mass of acrylonitrile-butadiene rubber (Nipol 1041, manufactured by JSR Corporation), 30 parts by mass of carbon black (N990, manufactured by Cancarb Ltd.), 5 parts by mass of zinc oxide (manufactured by Hystec Co., Ltd.), wet silica (Nipsil VN3) 15 parts by mass, manufactured by Nippon Silica Kogyo Co., Ltd., 1 part by mass of stearic acid (Lunac, manufactured by Kao Corporation), 2 parts by mass of anti-aging agent (A.O.224, manufactured by KING INDUSTRIES), plasticizer (Thiokol) TP95, 15 parts by mass from Morton International), 2 parts by mass of wax (carnauba wax, manufactured by Toa Kasei Co., Ltd.), 2 parts by mass of peroxide (Park Mill D-40, manufactured by Nippon Oil & Fats Co., Ltd.), amine compound ( N, N-dicinnamylidene-1,6-hexamethylenediamine (V3), Daikin Industries, Ltd.) 3 parts by mass, onium salt reagent (8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride (DBU-B), Wako Pure Chemical Industries, Ltd.) 2) parts by mass, 1 part by mass of onium salt reagent (SA-810, manufactured by San Apro Co., Ltd.), 5 parts by mass of epoxy compound (JER828, manufactured by Japan Epoxy Resin Co., Ltd.) And kneaded to obtain an elastomer composition.

A laminate was produced in the following combination according to the method described above. The adhesive strength of this laminate was evaluated by the method described above. The results are shown below.

Example 1
Adhesive evaluation of fluororesin layer (A) -non-fluorine-containing resin layer (B) laminate: ○

Example 2
Adhesive evaluation of fluorine-free resin layer (B) -elastomer layer (C) laminate: ○

Comparative Example 1
Evaluation of Adhesiveness of Fluororesin Layer (A) -Elastomer Layer (C) Laminate: Δ

Thus, it turned out that the laminated body which consists of a fluororesin layer-fluorine-free resin layer-elastomer layer shows favorable adhesiveness in each interface, and is useful as a fuel peripheral material.

The laminate of the present invention can be suitably used as various molded articles including a fuel hose.

1. 1. Fluororesin layer 2. Fluorine-free resin layer Elastomer layer

Claims (12)

A laminate in which the fluororesin layer (A), the non-fluorine-containing resin layer (B), and the elastomer layer (C) are bonded in this order. A laminate in which an elastomer layer (C), a fluorine-free resin layer (B), a fluorine resin layer (A), a fluorine-free resin layer (B) and an elastomer layer (C) are bonded in this order. The laminate according to claim 1 or 2, wherein the fluororesin layer (A) comprises a fluoropolymer having at least one adhesive functional group selected from the group consisting of a carbonyl group, a hydroxyl group and an amino group. The fluororesin layer (A) is composed of an ethylene / tetrafluoroethylene copolymer, a chlorotrifluoroethylene / tetrafluoroethylene copolymer, a tetrafluoroethylene / hexafluoropropylene copolymer, and a vinylidene fluoride / tetrafluoroethylene / The laminate according to claim 1, 2, or 3, comprising at least one fluoropolymer selected from the group consisting of hexafluoropropylene copolymers. The fluororesin layer (A)
It consists of ethylene / tetrafluoroethylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer. At least one fluorine-containing polymer selected from the group, 50.01 to 99.99 parts by mass;
0.01 to 49.99 parts by mass of at least one fluorine-free polymer selected from the group consisting of an ethylene / vinyl alcohol copolymer, polyamide and polyolefin;
The laminate according to claim 1, 2, or 3. The fluorine-free resin layer (B) comprises at least one fluorine-free polymer selected from the group consisting of ethylene / vinyl alcohol copolymer, polyamide and polyolefin. The laminated body of description. The elastomer layer (C) is composed of acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber. The laminate according to claim 1, comprising an elastomer composition comprising at least one elastomer selected from the group consisting of acrylic rubber and acrylic rubber. The laminate according to claim 1, 3, 4, 5, 6 or 7, wherein the layer (D) is adhered to the outside of the layer (A). The laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the layer (D) is bonded to the outside of the layer (C). A molded article formed from the laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. A fuel tube formed from the laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. The manufacturing method of the laminated body of Claim 1, 2, 3, 4, 5, 6, 7, 8, or 9.

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